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2022 Volume 33 Issue 7
2022, 33(7): 3297-3302
doi: 10.1016/j.cclet.2022.04.007
Abstract:
2022, 33(7): 3303-3314
doi: 10.1016/j.cclet.2022.03.057
Abstract:
Quantitative information, such as environmental migration, absorption, biodistribution, biotransformation, and elimination, is fundamental and essential for the nanosafety evaluations of nanomaterials. Due to the complexity of biological and environmental systems, it is challenging to develop quantitative approaches and tools that could characterize intrinsic behaviors of nanomaterials in the organisms. The isotopic tracers are ideal candidates to tune the physical properties of nanomaterials while preserving their chemical properties. In this review article, we summarized the stable isotope labeling methods of nanomaterials for evaluating their environmental and biological effects. The skeleton labeling protocols of carbon nanomaterials and metal/metal oxide nanoparticles were introduced. The advantages and disadvantages of stable isotope labeling were discussed in comparison with other quantitative methods for nanomaterials. The quantitative information of nanomaterials in environmental and biological systems was summarized along with the biosafety data. The benefits for drug development of nanomedicine were analyzed based on the targeting effects, persistent accumulation, and safety. Finally, the challenges and future perspectives of stable isotope labeling in nanoscience and nanotechnology were discussed.
Quantitative information, such as environmental migration, absorption, biodistribution, biotransformation, and elimination, is fundamental and essential for the nanosafety evaluations of nanomaterials. Due to the complexity of biological and environmental systems, it is challenging to develop quantitative approaches and tools that could characterize intrinsic behaviors of nanomaterials in the organisms. The isotopic tracers are ideal candidates to tune the physical properties of nanomaterials while preserving their chemical properties. In this review article, we summarized the stable isotope labeling methods of nanomaterials for evaluating their environmental and biological effects. The skeleton labeling protocols of carbon nanomaterials and metal/metal oxide nanoparticles were introduced. The advantages and disadvantages of stable isotope labeling were discussed in comparison with other quantitative methods for nanomaterials. The quantitative information of nanomaterials in environmental and biological systems was summarized along with the biosafety data. The benefits for drug development of nanomedicine were analyzed based on the targeting effects, persistent accumulation, and safety. Finally, the challenges and future perspectives of stable isotope labeling in nanoscience and nanotechnology were discussed.
2022, 33(7): 3315-3324
doi: 10.1016/j.cclet.2022.03.054
Abstract:
While radiotherapy is a mainstay therapeutic modality for malignant tumor, the intrinsic tumor resistance to radiotherapy, as well as the concomitant radiation injury to adjacent healthy tissues, greatly limits the efficacy of cancer radiotherapy. As a result, the development of novel radioenhancers and radioprotectants is highly desired for clinical radiotherapy. In recent years, nanozymes have inspired ever-growing research interest because of their multi-enzyme activities and microenvironment-responsive feature. In view of the significant progress of nanozymes in radiation medicine, we, in this review, systematically illustrate the impressive progress of nanozymes for potentiating radiotherapy and radiation protection. First, the types of nanozymes used in tumor radiotherapy are briefly discussed. Subsequently, the main strategies of nanozymes to enhance the radiotherapy efficiency, including promoting the generation of reactive oxygen species (ROS), relieving hypoxia in tumor microenvironment and combining with other cancer therapeutic regimens, are summarized. Finally, the advances of typical nanozymes for preventing radiation-induced hematopoietic damage and gastrointestinal damage are highlighted.
While radiotherapy is a mainstay therapeutic modality for malignant tumor, the intrinsic tumor resistance to radiotherapy, as well as the concomitant radiation injury to adjacent healthy tissues, greatly limits the efficacy of cancer radiotherapy. As a result, the development of novel radioenhancers and radioprotectants is highly desired for clinical radiotherapy. In recent years, nanozymes have inspired ever-growing research interest because of their multi-enzyme activities and microenvironment-responsive feature. In view of the significant progress of nanozymes in radiation medicine, we, in this review, systematically illustrate the impressive progress of nanozymes for potentiating radiotherapy and radiation protection. First, the types of nanozymes used in tumor radiotherapy are briefly discussed. Subsequently, the main strategies of nanozymes to enhance the radiotherapy efficiency, including promoting the generation of reactive oxygen species (ROS), relieving hypoxia in tumor microenvironment and combining with other cancer therapeutic regimens, are summarized. Finally, the advances of typical nanozymes for preventing radiation-induced hematopoietic damage and gastrointestinal damage are highlighted.
2022, 33(7): 3325-3338
doi: 10.1016/j.cclet.2022.03.025
Abstract:
Astatine-211 (211At, t1/2 = 7.21 h) emitting two α particles with energies of 5.87 and 7.45 MeV, can lead to a high linear energy transfer (LET = 98.84 keV/µm) and short tissue range (50~90 µm). Since the 1950s, 211At had stepped into endoradiotherapy and has always been regarded as one of the most promising α-emitters for targeted-alpha therapy (TAT) in various malignancies. In the past two decades, 211At related radiopharmaceuticals have achieved great progress in the studies of basic physicochemical properties of astatine, 211At labeling strategies, preclinical and clinical studies, producing profound effects in nuclear medicine. This work will give a panorama of 211At-related researches in the recent 20 years, which will cover both the fundamental insights of 211At radiochemistry and applied labeling compounds. It can provide some important hints for the studies of TAT and other radiopharmaceuticals applied in tumor radiotherapy.
Astatine-211 (211At, t1/2 = 7.21 h) emitting two α particles with energies of 5.87 and 7.45 MeV, can lead to a high linear energy transfer (LET = 98.84 keV/µm) and short tissue range (50~90 µm). Since the 1950s, 211At had stepped into endoradiotherapy and has always been regarded as one of the most promising α-emitters for targeted-alpha therapy (TAT) in various malignancies. In the past two decades, 211At related radiopharmaceuticals have achieved great progress in the studies of basic physicochemical properties of astatine, 211At labeling strategies, preclinical and clinical studies, producing profound effects in nuclear medicine. This work will give a panorama of 211At-related researches in the recent 20 years, which will cover both the fundamental insights of 211At radiochemistry and applied labeling compounds. It can provide some important hints for the studies of TAT and other radiopharmaceuticals applied in tumor radiotherapy.
2022, 33(7): 3339-3348
doi: 10.1016/j.cclet.2022.03.024
Abstract:
Abnormal Tau deposition is a crucial pathological hallmark of various neurodegenerative disorders defined as tauopathies, of which Alzheimer's disease is the most prominent one. To date, a large number of chemical entities with different structures have been developed as Tau imaging tracers for the early diagnosis of tauopathies. Several of them with excellent bio-properties are currently being assessed in clinical trials, and more recently, the TauvidTM ([18F]Flortaucipir, also known as [18F]AV1451 or [18F]T807) as the first Tau tracer was approved by the U.S. Food and Drug Administration in 2020. This review summarized the latest development of Tau tracers and analyzed their chemical structures, with particular attention to the effects of chemical structures on biological properties. In addition, we also discuss the limitations of current Tau imaging tracers, issues that need attention in the development of new tracers, and possible future directions.
Abnormal Tau deposition is a crucial pathological hallmark of various neurodegenerative disorders defined as tauopathies, of which Alzheimer's disease is the most prominent one. To date, a large number of chemical entities with different structures have been developed as Tau imaging tracers for the early diagnosis of tauopathies. Several of them with excellent bio-properties are currently being assessed in clinical trials, and more recently, the TauvidTM ([18F]Flortaucipir, also known as [18F]AV1451 or [18F]T807) as the first Tau tracer was approved by the U.S. Food and Drug Administration in 2020. This review summarized the latest development of Tau tracers and analyzed their chemical structures, with particular attention to the effects of chemical structures on biological properties. In addition, we also discuss the limitations of current Tau imaging tracers, issues that need attention in the development of new tracers, and possible future directions.
2022, 33(7): 3349-3360
doi: 10.1016/j.cclet.2022.02.070
Abstract:
The prevalence of positron emission tomography (PET) imaging has advanced biomedical applications for its ultrahigh sensitivity, deep tissue penetration and quantitative visualization of diseases in vivo. 64Cu with ideal half-life and decay characteristics has been designed as radioactive probes for disease diagnosis. The currently reported 64Cu-labeled nanomaterials have the advantages of long circulation time in serum, good biocompatibility and mature preparation methods, and have been used in vivo PET imaging, biodistribution and pharmacokinetic monitoring, and imaging guided therapy. At the same time, suitable carrier characteristics and radiolabeling strategies are particularly important in the 64Cu PET imaging process. In this review, we summarize different imaging probe designs and 64Cu radiolabeling strategies, as well as their eventual applications in biomedicine. The potential challenges and prospects of 64Cu labeled nanomaterials are also described, which provides broad prospects for radiolabeling strategies and further applications.
The prevalence of positron emission tomography (PET) imaging has advanced biomedical applications for its ultrahigh sensitivity, deep tissue penetration and quantitative visualization of diseases in vivo. 64Cu with ideal half-life and decay characteristics has been designed as radioactive probes for disease diagnosis. The currently reported 64Cu-labeled nanomaterials have the advantages of long circulation time in serum, good biocompatibility and mature preparation methods, and have been used in vivo PET imaging, biodistribution and pharmacokinetic monitoring, and imaging guided therapy. At the same time, suitable carrier characteristics and radiolabeling strategies are particularly important in the 64Cu PET imaging process. In this review, we summarize different imaging probe designs and 64Cu radiolabeling strategies, as well as their eventual applications in biomedicine. The potential challenges and prospects of 64Cu labeled nanomaterials are also described, which provides broad prospects for radiolabeling strategies and further applications.
2022, 33(7): 3361-3370
doi: 10.1016/j.cclet.2022.02.016
Abstract:
Radionuclide imaging is now the premier imaging method in clinical practice for its high sensitivity and tomographic capability. Current clinically available radio imaging methods mostly use positron-emission tomography (PET) and single-photon emission computed tomography (SPECT) to detect anatomic abnormalities that conventional imaging techniques typically have challenges for visualizing. Contrast agents are indispensable for radionuclide imaging, and the radionuclide is always attached to a suitable vector that achieves targeted delivery. Nowadays, peptides have attracted increasing interest in targeting vectors of contrast agents, mainly due to their high specificity for target receptors at nanomolar concentrations and low toxicity. Radiolabeled peptide probes as kinds of PET/SPECT tracers had become essential tools for clinical radionuclide diagnosis. This review mainly summarizes radiolabeled peptide probes for bioimaging, including fundamental concepts of radiolabeled peptide probe design, some typical peptide analogs radiocontrast agents for PET, SPECT, and the combination imaging.
Radionuclide imaging is now the premier imaging method in clinical practice for its high sensitivity and tomographic capability. Current clinically available radio imaging methods mostly use positron-emission tomography (PET) and single-photon emission computed tomography (SPECT) to detect anatomic abnormalities that conventional imaging techniques typically have challenges for visualizing. Contrast agents are indispensable for radionuclide imaging, and the radionuclide is always attached to a suitable vector that achieves targeted delivery. Nowadays, peptides have attracted increasing interest in targeting vectors of contrast agents, mainly due to their high specificity for target receptors at nanomolar concentrations and low toxicity. Radiolabeled peptide probes as kinds of PET/SPECT tracers had become essential tools for clinical radionuclide diagnosis. This review mainly summarizes radiolabeled peptide probes for bioimaging, including fundamental concepts of radiolabeled peptide probe design, some typical peptide analogs radiocontrast agents for PET, SPECT, and the combination imaging.
2022, 33(7): 3371-3383
doi: 10.1016/j.cclet.2022.03.079
Abstract:
Hepatocellular carcinoma (HCC) is the most common primary malignant tumor of the liver, but early diagnosis and effective treatment are still difficult. With the development of radionuclide applications in medicine, nuclear medicine is playing an increasingly important role in the diagnosis and treatment of HCC. Radionuclide-based positron emission tomography-computed tomography and single-photon emission computed tomography-computed tomography molecular imaging are indispensable for assessing progression, staging, differentiation, preoperative planning, postoperative prediction, and evaluation of HCC in clinical applications. Moreover, radionuclide-based endoradiotherapy provides an objective therapeutic strategy for patients with unresectable advanced HCC. This review highlights the application and development of radionuclides in the diagnosis and treatment of HCC. More efforts are warranted for the development of advanced radionuclides to make significant contributions in the treatment of HCC.
Hepatocellular carcinoma (HCC) is the most common primary malignant tumor of the liver, but early diagnosis and effective treatment are still difficult. With the development of radionuclide applications in medicine, nuclear medicine is playing an increasingly important role in the diagnosis and treatment of HCC. Radionuclide-based positron emission tomography-computed tomography and single-photon emission computed tomography-computed tomography molecular imaging are indispensable for assessing progression, staging, differentiation, preoperative planning, postoperative prediction, and evaluation of HCC in clinical applications. Moreover, radionuclide-based endoradiotherapy provides an objective therapeutic strategy for patients with unresectable advanced HCC. This review highlights the application and development of radionuclides in the diagnosis and treatment of HCC. More efforts are warranted for the development of advanced radionuclides to make significant contributions in the treatment of HCC.
2022, 33(7): 3384-3394
doi: 10.1016/j.cclet.2022.03.016
Abstract:
A relatively new branch of science - nuclear forensics, aiming at providing the nature, origin, history and possible trafficking route of seized nuclear materials/devices, has been established and rapidly developed over decades to screen illicit nuclear activities. This highly interdisciplinary science is built upon a foundation of analytical chemistry, radiochemistry, nuclear physics, material sciences, geology, and other scientific disciplines, within which radiochemical methodologies and radioanalytical techniques play a key role. The present review provides a brief overview about the crucial aspects of nuclear forensics, including basic content, procedure, concerned elements, common separation, analytical method, and so on. The state of the art and recent progresses of nuclear forensics by research communities in China are reviewed, while selected examples and practical applications are emphasized. The challenges associated with this new area and on-going developments are highlighted and discussed.
A relatively new branch of science - nuclear forensics, aiming at providing the nature, origin, history and possible trafficking route of seized nuclear materials/devices, has been established and rapidly developed over decades to screen illicit nuclear activities. This highly interdisciplinary science is built upon a foundation of analytical chemistry, radiochemistry, nuclear physics, material sciences, geology, and other scientific disciplines, within which radiochemical methodologies and radioanalytical techniques play a key role. The present review provides a brief overview about the crucial aspects of nuclear forensics, including basic content, procedure, concerned elements, common separation, analytical method, and so on. The state of the art and recent progresses of nuclear forensics by research communities in China are reviewed, while selected examples and practical applications are emphasized. The challenges associated with this new area and on-going developments are highlighted and discussed.
2022, 33(7): 3395-3404
doi: 10.1016/j.cclet.2022.04.017
Abstract:
Internal contamination of actinides has led to significant health hazards to the public and workers in the context of nuclear power plant accidents, uranium ore mining, and reprocessing of the used fuel. An effective sequestering agent that is able to remove accidentally incorporated actinides in vivo with low toxicity is always in urgent need. The molecular decorporation ligands have been the most widely researched agents for the past few decades, while preliminary studies of functionalized nanoparticles have shown their clear advantages in metal binding selectivity, toxicity, and oxidative stress alleviation. Herein, the state-of-the-art of those two types of decorporation agents is presented with special attention being paid on the correlation between the solution and solid-state chemistry of those agents with actinides and the corresponding decorporation efficacies.
Internal contamination of actinides has led to significant health hazards to the public and workers in the context of nuclear power plant accidents, uranium ore mining, and reprocessing of the used fuel. An effective sequestering agent that is able to remove accidentally incorporated actinides in vivo with low toxicity is always in urgent need. The molecular decorporation ligands have been the most widely researched agents for the past few decades, while preliminary studies of functionalized nanoparticles have shown their clear advantages in metal binding selectivity, toxicity, and oxidative stress alleviation. Herein, the state-of-the-art of those two types of decorporation agents is presented with special attention being paid on the correlation between the solution and solid-state chemistry of those agents with actinides and the corresponding decorporation efficacies.
2022, 33(7): 3405-3412
doi: 10.1016/j.cclet.2022.02.054
Abstract:
The radionuclide (RN) migration study is not only helpful to understand environmental behavior of RNs, but also can establish the basis for the safety assessment of geological disposal of high-level radioactive waste (HLW). In the context of China's HLW disposal, this review briefly summaries the progress of China's RN migration studies over the past decade regarding three aspects, RN sorption, RN transport and radioactive colloid. Domestic studies from other disciplines (such as geology and environmental science) are also included in this review because they can provide references for the RN migration study. Overall, China has achieved clear progress in RN migration study over the past decade, although large-scaled field experiments are lacked and a gap still exists comparing with the international advanced level. Finally, several suggestions are proposed for future RN migration research in China.
The radionuclide (RN) migration study is not only helpful to understand environmental behavior of RNs, but also can establish the basis for the safety assessment of geological disposal of high-level radioactive waste (HLW). In the context of China's HLW disposal, this review briefly summaries the progress of China's RN migration studies over the past decade regarding three aspects, RN sorption, RN transport and radioactive colloid. Domestic studies from other disciplines (such as geology and environmental science) are also included in this review because they can provide references for the RN migration study. Overall, China has achieved clear progress in RN migration study over the past decade, although large-scaled field experiments are lacked and a gap still exists comparing with the international advanced level. Finally, several suggestions are proposed for future RN migration research in China.
2022, 33(7): 3413-3421
doi: 10.1016/j.cclet.2022.03.017
Abstract:
With the rapid development of the nuclear industry, more-stringent requirements are proposed for high-level radioactive waste liquid treatment and the enrichment of isotope products. High-pressure ion exchange chromatography has been widely accepted for the fine separation of elements and nuclides due to its advantages, such as high efficiency, environmental friendliness, ease of operation, and feasibility for large-scale industrial applications. Here, we summarized the evolution of high-pressure ion exchange chromatography and the relevant research progress in ion exchange equilibrium and related separation technology. The prospects for application of high-pressure ion exchange chromatography to rare earth elements, actinide elements and isotope separation were discussed. High-pressure ion exchange chromatography represents a promising strategy for the extraction of rare earth elements and actinide elements from high-level radioactive waste liquid, as well as being an effective method for the automated production of high purity isotope products with great environmental benefits.
With the rapid development of the nuclear industry, more-stringent requirements are proposed for high-level radioactive waste liquid treatment and the enrichment of isotope products. High-pressure ion exchange chromatography has been widely accepted for the fine separation of elements and nuclides due to its advantages, such as high efficiency, environmental friendliness, ease of operation, and feasibility for large-scale industrial applications. Here, we summarized the evolution of high-pressure ion exchange chromatography and the relevant research progress in ion exchange equilibrium and related separation technology. The prospects for application of high-pressure ion exchange chromatography to rare earth elements, actinide elements and isotope separation were discussed. High-pressure ion exchange chromatography represents a promising strategy for the extraction of rare earth elements and actinide elements from high-level radioactive waste liquid, as well as being an effective method for the automated production of high purity isotope products with great environmental benefits.
2022, 33(7): 3422-3428
doi: 10.1016/j.cclet.2022.03.089
Abstract:
Separation and recovery of U(Ⅵ) and Th(Ⅳ) from rare earth minerals is a very challenging work in rare earth industrial production. In the present study, a homemade membrane emulsification circulation (MEC) extractor was used to separate U(Ⅵ) and Th(Ⅳ) from rare earth elements by using Cyphos IL 104 as an extractant. Batch experiments were carried out using a constant temperature oscillator to investigate the extraction parameters of the single element and the results indicated that Cyphos IL 104 could reach the extraction equilibrium within 30 min for all the three elements, i.e., U(Ⅵ), Th(Ⅳ), and Eu(Ⅲ). Besides, the MEC extractor possessed a strong phase separation ability. The extraction efficiencies of U(Ⅵ), Th(Ⅳ), La(Ⅲ), Eu(Ⅲ) and Yb (Ⅲ) increased with the increase of pH. La(Ⅲ), Eu(Ⅲ) and Yb(Ⅲ) were hardly extracted when pH ≤ 1.50, which was beneficial for effectively separating U(Ⅵ) and Th(Ⅳ) from La(Ⅲ), Eu(Ⅲ) and Yb(Ⅲ). In the multi-stages stripping experiments, when the stripping stage number was 3, the effective separation could be achieved by using HCl and H2SO4, since the stripping efficiency reached 80.0% and 100.0% for Th(Ⅳ) and U(Ⅵ), respectively. Slope method and FT-IR spectra showed that Cyphos IL 104 reacted with U(Ⅵ) and Th(Ⅳ) by chelation mechanism. The extraction of multi-elements indicated that U(Ⅵ) and Th(Ⅳ) could be well separated from the solution which contains all rare earth elements, and the extraction efficiencies of U(Ⅵ) and Th(Ⅳ) both were close to 100.0%. Based on the above experimental results, a flowchart for efficient separation of U(Ⅵ) and Th(Ⅳ) from rare earth elements was proposed.
Separation and recovery of U(Ⅵ) and Th(Ⅳ) from rare earth minerals is a very challenging work in rare earth industrial production. In the present study, a homemade membrane emulsification circulation (MEC) extractor was used to separate U(Ⅵ) and Th(Ⅳ) from rare earth elements by using Cyphos IL 104 as an extractant. Batch experiments were carried out using a constant temperature oscillator to investigate the extraction parameters of the single element and the results indicated that Cyphos IL 104 could reach the extraction equilibrium within 30 min for all the three elements, i.e., U(Ⅵ), Th(Ⅳ), and Eu(Ⅲ). Besides, the MEC extractor possessed a strong phase separation ability. The extraction efficiencies of U(Ⅵ), Th(Ⅳ), La(Ⅲ), Eu(Ⅲ) and Yb (Ⅲ) increased with the increase of pH. La(Ⅲ), Eu(Ⅲ) and Yb(Ⅲ) were hardly extracted when pH ≤ 1.50, which was beneficial for effectively separating U(Ⅵ) and Th(Ⅳ) from La(Ⅲ), Eu(Ⅲ) and Yb(Ⅲ). In the multi-stages stripping experiments, when the stripping stage number was 3, the effective separation could be achieved by using HCl and H2SO4, since the stripping efficiency reached 80.0% and 100.0% for Th(Ⅳ) and U(Ⅵ), respectively. Slope method and FT-IR spectra showed that Cyphos IL 104 reacted with U(Ⅵ) and Th(Ⅳ) by chelation mechanism. The extraction of multi-elements indicated that U(Ⅵ) and Th(Ⅳ) could be well separated from the solution which contains all rare earth elements, and the extraction efficiencies of U(Ⅵ) and Th(Ⅳ) both were close to 100.0%. Based on the above experimental results, a flowchart for efficient separation of U(Ⅵ) and Th(Ⅳ) from rare earth elements was proposed.
2022, 33(7): 3429-3434
doi: 10.1016/j.cclet.2022.02.011
Abstract:
Separation of the minor actinides (Am and Cm) from lanthanides in high-level liquid wastes (HLLW) is one of the most challenging chemical separation tasks known owing to their chemical similarities and is highly significant in nuclear fuel reprocessing plants because it could practically lead to sustainable nuclear energy by closing the nuclear fuel cycle. The solid phase extraction is proposed to be a possible strategy but all reported sorbent materials severely suffer from limited stability and/or efficiency caused by the harsh conditions of high acidity coupled with intense irradiation. Herein, a phenanthroline-based polymeric organic framework (PhenTAPB-POF) was designed and tested for the separation of trivalent americium from lanthanides for the first time. Due to its fully conjugated structure, PhenTAPB-POF exhibits previously unachieved stability under the combined extreme conditions of strong acids and high irradiation field. The americium partitioning experiment indicates that PhenTAPB-POF possesses an ultrahigh adsorption selectivity towards Am(Ⅲ) over lanthanides (e.g., SFAm(Ⅲ)/Eu(Ⅲ) = 3326) in highly acidic simulated HLLW and relatively fast adsorption kinetics in both static and dynamic experiments. Am(Ⅲ) can be almost quantitatively eluted from the PhenTAPB-POF packed-column using a concentrated nitric acid elution. The high stability and superior separation performance endow PhenTAPB-POF with the promising alternative for separating minor actinides over lanthanides from highly acidic HLLW streams.
Separation of the minor actinides (Am and Cm) from lanthanides in high-level liquid wastes (HLLW) is one of the most challenging chemical separation tasks known owing to their chemical similarities and is highly significant in nuclear fuel reprocessing plants because it could practically lead to sustainable nuclear energy by closing the nuclear fuel cycle. The solid phase extraction is proposed to be a possible strategy but all reported sorbent materials severely suffer from limited stability and/or efficiency caused by the harsh conditions of high acidity coupled with intense irradiation. Herein, a phenanthroline-based polymeric organic framework (PhenTAPB-POF) was designed and tested for the separation of trivalent americium from lanthanides for the first time. Due to its fully conjugated structure, PhenTAPB-POF exhibits previously unachieved stability under the combined extreme conditions of strong acids and high irradiation field. The americium partitioning experiment indicates that PhenTAPB-POF possesses an ultrahigh adsorption selectivity towards Am(Ⅲ) over lanthanides (e.g., SFAm(Ⅲ)/Eu(Ⅲ) = 3326) in highly acidic simulated HLLW and relatively fast adsorption kinetics in both static and dynamic experiments. Am(Ⅲ) can be almost quantitatively eluted from the PhenTAPB-POF packed-column using a concentrated nitric acid elution. The high stability and superior separation performance endow PhenTAPB-POF with the promising alternative for separating minor actinides over lanthanides from highly acidic HLLW streams.
2022, 33(7): 3435-3438
doi: 10.1016/j.cclet.2022.02.069
Abstract:
In this work, a technique was proposed to prepare UO2 from UO3 by the two processes of fluorination reaction of UO3 with NH4HF2 and electrochemical reduction of UO22+ for the recycle uranium. The feasibility of fluorination reaction was firstly confirmed using thermodynamic calculation; then, the products were analyzed using XRD, Raman and fluorescence to be UO2F2. The fluorination mechanism was inferred to be UO3(s) + NH4HF2 → (NH4)3UO2F5→ NH4(UO2)2F5 → UO2F2. The redox behavior of UO22+ on W electrode was investigated by cyclic voltammetry and square wave voltammetry, which indicated that UO22+ was reduced to UO2 via a two-step single electron transfer with diffusion-controlled. The diffusion coefficient of UO22+ was calculated to be 6.22 × 10−5 cm2/s. The disproportionation reaction of UO22+ was observed, and the relationship between the disproportionation reaction and scan rate was discussed. Moreover, the electrochemical fabrication of UO2 was conducted by electrolysis at −0.8 V, and the product was analyzed by XRD, SEM and EDS to be UO2. ICP-AES results showed that the extraction efficiency of UO2 could reach 98.53%.
In this work, a technique was proposed to prepare UO2 from UO3 by the two processes of fluorination reaction of UO3 with NH4HF2 and electrochemical reduction of UO22+ for the recycle uranium. The feasibility of fluorination reaction was firstly confirmed using thermodynamic calculation; then, the products were analyzed using XRD, Raman and fluorescence to be UO2F2. The fluorination mechanism was inferred to be UO3(s) + NH4HF2 → (NH4)3UO2F5→ NH4(UO2)2F5 → UO2F2. The redox behavior of UO22+ on W electrode was investigated by cyclic voltammetry and square wave voltammetry, which indicated that UO22+ was reduced to UO2 via a two-step single electron transfer with diffusion-controlled. The diffusion coefficient of UO22+ was calculated to be 6.22 × 10−5 cm2/s. The disproportionation reaction of UO22+ was observed, and the relationship between the disproportionation reaction and scan rate was discussed. Moreover, the electrochemical fabrication of UO2 was conducted by electrolysis at −0.8 V, and the product was analyzed by XRD, SEM and EDS to be UO2. ICP-AES results showed that the extraction efficiency of UO2 could reach 98.53%.
2022, 33(7): 3439-3443
doi: 10.1016/j.cclet.2022.04.001
Abstract:
A process for actinide(Ⅲ) and lanthanum(Ⅲ) extraction separation from high-level liquid waste (HLLW) was proposed, with N,N,N',N'-tetraoctyl diglycolamide (TODGA) as the extractant, tri-n‑butyl phosphate (TBP) as the phase modifier and 2,6-bis[1-(propan-1-ol)-1,2,3-triazol-4-yl]pyridine (PyTri-Diol or PTD) as hydrophilic stripping agent. This 'hot test' was successfully carried out, achieving 99.92% removal of americium-241 (241Am) with a separation factor SF(Eu/Am) of 3.8 × 103 in the actinide(Ⅲ) product solution. The results show that bisamide podand extractants can effectively realize the extraction and separation of actinide(Ⅲ) and lanthanum(Ⅲ) from Chinese commercial HLLW and thus have a bright practical application potential for the treatment of commercial HLLW.
A process for actinide(Ⅲ) and lanthanum(Ⅲ) extraction separation from high-level liquid waste (HLLW) was proposed, with N,N,N',N'-tetraoctyl diglycolamide (TODGA) as the extractant, tri-n‑butyl phosphate (TBP) as the phase modifier and 2,6-bis[1-(propan-1-ol)-1,2,3-triazol-4-yl]pyridine (PyTri-Diol or PTD) as hydrophilic stripping agent. This 'hot test' was successfully carried out, achieving 99.92% removal of americium-241 (241Am) with a separation factor SF(Eu/Am) of 3.8 × 103 in the actinide(Ⅲ) product solution. The results show that bisamide podand extractants can effectively realize the extraction and separation of actinide(Ⅲ) and lanthanum(Ⅲ) from Chinese commercial HLLW and thus have a bright practical application potential for the treatment of commercial HLLW.
2022, 33(7): 3444-3450
doi: 10.1016/j.cclet.2022.03.002
Abstract:
A simple and convenient method has been developed for the pre-concentration and separation of inorganic selenium species from environmental water samples using anion exchange chromatographic column combined with high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) measurement. 75Se(Ⅳ) and 75Se(Ⅵ) were prepared and used as tracers during the experiments. The volatility of selenium during solution evaporation was investigated to establish a reliable water samples pretreatment procedure. The parameters which affect the uptake of Se(Ⅳ) and Se(Ⅵ) on Dowex1 × 8 resin was optimized and the procedure for Se(Ⅳ) and Se(Ⅵ) separation was proposed. Both Se(Ⅳ) and Se(Ⅵ) are retained on the column in natural or alkaline solution with high distribution coefficient. The successive gradient elution of pre-concentrated species of selenium with HNO3 solution allows to differentiate between them. Se(Ⅳ) and Se(Ⅵ) finally were eluted with 0.05 mol/L HNO3 and 5.0 mol/L HNO3, respectively. The proposed method has been successfully verified using the certified reference materials (CRMs) of real water samples, and spiked recoveries for real samples were 98%-104% with 5% relative standard deviations (RSDs). The developed procedure is proved to be reliable and can be used for the rapid determination of selenium species in environmental water samples.
A simple and convenient method has been developed for the pre-concentration and separation of inorganic selenium species from environmental water samples using anion exchange chromatographic column combined with high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) measurement. 75Se(Ⅳ) and 75Se(Ⅵ) were prepared and used as tracers during the experiments. The volatility of selenium during solution evaporation was investigated to establish a reliable water samples pretreatment procedure. The parameters which affect the uptake of Se(Ⅳ) and Se(Ⅵ) on Dowex1 × 8 resin was optimized and the procedure for Se(Ⅳ) and Se(Ⅵ) separation was proposed. Both Se(Ⅳ) and Se(Ⅵ) are retained on the column in natural or alkaline solution with high distribution coefficient. The successive gradient elution of pre-concentrated species of selenium with HNO3 solution allows to differentiate between them. Se(Ⅳ) and Se(Ⅵ) finally were eluted with 0.05 mol/L HNO3 and 5.0 mol/L HNO3, respectively. The proposed method has been successfully verified using the certified reference materials (CRMs) of real water samples, and spiked recoveries for real samples were 98%-104% with 5% relative standard deviations (RSDs). The developed procedure is proved to be reliable and can be used for the rapid determination of selenium species in environmental water samples.
2022, 33(7): 3451-3455
doi: 10.1016/j.cclet.2021.12.066
Abstract:
The extraction complexes of uranyl(Ⅵ) in HNO3 to a hydroxyl-functionalized ionic liquid (IL) phase, HOEtmimNTf2 bearing CMPO, were investigated. Three possibly successive extraction complexes, UO2L2+ (L = CMPO), UO2L22+ and UO2L32+, were detected based on variable U/L ratios. Uranyl(Ⅵ) prefers to be extracted as complex UO2L32+, combining with the ions from HOEtmimNTf2 to construct a solid material through self-assembly. The thermodynamics of complexes, UO2L2+ (j = 1-3), were studied by spectrophotometry and microcalorimetry. All the formation reactions are principally driven by entropy, although a small part of the driving force of complexes UO2L22+ and UO2L32+ comes from enthalpy. Based on the thermodynamic properties for complex UO2L32+, we provide a possible coordination mode in HOEtmimNTf2: the first CMPO molecule coordinates with UO22+ in a bidentate fashion while the others do in a monodentate fashion. The results offer a thermodynamic insight into the formation behaviors of the uranyl(Ⅵ)/CMPO complexes involving the special IL HOEtmimNTf2, which is of significance to advance the novel IL extraction strategy.
The extraction complexes of uranyl(Ⅵ) in HNO3 to a hydroxyl-functionalized ionic liquid (IL) phase, HOEtmimNTf2 bearing CMPO, were investigated. Three possibly successive extraction complexes, UO2L2+ (L = CMPO), UO2L22+ and UO2L32+, were detected based on variable U/L ratios. Uranyl(Ⅵ) prefers to be extracted as complex UO2L32+, combining with the ions from HOEtmimNTf2 to construct a solid material through self-assembly. The thermodynamics of complexes, UO2L2+ (j = 1-3), were studied by spectrophotometry and microcalorimetry. All the formation reactions are principally driven by entropy, although a small part of the driving force of complexes UO2L22+ and UO2L32+ comes from enthalpy. Based on the thermodynamic properties for complex UO2L32+, we provide a possible coordination mode in HOEtmimNTf2: the first CMPO molecule coordinates with UO22+ in a bidentate fashion while the others do in a monodentate fashion. The results offer a thermodynamic insight into the formation behaviors of the uranyl(Ⅵ)/CMPO complexes involving the special IL HOEtmimNTf2, which is of significance to advance the novel IL extraction strategy.
2022, 33(7): 3456-3460
doi: 10.1016/j.cclet.2021.11.019
Abstract:
The development of uranyl ion detection technology has exhibited its significance in public security and environmental fields for the radioactivity and chemical toxicity of uranyl ion. The WHO standard of uranyl ion makes it necessary to develop highly sensitive uranyl rapid warning system in drinking water monitoring. Herein, a visualized rapid warning system for trace uranyl ion is carried out based on electrochemiluminescence (ECL) imaging technology to give an ultra-low limit of detection (LOD) and high selectivity. Amidoxime, a bi-functional group with both uranyl ion capturing and co-reactive functions, is modified on a conjugated polymer backbone with strong ECL signal to be prepared into three-in-one polymer nanoparticles (PNPs) with self-enhanced ECL property. The captured uranyl ion can enhance the ECL signal of PNPs via resonance energy transfer process to give the LOD as 0.5 ng/L, which is much lower than the known luminescent uranyl sensors. Furthermore, ECL imaging technology is introduced into realizing visualized uranyl rapid warning, and can be successfully applied on natural water samples. This study provides a novel strategy for uranyl rapid warning, and shows its potential meaning in public security and environmental fields.
The development of uranyl ion detection technology has exhibited its significance in public security and environmental fields for the radioactivity and chemical toxicity of uranyl ion. The WHO standard of uranyl ion makes it necessary to develop highly sensitive uranyl rapid warning system in drinking water monitoring. Herein, a visualized rapid warning system for trace uranyl ion is carried out based on electrochemiluminescence (ECL) imaging technology to give an ultra-low limit of detection (LOD) and high selectivity. Amidoxime, a bi-functional group with both uranyl ion capturing and co-reactive functions, is modified on a conjugated polymer backbone with strong ECL signal to be prepared into three-in-one polymer nanoparticles (PNPs) with self-enhanced ECL property. The captured uranyl ion can enhance the ECL signal of PNPs via resonance energy transfer process to give the LOD as 0.5 ng/L, which is much lower than the known luminescent uranyl sensors. Furthermore, ECL imaging technology is introduced into realizing visualized uranyl rapid warning, and can be successfully applied on natural water samples. This study provides a novel strategy for uranyl rapid warning, and shows its potential meaning in public security and environmental fields.
2022, 33(7): 3461-3467
doi: 10.1016/j.cclet.2022.01.019
Abstract:
During the chemical weathering of the uranium mill tailings, released uranium could be immobilized by the newly formed secondary minerals such as oxyhydroxides. A deeper understanding of the interaction between uranium and common oxyhydroxides under environmental conditions is necessary. In this work, uranium sorption behaviors on Al-, Mn- and Fe-oxyhydroxide minerals (boehmite, manganite, goethite, and lepidocrocite) were investigated by batch experiments. Results showed that the uranium sorption on Al-oxyhydroxide behaved significantly differently from the other three minerals. The sorption edge of the Mn- and Fe-oxyhydroxides located around pH 5, while the sorption edge of boehmite shifted about 1.5 pH unit to near neutral. The sorption isotherms of uranium on manganite, goethite and lepidocrocite at pH 5.0 could be well fitted by the Langmuir model. Instead of surface complexation, sorption on boehmite happened mainly by uranium-bearing carbonates and hydroxides precipitation as illustrated by the characterization results. Both carbonate and phosphate strongly affected the uranium sorption behavior. The removal efficiency of uranium by boehmite exceeded 98% after three sorption-desorption cycles, indicating it may be a potential material for uranium removal and recovery.
During the chemical weathering of the uranium mill tailings, released uranium could be immobilized by the newly formed secondary minerals such as oxyhydroxides. A deeper understanding of the interaction between uranium and common oxyhydroxides under environmental conditions is necessary. In this work, uranium sorption behaviors on Al-, Mn- and Fe-oxyhydroxide minerals (boehmite, manganite, goethite, and lepidocrocite) were investigated by batch experiments. Results showed that the uranium sorption on Al-oxyhydroxide behaved significantly differently from the other three minerals. The sorption edge of the Mn- and Fe-oxyhydroxides located around pH 5, while the sorption edge of boehmite shifted about 1.5 pH unit to near neutral. The sorption isotherms of uranium on manganite, goethite and lepidocrocite at pH 5.0 could be well fitted by the Langmuir model. Instead of surface complexation, sorption on boehmite happened mainly by uranium-bearing carbonates and hydroxides precipitation as illustrated by the characterization results. Both carbonate and phosphate strongly affected the uranium sorption behavior. The removal efficiency of uranium by boehmite exceeded 98% after three sorption-desorption cycles, indicating it may be a potential material for uranium removal and recovery.
2022, 33(7): 3468-3473
doi: 10.1016/j.cclet.2022.03.097
Abstract:
Nitrogen enrichment and increased nitrogen content is an effective strategy for enhancing adsorption of uranium by carbon nitride polymers. Herein, we reported the uranium absorption by using a structurally well-defined and nitrogen-rich carbon nitride polymer with C3N5 stoichiometry for the first time. In comparison with the adsorption performance of g-C3N4 for U(VI), the conjugation system of the material was increased by connecting the heptazine unit through the azo bridge in the structure of C3N5, so that C3N5 exhibited several times higher adsorption performance than that of g-C3N4. The C3N5 has high kinetics for uranyl ions, which can adsorb 100 mg/g U(VI) in only 10 min and reach complete adsorption equilibrium in 60 min; the theoretical maximum adsorption capacity is 207 mg/g, meanwhile, the material exhibits high selectivity. The results of spectral analysis and theoretical calculations indicate that the process of uranyl ion capture by C3N5 is a combination of physical and chemical adsorption, and its higher density of electronic states makes the electrostatic binding ability enhanced, which is favorable to the adsorption of uranyl ions by C3N5. This work indicates that C3N5 has great promise and application in the separation and enrichment of uranyl ions, and also provides a reference for the systematic investigation of the adsorption ability of nitrogen-rich carbon nitrogen polymers on uranyl ions.
Nitrogen enrichment and increased nitrogen content is an effective strategy for enhancing adsorption of uranium by carbon nitride polymers. Herein, we reported the uranium absorption by using a structurally well-defined and nitrogen-rich carbon nitride polymer with C3N5 stoichiometry for the first time. In comparison with the adsorption performance of g-C3N4 for U(VI), the conjugation system of the material was increased by connecting the heptazine unit through the azo bridge in the structure of C3N5, so that C3N5 exhibited several times higher adsorption performance than that of g-C3N4. The C3N5 has high kinetics for uranyl ions, which can adsorb 100 mg/g U(VI) in only 10 min and reach complete adsorption equilibrium in 60 min; the theoretical maximum adsorption capacity is 207 mg/g, meanwhile, the material exhibits high selectivity. The results of spectral analysis and theoretical calculations indicate that the process of uranyl ion capture by C3N5 is a combination of physical and chemical adsorption, and its higher density of electronic states makes the electrostatic binding ability enhanced, which is favorable to the adsorption of uranyl ions by C3N5. This work indicates that C3N5 has great promise and application in the separation and enrichment of uranyl ions, and also provides a reference for the systematic investigation of the adsorption ability of nitrogen-rich carbon nitrogen polymers on uranyl ions.
2022, 33(7): 3474-3477
doi: 10.1016/j.cclet.2022.02.012
Abstract:
Targeted alpha-therapy (TAT) is increasingly attractive due to its extraordinary antitumor efficacy. However, the supply of α-emitters for TAT is insufficient and under control by a limited number of countries. 212Pb is a promising α-emitter with an optimal half-life (10.6 h) and favored decay chain. Of interest, 212Pb can be extracted directly from natural thorium, which may be abundant in the mining waste of rare-earth, uranium, etc. Indeed, radioactive thorium waste has been a longstanding environmental challenge that needs immediate action. Developing an on-demand and facile process to isolate 212Pb from natural thorium would be ideal to meet the above challenges, yet is difficult. In theory, the ratio of 212Pb to natTh is below 10−13 in commercially available thorium salts. As a pilot study, 2.2 MBq of 212Pb was successfully extracted from a 5 L solution of thorium nitrate by using a Pb-selective resin. The radiochemical purity of 212Pb is over 99.9% according to gamma-ray analysis. The purified 212Pb was applied to radiolabel a couple of peptides used in clinics (i.e. PSMA, TATE and FAPI-04), and the radiochemical yields are > 85%. Of note, 212Pb can be repeatedly separated from the thorium solution every 2 days. In summary, a practical and scalable method was developed to isolate 212Pb for potentially clinical use, which may be of great importance as it does not require either cyclotron or nuclear reactor.
Targeted alpha-therapy (TAT) is increasingly attractive due to its extraordinary antitumor efficacy. However, the supply of α-emitters for TAT is insufficient and under control by a limited number of countries. 212Pb is a promising α-emitter with an optimal half-life (10.6 h) and favored decay chain. Of interest, 212Pb can be extracted directly from natural thorium, which may be abundant in the mining waste of rare-earth, uranium, etc. Indeed, radioactive thorium waste has been a longstanding environmental challenge that needs immediate action. Developing an on-demand and facile process to isolate 212Pb from natural thorium would be ideal to meet the above challenges, yet is difficult. In theory, the ratio of 212Pb to natTh is below 10−13 in commercially available thorium salts. As a pilot study, 2.2 MBq of 212Pb was successfully extracted from a 5 L solution of thorium nitrate by using a Pb-selective resin. The radiochemical purity of 212Pb is over 99.9% according to gamma-ray analysis. The purified 212Pb was applied to radiolabel a couple of peptides used in clinics (i.e. PSMA, TATE and FAPI-04), and the radiochemical yields are > 85%. Of note, 212Pb can be repeatedly separated from the thorium solution every 2 days. In summary, a practical and scalable method was developed to isolate 212Pb for potentially clinical use, which may be of great importance as it does not require either cyclotron or nuclear reactor.
2022, 33(7): 3478-3483
doi: 10.1016/j.cclet.2022.03.023
Abstract:
Phototheranostics have attracted tremendous attention in cancer diagnosis and treatment because of the noninvasiveness and promising effectiveness. Developing advanced phototheranostic agents with long emission wavelength, excellent biocompatibility, great tumor-targeting capability, and efficient therapeutic effect is highly desirable. However, the mutual constraint between imaging and therapeutic functions usually hinders their wide applications in biomedical field. To balance this contradiction, we herein rationally designed and synthesized three novel tumor-targeted NIR-II probes (QR-2PEG321, QR-2PEG1000, and QR-2PEG5000) by conjugating three different chain lengths of PEG onto an integrin αvβ3-targeted NIR-II heptamethine cyanine fluorophore, respectively. In virtue of the essential amphiphilic characteristics of PEG polymers, these probes display various degree of aggregation in aqueous buffer accompanying with differential NIR-II imaging and photothermal (PTT) therapeutic performance. Both in vitro and in vivo results have demonstrated that probe QR-2PEG5000 has the best NIR-II imaging performance with prominent renal clearance, whereas QR-2PEG321 possesses excellent photoacoustic signal as well as PTT effect, which undoubtedly provides a promising toolbox for tumor diagnosis and therapy. We thus envision that these synthesized probes have great potential to be explored as a toolkit for precise diagnosis and treatment of malignant tumors.
Phototheranostics have attracted tremendous attention in cancer diagnosis and treatment because of the noninvasiveness and promising effectiveness. Developing advanced phototheranostic agents with long emission wavelength, excellent biocompatibility, great tumor-targeting capability, and efficient therapeutic effect is highly desirable. However, the mutual constraint between imaging and therapeutic functions usually hinders their wide applications in biomedical field. To balance this contradiction, we herein rationally designed and synthesized three novel tumor-targeted NIR-II probes (QR-2PEG321, QR-2PEG1000, and QR-2PEG5000) by conjugating three different chain lengths of PEG onto an integrin αvβ3-targeted NIR-II heptamethine cyanine fluorophore, respectively. In virtue of the essential amphiphilic characteristics of PEG polymers, these probes display various degree of aggregation in aqueous buffer accompanying with differential NIR-II imaging and photothermal (PTT) therapeutic performance. Both in vitro and in vivo results have demonstrated that probe QR-2PEG5000 has the best NIR-II imaging performance with prominent renal clearance, whereas QR-2PEG321 possesses excellent photoacoustic signal as well as PTT effect, which undoubtedly provides a promising toolbox for tumor diagnosis and therapy. We thus envision that these synthesized probes have great potential to be explored as a toolkit for precise diagnosis and treatment of malignant tumors.
2022, 33(7): 3484-3487
doi: 10.1016/j.cclet.2022.03.098
Abstract:
The in vivo degradation behavior of metallic nanoparticles (NPs) is very important for their biomedical applications and safety evaluation. Here, a method of laser ablation-single particle inductively coupled plasma mass spectrometry (LA-sp-ICP-MS) is shown to have high spatial resolution, sensitivity and accuracy for simultaneous imaging the in situ distribution of particulate Ag (P-Ag) and released ionic Ag (Ion-Ag) in the sub-organs of spleen, liver and kidney after intravenous injection of Ag nanoparticles (50 nm, AgNPs) to mice. Under the optimized parameters of 0.4 J/cm2 laser fluence on a 30 µm spot with dwell time at 100 µs, the signals of P-Ag and Ion-Ag in the organic tissues can be easily distinguished from the mass spectra. The method of iterative threshold algorithm has been used to distract the signals of P-Ag and Ion-Ag and separate each other. The resulting images for the first time provide visualized evidence that a considerable amount of P-Ag accumulated in the splenic marginal zone, but widely distributed in the liver parenchyma at 24 h after injection of AgNPs, and in the meantime, obvious amounts of ionic Ag released and distributed in the organs. In addition, the imaging results indicate that the AgNP excretion in the kidney is mainly in ionic forms. The investigation here demonstrates that the developed LA-sp-ICP-MS method with high spatial resolution, sensitivity and visualization capability can become a powerful tool in the clinical context of metallic NPs.
The in vivo degradation behavior of metallic nanoparticles (NPs) is very important for their biomedical applications and safety evaluation. Here, a method of laser ablation-single particle inductively coupled plasma mass spectrometry (LA-sp-ICP-MS) is shown to have high spatial resolution, sensitivity and accuracy for simultaneous imaging the in situ distribution of particulate Ag (P-Ag) and released ionic Ag (Ion-Ag) in the sub-organs of spleen, liver and kidney after intravenous injection of Ag nanoparticles (50 nm, AgNPs) to mice. Under the optimized parameters of 0.4 J/cm2 laser fluence on a 30 µm spot with dwell time at 100 µs, the signals of P-Ag and Ion-Ag in the organic tissues can be easily distinguished from the mass spectra. The method of iterative threshold algorithm has been used to distract the signals of P-Ag and Ion-Ag and separate each other. The resulting images for the first time provide visualized evidence that a considerable amount of P-Ag accumulated in the splenic marginal zone, but widely distributed in the liver parenchyma at 24 h after injection of AgNPs, and in the meantime, obvious amounts of ionic Ag released and distributed in the organs. In addition, the imaging results indicate that the AgNP excretion in the kidney is mainly in ionic forms. The investigation here demonstrates that the developed LA-sp-ICP-MS method with high spatial resolution, sensitivity and visualization capability can become a powerful tool in the clinical context of metallic NPs.
2022, 33(7): 3488-3491
doi: 10.1016/j.cclet.2022.04.004
Abstract:
Thioredoxin reductase 1 (TrxR1) is over activity in tumor cell to maintain their redox balance. Although gold clusters have great potential in antitumor drug as they could well inhibit TrxR1, the molecular mechanism has not been disclosed yet. In this work, we revealed gold clusters can well inhibit the activity of TrxR1 in lung tumor cells and further disclosed the inhibition mechanism by using computational simulation methods. We firstly inferred the binding sites of gold in the hydrophobic cavities on TrxR1. The simulation results show that the gold ion (released from Au cluster) interact with –SH of Cys189 in TrxR1, this greatly increase the distance between the C-terminal redox center of TrxR1 and the Trx redox center, thereby destroy the electron transfer pathway between them. Our electron transfer destroying mechanism is different from the previous hypothesis that gold binds to the Sec498 of TrxR1 which has never been proved by experimental and theory studies. This work provides a new understanding of the gold clusters to inhibit TrxR1 activity.
Thioredoxin reductase 1 (TrxR1) is over activity in tumor cell to maintain their redox balance. Although gold clusters have great potential in antitumor drug as they could well inhibit TrxR1, the molecular mechanism has not been disclosed yet. In this work, we revealed gold clusters can well inhibit the activity of TrxR1 in lung tumor cells and further disclosed the inhibition mechanism by using computational simulation methods. We firstly inferred the binding sites of gold in the hydrophobic cavities on TrxR1. The simulation results show that the gold ion (released from Au cluster) interact with –SH of Cys189 in TrxR1, this greatly increase the distance between the C-terminal redox center of TrxR1 and the Trx redox center, thereby destroy the electron transfer pathway between them. Our electron transfer destroying mechanism is different from the previous hypothesis that gold binds to the Sec498 of TrxR1 which has never been proved by experimental and theory studies. This work provides a new understanding of the gold clusters to inhibit TrxR1 activity.
2022, 33(7): 3492-3496
doi: 10.1016/j.cclet.2022.01.007
Abstract:
As one of the most common cancers in the world, hepatocellular carcinoma (HCC) has become a major threat to human health. Radioembolization is a first-line option for the treatment of HCC, especially when other conventional treatments fail or there exist some relative contraindications. Herein, we developed a facile and efficient method for preparing 177Lu-microspheres potentially useful for precise radioembolization therapy of HCC. The radiolabeling efficiency of 177Lu-microspheres was as high as 96.8% ± 0.5%, and the radiolabeling process did not alter the morphology of the mother microspheres. The SPECT/CT studies enabled by the unique emissions of 177Lu suggested that almost no 177Lu ion loaded by the microspheres was released over more than 32 d in vivo, which led to remarkable inhibition effect on the growth of HepG2 tumors subcutaneously transplanted in mice. The current approach may thus offer promising 177Lu-microspheres for clinical radioembolization of HCC.
As one of the most common cancers in the world, hepatocellular carcinoma (HCC) has become a major threat to human health. Radioembolization is a first-line option for the treatment of HCC, especially when other conventional treatments fail or there exist some relative contraindications. Herein, we developed a facile and efficient method for preparing 177Lu-microspheres potentially useful for precise radioembolization therapy of HCC. The radiolabeling efficiency of 177Lu-microspheres was as high as 96.8% ± 0.5%, and the radiolabeling process did not alter the morphology of the mother microspheres. The SPECT/CT studies enabled by the unique emissions of 177Lu suggested that almost no 177Lu ion loaded by the microspheres was released over more than 32 d in vivo, which led to remarkable inhibition effect on the growth of HepG2 tumors subcutaneously transplanted in mice. The current approach may thus offer promising 177Lu-microspheres for clinical radioembolization of HCC.
2022, 33(7): 3497-3501
doi: 10.1016/j.cclet.2022.02.068
Abstract:
Tumor-related PD-L2 expression is associated with the clinical efficacy of PD-1/PD-L1 blockade therapy. PD-L2-specific imaging can help selecting patients for appropriate immunotherapy. In this study, a PD-L2-targeting peptide (PDP2) was screened by the one-bead one-compound combinatorial library approach. Using the retro-inverso D-peptide of PDP2 (RD-PDP2) and PEGylation strategies, we developed a novel Tc-99m-labeled PD-L2-targeting peptide as a SPECT tracer (99mTc-PEG6-RD-PDP2) for imaging of tumor PD-L2 expression. The radiolabeling yield of 99mTc-PEG6-RD-PDP2 was greater than 95% by the standard HYNIC/tricine/TPPTS labeling procedure. 99mTc-PEG6-RD-PDP2 displayed high PD-L2-binding specificity both in vitro and in vivo. SPECT/CT imaging with 99mTc-PEG6-RD-PDP2 showed that the A549-PD-L2 tumors were clearly visualized, whereas the signals in PD-L2-negative A549 tumors were much lower. In vivo blocking study suggested that the tumor uptake of 99mTc-PEG6-RD-PDP2 was PD-L2 specifically mediated. 99mTc-PEG6-RD-PDP2 is a promising SPECT probe for the non-invasive imaging of tumor PD-L2 expression and has a great potential in guiding the anti-PD-1 or anti-PD-L1 immunotherapy of cancer.
Tumor-related PD-L2 expression is associated with the clinical efficacy of PD-1/PD-L1 blockade therapy. PD-L2-specific imaging can help selecting patients for appropriate immunotherapy. In this study, a PD-L2-targeting peptide (PDP2) was screened by the one-bead one-compound combinatorial library approach. Using the retro-inverso D-peptide of PDP2 (RD-PDP2) and PEGylation strategies, we developed a novel Tc-99m-labeled PD-L2-targeting peptide as a SPECT tracer (99mTc-PEG6-RD-PDP2) for imaging of tumor PD-L2 expression. The radiolabeling yield of 99mTc-PEG6-RD-PDP2 was greater than 95% by the standard HYNIC/tricine/TPPTS labeling procedure. 99mTc-PEG6-RD-PDP2 displayed high PD-L2-binding specificity both in vitro and in vivo. SPECT/CT imaging with 99mTc-PEG6-RD-PDP2 showed that the A549-PD-L2 tumors were clearly visualized, whereas the signals in PD-L2-negative A549 tumors were much lower. In vivo blocking study suggested that the tumor uptake of 99mTc-PEG6-RD-PDP2 was PD-L2 specifically mediated. 99mTc-PEG6-RD-PDP2 is a promising SPECT probe for the non-invasive imaging of tumor PD-L2 expression and has a great potential in guiding the anti-PD-1 or anti-PD-L1 immunotherapy of cancer.
2022, 33(7): 3502-3506
doi: 10.1016/j.cclet.2022.03.056
Abstract:
Carbohydrate antigen 19-9 (CA19-9) with multi epitopes relatively high expresses on colorectal cancer (CRC) cells, making it an attractive target for developing radioimmunotherapy (RIT) for CRC. The lutetium-177 (177Lu) labeled monoclonal antibodies (mAbs) can selectively bind the corresponding antigens and release targeted cytotoxic radiation, which could induce cell apoptosis and reduce the drug-induced resistance. Here, a series of CA19-9 mAbs were labeled with zirconium-89 (89Zr), and one with high tumor uptake was screened via PET imaging, which has potential application for the diagnosis of CRC. Then the screened mAb (C003) labeled with 177Lu was utilized for CA19-9 targeted RIT, which presents a significant suppression effect on the growth of colo205 xenografts than immunotherapy alone. Meanwhile, the side effects of 177Lu-DOTA-C003 are limited according to the results of in vivo study. Both 89Zr-DFO-C003 for CRC immune-PET imaging and 177Lu-DOTA-C003 for RIT against CRC exhibit good potential in clinical applications.
Carbohydrate antigen 19-9 (CA19-9) with multi epitopes relatively high expresses on colorectal cancer (CRC) cells, making it an attractive target for developing radioimmunotherapy (RIT) for CRC. The lutetium-177 (177Lu) labeled monoclonal antibodies (mAbs) can selectively bind the corresponding antigens and release targeted cytotoxic radiation, which could induce cell apoptosis and reduce the drug-induced resistance. Here, a series of CA19-9 mAbs were labeled with zirconium-89 (89Zr), and one with high tumor uptake was screened via PET imaging, which has potential application for the diagnosis of CRC. Then the screened mAb (C003) labeled with 177Lu was utilized for CA19-9 targeted RIT, which presents a significant suppression effect on the growth of colo205 xenografts than immunotherapy alone. Meanwhile, the side effects of 177Lu-DOTA-C003 are limited according to the results of in vivo study. Both 89Zr-DFO-C003 for CRC immune-PET imaging and 177Lu-DOTA-C003 for RIT against CRC exhibit good potential in clinical applications.
2022, 33(7): 3507-3515
doi: 10.1016/j.cclet.2022.02.073
Abstract:
Heavy haze events have become a serious environment and health problem in China and many developing countries, especially in big cities, like Beijing. However, the factors and processes triggered the formation of secondary particles from the gaseous pollutants are still not clear, and the processes driving evolution and degradation of heavy haze events are not well understood. Iodine isotopes (127I and 129I) as tracers were analyzed in time series aerosol samples collected from Beijing. It was observed that the 127I concentrations in aerosols peaked during the heavy haze events. The conversion of gaseous iodine to particular iodine oxides through photochemical reactions provides primary nuclei in nucleation and formation of secondary air particles, which was strengthened as the external iodine input from the fossil fuel burning in the south/southeast industrial cities and consequentially induced heavy haze events. Anthropogenic 129I concentrations peaked during clean air conditions and showed high levels in spring and later autumn compared to that in summer. 129I originated from the direct air discharges and re-emissions from contaminated seawaters by the European nuclear fuel reprocessing plants was transported to Beijing by the interaction of Westerlies and East Asian winter monsoon. Three types of mechanisms were found in the formation and evolution of heavy haze events in Beijing by the variation of 127I and 129I, i.e., iodine oxides intermediated secondary air particles, dust storm and mixed mode by both secondary air particles and dust storm induced processes.
Heavy haze events have become a serious environment and health problem in China and many developing countries, especially in big cities, like Beijing. However, the factors and processes triggered the formation of secondary particles from the gaseous pollutants are still not clear, and the processes driving evolution and degradation of heavy haze events are not well understood. Iodine isotopes (127I and 129I) as tracers were analyzed in time series aerosol samples collected from Beijing. It was observed that the 127I concentrations in aerosols peaked during the heavy haze events. The conversion of gaseous iodine to particular iodine oxides through photochemical reactions provides primary nuclei in nucleation and formation of secondary air particles, which was strengthened as the external iodine input from the fossil fuel burning in the south/southeast industrial cities and consequentially induced heavy haze events. Anthropogenic 129I concentrations peaked during clean air conditions and showed high levels in spring and later autumn compared to that in summer. 129I originated from the direct air discharges and re-emissions from contaminated seawaters by the European nuclear fuel reprocessing plants was transported to Beijing by the interaction of Westerlies and East Asian winter monsoon. Three types of mechanisms were found in the formation and evolution of heavy haze events in Beijing by the variation of 127I and 129I, i.e., iodine oxides intermediated secondary air particles, dust storm and mixed mode by both secondary air particles and dust storm induced processes.
2022, 33(7): 3516-3521
doi: 10.1016/j.cclet.2022.03.030
Abstract:
Plutonium (Pu) is an anthropogenic radionuclide which mainly derived from atmospheric nuclear tests in the environment. In this study, the Pu isotopes (239Pu and 240Pu) in aerosol samples collected during the sandstorm and non-sandstorm period were measured by accelerator mass spectrometry (AMS) and the behavior of Pu was studied. The activity concentrations of 239Pu and 240Pu in the aerosol samples of Beijing were ranged from 0.62 nBq/m3 to 99.6 nBq/m3 for 239Pu and 3.51 nBq/m3 to 60.23 nBq/m3 for 240Pu, respectively. 239Pu and 240Pu concentrations exhibited a remarkable seasonal variation trend, with the higher results showed in spring, and the relatively lower concentrations in winter. The observed higher concentration of 239Pu and 240Pu detected in sandstorm samples further indicated Pu was closely related to the occurrence of sandstorms. The global fallout characteristics of 240Pu/239Pu atom ratios (average 0.20, ranging from 0.16 to 0.27) in aerosol samples indicating that global fallout was the major source of Pu in the atmosphere. Using aluminum (Al) as an indicator of soil resuspension, significant positive correlation between 239Pu and Al (r2 = 0.934), 240Pu and Al (r2 = 0.525) revealed that soil resuspension was a primary source of atmospheric Pu in Beijing. These results implied that the combination of 239Pu, 240Pu and Al could be used as the potential tracer of sandstorm.
Plutonium (Pu) is an anthropogenic radionuclide which mainly derived from atmospheric nuclear tests in the environment. In this study, the Pu isotopes (239Pu and 240Pu) in aerosol samples collected during the sandstorm and non-sandstorm period were measured by accelerator mass spectrometry (AMS) and the behavior of Pu was studied. The activity concentrations of 239Pu and 240Pu in the aerosol samples of Beijing were ranged from 0.62 nBq/m3 to 99.6 nBq/m3 for 239Pu and 3.51 nBq/m3 to 60.23 nBq/m3 for 240Pu, respectively. 239Pu and 240Pu concentrations exhibited a remarkable seasonal variation trend, with the higher results showed in spring, and the relatively lower concentrations in winter. The observed higher concentration of 239Pu and 240Pu detected in sandstorm samples further indicated Pu was closely related to the occurrence of sandstorms. The global fallout characteristics of 240Pu/239Pu atom ratios (average 0.20, ranging from 0.16 to 0.27) in aerosol samples indicating that global fallout was the major source of Pu in the atmosphere. Using aluminum (Al) as an indicator of soil resuspension, significant positive correlation between 239Pu and Al (r2 = 0.934), 240Pu and Al (r2 = 0.525) revealed that soil resuspension was a primary source of atmospheric Pu in Beijing. These results implied that the combination of 239Pu, 240Pu and Al could be used as the potential tracer of sandstorm.
2022, 33(7): 3522-3526
doi: 10.1016/j.cclet.2022.03.036
Abstract:
The abundances of heavy elements produced in r-process nucleosynthesis in the early solar system need experimental verification. 244Pu could be the heaviest primordial nuclide produced before the formation of the Earth still being detectable today. As recent attempts failed to confirm the discovery of 244Pu signals at a concentration of 1.0 × 10−18 g/g in bastnaesite reported by Hoffman et al. in this study, the total primordial 244Pu in 450 g bastnaesite sample from Bayan Obo ore (China) was measured using ultra-sensitive compact accelerator mass spectrometry (AMS). As no 244Pu signal was detected, an upper limit for the 244Pu in our bastnaesite sample was estimated to be 2.1 × 10−20 g/g at 99% confidence level.
The abundances of heavy elements produced in r-process nucleosynthesis in the early solar system need experimental verification. 244Pu could be the heaviest primordial nuclide produced before the formation of the Earth still being detectable today. As recent attempts failed to confirm the discovery of 244Pu signals at a concentration of 1.0 × 10−18 g/g in bastnaesite reported by Hoffman et al. in this study, the total primordial 244Pu in 450 g bastnaesite sample from Bayan Obo ore (China) was measured using ultra-sensitive compact accelerator mass spectrometry (AMS). As no 244Pu signal was detected, an upper limit for the 244Pu in our bastnaesite sample was estimated to be 2.1 × 10−20 g/g at 99% confidence level.
2022, 33(7): 3527-3530
doi: 10.1016/j.cclet.2022.03.026
Abstract:
Two tetravalent uranium silicate and germanate M2UIVT3O9 (M = K, Cs; T = Si, Ge) crystals were crystalized under inert gas by molten salt flux growth method. K2USi3O9 (1) crystallizes in the monoclinic space group P121/n1 with lattice parameters a = 7.1076 Å, b = 10.4776 Å, c = 12.2957 Å, γ = 120° and V = 915.67 Å3. Cs2UGe3O9 (2) crystallizes in a hexagonal space group P-6 with lattice constants of a = 7.5138 Å, b = 7.5138 Å, c = 11.0114 Å, γ = 120° and V = 538.38 Å3. Bond valence calculations indicate tetravalent uranium in both structures, which contain three-membered single-ring T3O96− trimers. K2USi3O9 is the first uranium silicate that contains the Si3O96− trimers.
Two tetravalent uranium silicate and germanate M2UIVT3O9 (M = K, Cs; T = Si, Ge) crystals were crystalized under inert gas by molten salt flux growth method. K2USi3O9 (1) crystallizes in the monoclinic space group P121/n1 with lattice parameters a = 7.1076 Å, b = 10.4776 Å, c = 12.2957 Å, γ = 120° and V = 915.67 Å3. Cs2UGe3O9 (2) crystallizes in a hexagonal space group P-6 with lattice constants of a = 7.5138 Å, b = 7.5138 Å, c = 11.0114 Å, γ = 120° and V = 538.38 Å3. Bond valence calculations indicate tetravalent uranium in both structures, which contain three-membered single-ring T3O96− trimers. K2USi3O9 is the first uranium silicate that contains the Si3O96− trimers.
2022, 33(7): 3531-3533
doi: 10.1016/j.cclet.2022.02.057
Abstract:
The complexation of pentavalent neptunium, Np(V), with nitrate ion in an ionic liquid solution has been studied spectroscopically for the first time. The characteristic f-f transition absorption band of Np(V) in the NIR region changes significantly upon the titration of nitrate ion into the solution, revealing strong complexation of Np(V) with nitrate ion in the ionic liquid. Most notably, the absorption band of Np(V) almost disappears when a sufficiently high concentration of nitrate ion is present in the solution. Such a rare optically "silent" species can be assigned to the 1:2 Np(V)/nitrate complex with a centrosymmetric coordination environment where Np sits at the inversion center.
The complexation of pentavalent neptunium, Np(V), with nitrate ion in an ionic liquid solution has been studied spectroscopically for the first time. The characteristic f-f transition absorption band of Np(V) in the NIR region changes significantly upon the titration of nitrate ion into the solution, revealing strong complexation of Np(V) with nitrate ion in the ionic liquid. Most notably, the absorption band of Np(V) almost disappears when a sufficiently high concentration of nitrate ion is present in the solution. Such a rare optically "silent" species can be assigned to the 1:2 Np(V)/nitrate complex with a centrosymmetric coordination environment where Np sits at the inversion center.
2022, 33(7): 3534-3538
doi: 10.1016/j.cclet.2022.03.068
Abstract:
Due to the rigid Si-O-Si backbone, silicone rubber (SR) have a widespread application in extreme environment such as high temperature and high-level radiation. However, the radiation stability of SR still does not meet the practical needs in special radiation environments. Herein we prepared epoxy POSS(ePOSS)/SR nanocomposites with excellent thermal stability and radiation resistance. As a physical crosslinking point in the SR, addition of small amount of ePOSS not only enhanced the mechanical properties of the matrix, but also improved its thermal stability greatly due to their good compatibility. ePOSS/SR had higher radiation stability in air than SR owing to the inhibition of radiation oxidation by ePOSS, and the yield of main gaseous radiolysis products (CH4, H2, CO and CO2) of SR and ePOSS/SR nanocomposites was determined. By analyzing the changes of chemical structure, thermal properties and mechanical properties of the ePOSS/SR nanocomposite, combined with the characteristics of gas products after γ-irradiation, the radiation induced crosslinking and degradation mechanism of the nanocomposites was proposed comprehensively.
Due to the rigid Si-O-Si backbone, silicone rubber (SR) have a widespread application in extreme environment such as high temperature and high-level radiation. However, the radiation stability of SR still does not meet the practical needs in special radiation environments. Herein we prepared epoxy POSS(ePOSS)/SR nanocomposites with excellent thermal stability and radiation resistance. As a physical crosslinking point in the SR, addition of small amount of ePOSS not only enhanced the mechanical properties of the matrix, but also improved its thermal stability greatly due to their good compatibility. ePOSS/SR had higher radiation stability in air than SR owing to the inhibition of radiation oxidation by ePOSS, and the yield of main gaseous radiolysis products (CH4, H2, CO and CO2) of SR and ePOSS/SR nanocomposites was determined. By analyzing the changes of chemical structure, thermal properties and mechanical properties of the ePOSS/SR nanocomposite, combined with the characteristics of gas products after γ-irradiation, the radiation induced crosslinking and degradation mechanism of the nanocomposites was proposed comprehensively.
2022, 33(7): 3539-3542
doi: 10.1016/j.cclet.2022.03.092
Abstract:
Actinide metallacycles are an emerging class of functional coordination assemblies, but multi-level assembly from metallacycle units toward hierarchical supramolecular structures are still rarely investigated. In this work, we put forward a novel supramolecular inclusion-based method through introducing two macrocyclic hosts, cucurbit[7]uril (CB[7]) and cucurbit[8]uril (CB[8]) to facilitate hierarchical assembly of uranyl metallacycles with higher complexity, and successfully prepare two different kinds of uranyl metallacycle-based complexes with intriguing hierarchical structures, a CB[7]-based four-member molecular necklace ([4]MN) and a CB[8]-involved ring-in-ring supramolecular polymer chain. The results obtained here prove the feasibility of supramolecular inclusion for regulating coordination assembly of uranyl metallacycles and related hierarchical structures. It is believed that this method can be used to achieve the construction of actinide coordination assemblies with higher structural complexity.
Actinide metallacycles are an emerging class of functional coordination assemblies, but multi-level assembly from metallacycle units toward hierarchical supramolecular structures are still rarely investigated. In this work, we put forward a novel supramolecular inclusion-based method through introducing two macrocyclic hosts, cucurbit[7]uril (CB[7]) and cucurbit[8]uril (CB[8]) to facilitate hierarchical assembly of uranyl metallacycles with higher complexity, and successfully prepare two different kinds of uranyl metallacycle-based complexes with intriguing hierarchical structures, a CB[7]-based four-member molecular necklace ([4]MN) and a CB[8]-involved ring-in-ring supramolecular polymer chain. The results obtained here prove the feasibility of supramolecular inclusion for regulating coordination assembly of uranyl metallacycles and related hierarchical structures. It is believed that this method can be used to achieve the construction of actinide coordination assemblies with higher structural complexity.
2022, 33(7): 3543-3548
doi: 10.1016/j.cclet.2022.03.099
Abstract:
Racemic [18F]FBFP ([18F]1) proved to be a potent σ1 receptor radiotracer with superior imaging properties. The pure enantiomers of unlabeled compounds (S)- and (R)-1 and the corresponding iodonium ylide precursors were synthesized and characterized. The two enantiomers (S)-1 and (R)-1 exhibited comparable high affinity for σ1 receptors and selectivity over σ2 receptors. The Ca2+ fluorescence assay indicated that (R)-1 behaved as an antagonist and (S)-1 as an agonist for σ1 receptors. The 18F-labeled enantiomers (S)- and (R)-[18F]1 were obtained in > 99% enantiomeric purity from the corresponding enantiopure iodonium ylide precursors with radiochemical yield of 24.4% ± 2.6% and molar activity of 86-214 GBq/µmol. In ICR mice both (S)- and (R)-[18F]1 displayed comparable high brain uptake, brain-to-blood ratio, in vivo stability and binding specificity in the brain and peripheral organs. In micro-positron emission tomography (PET) imaging studies in rats, (S)-[18F]1 exhibited faster clearance from the brain than (R)-[18F]1, indicating different brain kinetics of the two enantiomers. Both (S)- and (R)-[18F]1 warrant further evaluation in primates to translate a single enantiomer with more suitable kinetics for imaging the σ1 receptors in humans.
Racemic [18F]FBFP ([18F]1) proved to be a potent σ1 receptor radiotracer with superior imaging properties. The pure enantiomers of unlabeled compounds (S)- and (R)-1 and the corresponding iodonium ylide precursors were synthesized and characterized. The two enantiomers (S)-1 and (R)-1 exhibited comparable high affinity for σ1 receptors and selectivity over σ2 receptors. The Ca2+ fluorescence assay indicated that (R)-1 behaved as an antagonist and (S)-1 as an agonist for σ1 receptors. The 18F-labeled enantiomers (S)- and (R)-[18F]1 were obtained in > 99% enantiomeric purity from the corresponding enantiopure iodonium ylide precursors with radiochemical yield of 24.4% ± 2.6% and molar activity of 86-214 GBq/µmol. In ICR mice both (S)- and (R)-[18F]1 displayed comparable high brain uptake, brain-to-blood ratio, in vivo stability and binding specificity in the brain and peripheral organs. In micro-positron emission tomography (PET) imaging studies in rats, (S)-[18F]1 exhibited faster clearance from the brain than (R)-[18F]1, indicating different brain kinetics of the two enantiomers. Both (S)- and (R)-[18F]1 warrant further evaluation in primates to translate a single enantiomer with more suitable kinetics for imaging the σ1 receptors in humans.
2022, 33(7): 3549-3555
doi: 10.1016/j.cclet.2022.03.001
Abstract:
Exploring efficient materials for capturing radioactive iodine in nuclear waste is of great significance for the progress of nuclear energy as well as the protection of ecological environment. Covalent organic frameworks (COFs) have emerged as promising adsorbents because of their predesignable and functionalizable skeleton structures. However, it remains a grand challenge to achieve large scale preparation of COFs. In this work, we developed a mild and efficient microwave irradiation method instead of the traditional solvothermal method to prepare copper phthalocyanine-based covalent organic frameworks (CuPc-COFs) within only 15 min. The nitrogen-rich 1, 2, 4, 5-tetracarbonitrilebenzene (TCNB) was selected as the solely organic ligand to construct copper phthalocyanine-based 2D conjugated COFs. The resultant CuPc-COFs exhibited excellent iodine enrichment with 2.99 g/g for volatile iodine and 492.27 mg/g for iodine-cyclohexane solution, respectively, outperforming that of many porous materials. As indicated by spectroscopic analysis and DFT calculations, this impressive adsorption performance can be attributed to the charge transfer arising from nitrogen-rich phthalocyanine structures and electron-rich π-conjugated systems with iodine molecules. Moreover, the strong electrostatic interaction between Cu(II) on chelate centers and polyiodide anions (Ix-) also play an important role in the firmly trapping radioactive iodine. Therefore, this study provides a facile and intelligent approach to implement metal-based COFs for the remediation of toxic radioactive iodine.
Exploring efficient materials for capturing radioactive iodine in nuclear waste is of great significance for the progress of nuclear energy as well as the protection of ecological environment. Covalent organic frameworks (COFs) have emerged as promising adsorbents because of their predesignable and functionalizable skeleton structures. However, it remains a grand challenge to achieve large scale preparation of COFs. In this work, we developed a mild and efficient microwave irradiation method instead of the traditional solvothermal method to prepare copper phthalocyanine-based covalent organic frameworks (CuPc-COFs) within only 15 min. The nitrogen-rich 1, 2, 4, 5-tetracarbonitrilebenzene (TCNB) was selected as the solely organic ligand to construct copper phthalocyanine-based 2D conjugated COFs. The resultant CuPc-COFs exhibited excellent iodine enrichment with 2.99 g/g for volatile iodine and 492.27 mg/g for iodine-cyclohexane solution, respectively, outperforming that of many porous materials. As indicated by spectroscopic analysis and DFT calculations, this impressive adsorption performance can be attributed to the charge transfer arising from nitrogen-rich phthalocyanine structures and electron-rich π-conjugated systems with iodine molecules. Moreover, the strong electrostatic interaction between Cu(II) on chelate centers and polyiodide anions (Ix-) also play an important role in the firmly trapping radioactive iodine. Therefore, this study provides a facile and intelligent approach to implement metal-based COFs for the remediation of toxic radioactive iodine.
2022, 33(7): 3556-3560
doi: 10.1016/j.cclet.2022.03.053
Abstract:
Based on the outstanding application advantages of nitrogen-rich materials with regular porous frameworks in the capture of gaseous radioactive iodine, a series of covalent organic frameworks (COFs) with dual channels and abundant tertiary-amine active sites were constructed herein via a unique multi-nitrogen node design. The high density of up-to-six nitrogen adsorption sites in a single structural unit of the products effectively improved the adsorption capacities of the materials for iodine. Moreover, the adsorption affinity of the active sites can be further regulated by charge-induced effect of different electron-donating groups introduced into the COFs. Adsorption experiments combined with DFT theoretical calculations confirmed that the introduction of electron-donating groups can effectively increase the electron density around the active sites and enhance the binding energy between the materials and iodine, and thus improve the iodine adsorption capacity to 5.54 g/g. The construction strategy of multi-nitrogen node and charge-induced effect proposed in this study provides an important guidance for the study of the structure-activity relationship of functional materials and the design and preparation of high-performance iodine adsorption materials.
Based on the outstanding application advantages of nitrogen-rich materials with regular porous frameworks in the capture of gaseous radioactive iodine, a series of covalent organic frameworks (COFs) with dual channels and abundant tertiary-amine active sites were constructed herein via a unique multi-nitrogen node design. The high density of up-to-six nitrogen adsorption sites in a single structural unit of the products effectively improved the adsorption capacities of the materials for iodine. Moreover, the adsorption affinity of the active sites can be further regulated by charge-induced effect of different electron-donating groups introduced into the COFs. Adsorption experiments combined with DFT theoretical calculations confirmed that the introduction of electron-donating groups can effectively increase the electron density around the active sites and enhance the binding energy between the materials and iodine, and thus improve the iodine adsorption capacity to 5.54 g/g. The construction strategy of multi-nitrogen node and charge-induced effect proposed in this study provides an important guidance for the study of the structure-activity relationship of functional materials and the design and preparation of high-performance iodine adsorption materials.
2022, 33(7): 3561-3564
doi: 10.1016/j.cclet.2022.02.024
Abstract:
The treatment of anionic 99TcO4- in the waste tank with high alkalinity is still very challenging. In this work, a new temperature-responsive alkaline aqueous biphasic system (ABS) based on (tri-n-butyl)-n-tetradecyl phosphonium chloride (P44414Cl) was developed to remove radioactive 99TcO4-. The phase transition mechanism was studied by cloud point titration, small-angel X-ray scattering, dynamic light scattering, and molecular dynamic simulations. As the NaOH concentration or temperature increased, the P44414+ micelle could grow and aggregate. This micelle showed a particularly high affinity toward ReO4-/99TcO4- compared to other competing anions and could directly extract more than 98.6% of 99TcO4- from simulated radioactive tank waste supernatant. Furthermore, the loaded 99TcO4- could be easily stripped by using concentrated nitric acid rather than metal salt-based reductants. This work clearly demonstrates that the alkaline ABS is a promising separation system for solving the technetium problem in the alkaline waste tank.
The treatment of anionic 99TcO4- in the waste tank with high alkalinity is still very challenging. In this work, a new temperature-responsive alkaline aqueous biphasic system (ABS) based on (tri-n-butyl)-n-tetradecyl phosphonium chloride (P44414Cl) was developed to remove radioactive 99TcO4-. The phase transition mechanism was studied by cloud point titration, small-angel X-ray scattering, dynamic light scattering, and molecular dynamic simulations. As the NaOH concentration or temperature increased, the P44414+ micelle could grow and aggregate. This micelle showed a particularly high affinity toward ReO4-/99TcO4- compared to other competing anions and could directly extract more than 98.6% of 99TcO4- from simulated radioactive tank waste supernatant. Furthermore, the loaded 99TcO4- could be easily stripped by using concentrated nitric acid rather than metal salt-based reductants. This work clearly demonstrates that the alkaline ABS is a promising separation system for solving the technetium problem in the alkaline waste tank.
2022, 33(7): 3565-3569
doi: 10.1016/j.cclet.2022.02.074
Abstract:
Soft N-donor bis-triazin bipyridines derives (R-BTBP) are a type of very promising extratant for extraction and complexation with long-lived trivalent minor actinides over lanthanides from highly active liquid waste (HLW). In addition to minor actinides, R-BTBP also holds very strong complexation ability toward fission palladium. However, few studies have been focused on the separation and complexation with the fission product Pd(Ⅱ) by R-BTBP. Herein, the complexation behaviors of Pd(Ⅱ) with four typical R-BTBP ligands were systematically studied by single crystal X-ray diffraction, 1H NMR titration and theoretical calculation. The effects of R-BTBP initial conformation and nitrate anions on the complexation behaviors of R-BTBP with Pd(Ⅱ) were thoughtfully analyzed. Both the 1:1 and 2:1 binuclear complexes could be formed between Pd(Ⅱ) and R-BTBP with initial Ⅱ conformation in the presence of nitrate anions, while only one 1:1 type Pd(Ⅱ) complex could be formed for those with initial OO conformation. Without nitrate anion, only one 1:1 type complex was formed in solution. The structure of the 1:1 Pd(Ⅱ)/R-BTBP complex was firstly characterized by single crystal crystallography. DFT calculation results showed that a significant large rotational energy barrier (21.8~22.6 kcal/mol) must be overcome to form the Ⅱ type 2:1 Pd(Ⅱ) complex for those OO type R-BTBP ligands, however which would not prevent them from forming the 1:1 type complex.
Soft N-donor bis-triazin bipyridines derives (R-BTBP) are a type of very promising extratant for extraction and complexation with long-lived trivalent minor actinides over lanthanides from highly active liquid waste (HLW). In addition to minor actinides, R-BTBP also holds very strong complexation ability toward fission palladium. However, few studies have been focused on the separation and complexation with the fission product Pd(Ⅱ) by R-BTBP. Herein, the complexation behaviors of Pd(Ⅱ) with four typical R-BTBP ligands were systematically studied by single crystal X-ray diffraction, 1H NMR titration and theoretical calculation. The effects of R-BTBP initial conformation and nitrate anions on the complexation behaviors of R-BTBP with Pd(Ⅱ) were thoughtfully analyzed. Both the 1:1 and 2:1 binuclear complexes could be formed between Pd(Ⅱ) and R-BTBP with initial Ⅱ conformation in the presence of nitrate anions, while only one 1:1 type Pd(Ⅱ) complex could be formed for those with initial OO conformation. Without nitrate anion, only one 1:1 type complex was formed in solution. The structure of the 1:1 Pd(Ⅱ)/R-BTBP complex was firstly characterized by single crystal crystallography. DFT calculation results showed that a significant large rotational energy barrier (21.8~22.6 kcal/mol) must be overcome to form the Ⅱ type 2:1 Pd(Ⅱ) complex for those OO type R-BTBP ligands, however which would not prevent them from forming the 1:1 type complex.
2022, 33(7): 3570-3572
doi: 10.1016/j.cclet.2022.03.052
Abstract:
The hunt for agents that are suitable for actinide decorporation to reduce the whole-body load of actinide in accidental internal exposure is the ever-lasting goal in radiation protection and medical treatment in nuclear emergency. All current decorporation agents can be categorized as two groups, one is the molecular ligands, and the other is the nanoparticles decorated with molecular ligands. Here in this work, functional nanodiamonds (fNDs) with ssDNA (the endogenous biomacromolecule rich in phosphate groups) loaded on the NDs is reported, which poses good uranyl adsorption selectivity, high cellular uptake, fast excretion, and effective decorporation of uranyl from rat renal proximal tubular epithelial cells (NRK-52E). All those results corroborate that fNDs can potentially serve as a brand new family of chelators for actinide decorporation.
The hunt for agents that are suitable for actinide decorporation to reduce the whole-body load of actinide in accidental internal exposure is the ever-lasting goal in radiation protection and medical treatment in nuclear emergency. All current decorporation agents can be categorized as two groups, one is the molecular ligands, and the other is the nanoparticles decorated with molecular ligands. Here in this work, functional nanodiamonds (fNDs) with ssDNA (the endogenous biomacromolecule rich in phosphate groups) loaded on the NDs is reported, which poses good uranyl adsorption selectivity, high cellular uptake, fast excretion, and effective decorporation of uranyl from rat renal proximal tubular epithelial cells (NRK-52E). All those results corroborate that fNDs can potentially serve as a brand new family of chelators for actinide decorporation.
2022, 33(7): 3573-3576
doi: 10.1016/j.cclet.2022.01.050
Abstract:
Photocatalytic removal of uranium has attracted much attention in nuclear wastewater treatment and it is highly needed to develop functional photocatalyst with excellent removal performance. In this work, seven kinds of carbon dots/carbon nitride (CDs/CN) composites were synthesized and SerCDs/CN with the best photo-assisted uranium removal performance was screened out. It was found that the introduction of CDs could bring in higher photocurrent density, lower interfacial charge transfer impedance and narrower band gap, resulting in a much-improved removal performance. SerCDs/CN had shown a removal capacity as high as 1690 mg/g and the reaction could be operated under air atmosphere which is promising in real application.
Photocatalytic removal of uranium has attracted much attention in nuclear wastewater treatment and it is highly needed to develop functional photocatalyst with excellent removal performance. In this work, seven kinds of carbon dots/carbon nitride (CDs/CN) composites were synthesized and SerCDs/CN with the best photo-assisted uranium removal performance was screened out. It was found that the introduction of CDs could bring in higher photocurrent density, lower interfacial charge transfer impedance and narrower band gap, resulting in a much-improved removal performance. SerCDs/CN had shown a removal capacity as high as 1690 mg/g and the reaction could be operated under air atmosphere which is promising in real application.
2022, 33(7): 3577-3580
doi: 10.1016/j.cclet.2022.01.062
Abstract:
In this work, we proposed a new U(Ⅵ) removal strategy combining adsorption and photocatalytic reduction by the PMo12/UiO-66 heterojunctions. The PMo12 has been encapsulated in the cavities of UiO-66 by a one-step hydrothermal method, and the PMo12/UiO-66 exhibited high adsorption capacity and photocatalytic activity. The maximal theoretical sorption capacity of U(Ⅵ) on 15% PMo12/UiO-66 reached 225.36 mg/g and the photoreduction rate of 15% PMo12/UiO-66 is about thirty times as much as UiO-66. Under the light irradiation, the photogenerated electrons rapidly transport from UiO-66 to PMo12, and the photo-generated electrons could efficiently reduce the pre-enriched U(Ⅵ) to U(Ⅳ). This work provides new insights into remediation of the radioactive environment.
In this work, we proposed a new U(Ⅵ) removal strategy combining adsorption and photocatalytic reduction by the PMo12/UiO-66 heterojunctions. The PMo12 has been encapsulated in the cavities of UiO-66 by a one-step hydrothermal method, and the PMo12/UiO-66 exhibited high adsorption capacity and photocatalytic activity. The maximal theoretical sorption capacity of U(Ⅵ) on 15% PMo12/UiO-66 reached 225.36 mg/g and the photoreduction rate of 15% PMo12/UiO-66 is about thirty times as much as UiO-66. Under the light irradiation, the photogenerated electrons rapidly transport from UiO-66 to PMo12, and the photo-generated electrons could efficiently reduce the pre-enriched U(Ⅵ) to U(Ⅳ). This work provides new insights into remediation of the radioactive environment.
2022, 33(7): 3581-3584
doi: 10.1016/j.cclet.2022.03.043
Abstract:
Uranium removal from aqueous solutions using environmentally friendly photocatalytic technology is a novel approach for resource recovery. Herein, carbon nitride/activated carbon composite materials (CN/AC) were investigated for U(Ⅵ) reduction under visible light. An exceptional boost in photocatalytic activity was observed for CN/AC composites (up to 70 times over the conventional bulk g-C3N4). The strong interactive conjugated π-bond structure between g-C3N4 and AC accelerated the migration of carriers and then prolonged the electron lifetime. CN/AC composites exhibited excellent compatibility with different water substrates and were resilience to a wide range of pH changes and abundant competitive anions/cations. Quenching experiments and electron microscopy characterization indicated that U(Ⅵ) was reduced by photogenerated electrons and deposited on the edge of CN/AC composites. The low-cost, high-performance carbon-based composite material proposed in this work is a potential candidate for the efficient treatment of radioactive wastewater.
Uranium removal from aqueous solutions using environmentally friendly photocatalytic technology is a novel approach for resource recovery. Herein, carbon nitride/activated carbon composite materials (CN/AC) were investigated for U(Ⅵ) reduction under visible light. An exceptional boost in photocatalytic activity was observed for CN/AC composites (up to 70 times over the conventional bulk g-C3N4). The strong interactive conjugated π-bond structure between g-C3N4 and AC accelerated the migration of carriers and then prolonged the electron lifetime. CN/AC composites exhibited excellent compatibility with different water substrates and were resilience to a wide range of pH changes and abundant competitive anions/cations. Quenching experiments and electron microscopy characterization indicated that U(Ⅵ) was reduced by photogenerated electrons and deposited on the edge of CN/AC composites. The low-cost, high-performance carbon-based composite material proposed in this work is a potential candidate for the efficient treatment of radioactive wastewater.
