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2013 Volume 24 Issue 5
2013, 24(05): 351-358
Abstract:
Inspired by sophisticated biological structures and their physiological processes, supramolecular chemistry has been developed for understanding and mimicking the behaviors of natural species. Through spontaneous self-assembly of functional building blocks, we are able to control the structures and regulate the functions of resulting supramolecular assemblies. Up to now, numerous functional supramolecular assemblies have been constructed and successfully employed as molecular devices, machines and biological diagnostic platforms. This review will focus on molecular structures of functional molecular building blocks and their assembled superstructures for biological detection and delivery.
Inspired by sophisticated biological structures and their physiological processes, supramolecular chemistry has been developed for understanding and mimicking the behaviors of natural species. Through spontaneous self-assembly of functional building blocks, we are able to control the structures and regulate the functions of resulting supramolecular assemblies. Up to now, numerous functional supramolecular assemblies have been constructed and successfully employed as molecular devices, machines and biological diagnostic platforms. This review will focus on molecular structures of functional molecular building blocks and their assembled superstructures for biological detection and delivery.
2013, 24(05): 359-361
Abstract:
A simply synthesized 4-aminonaphthalimide derivative 1 expresses both polarity and viscosity sensitive fluorescence spectra, indicating its potential usage as an environmentally sensitive fluorescence probe. By comparing the fluorescence behavior of 1 with that of a known 4-aminonaphthalimide derivative 2, it was found that the substitution of the 4-amino group has profound influence on the environmentally sensitive fluorescence properties of 4-aminonaphthalimide.
A simply synthesized 4-aminonaphthalimide derivative 1 expresses both polarity and viscosity sensitive fluorescence spectra, indicating its potential usage as an environmentally sensitive fluorescence probe. By comparing the fluorescence behavior of 1 with that of a known 4-aminonaphthalimide derivative 2, it was found that the substitution of the 4-amino group has profound influence on the environmentally sensitive fluorescence properties of 4-aminonaphthalimide.
2013, 24(05): 362-366
Abstract:
Sym-bis(benzimidazole)-2,2'-ethylene cations act as a new axle template for threading cucurbit[6]uril derivatives on, forming [2]pseudorotaxane and [3]pseudorotaxane. These new complexes have been studied using 1H NMR, UV-vis absorption spectroscopy and X-ray analysis. Changes in the 1H NMR spectra indicate that the two types of pseudorotaxane can be formed by varying the host concentration. UV-vis absorption titration experiments at different pH values demonstrate that interesting pKa shifts of the bis-benzimidazole derivatives can be induced by the host-guest complexation. The associated constants were calculated to be 2.81×104 L/mol and 9.06×106 L/mol for the [2]pseudorotaxanes and [3]pseudorotaxanes, respectively. Furthermore, X-ray diffraction studies of the solid state structures provide unequivocal proof of the host concentration dependent pseudorotaxane, which is strongly in line with the evidences in solution.
Sym-bis(benzimidazole)-2,2'-ethylene cations act as a new axle template for threading cucurbit[6]uril derivatives on, forming [2]pseudorotaxane and [3]pseudorotaxane. These new complexes have been studied using 1H NMR, UV-vis absorption spectroscopy and X-ray analysis. Changes in the 1H NMR spectra indicate that the two types of pseudorotaxane can be formed by varying the host concentration. UV-vis absorption titration experiments at different pH values demonstrate that interesting pKa shifts of the bis-benzimidazole derivatives can be induced by the host-guest complexation. The associated constants were calculated to be 2.81×104 L/mol and 9.06×106 L/mol for the [2]pseudorotaxanes and [3]pseudorotaxanes, respectively. Furthermore, X-ray diffraction studies of the solid state structures provide unequivocal proof of the host concentration dependent pseudorotaxane, which is strongly in line with the evidences in solution.
2013, 24(05): 367-369
Abstract:
Several water-soluble calix[4]arenes were synthesized via radical addition reaction between thiols and alkenes under UV lamp irradiation (λ= 365 nm) in good yields. The structures of these compounds synthesized herein were fully confirmed by 1H NMR, ESI-MS and elemental analysis.
Several water-soluble calix[4]arenes were synthesized via radical addition reaction between thiols and alkenes under UV lamp irradiation (λ= 365 nm) in good yields. The structures of these compounds synthesized herein were fully confirmed by 1H NMR, ESI-MS and elemental analysis.
2013, 24(05): 370-372
Abstract:
The magnetic nanoparticles supported silica sulfuric acid was used as an efficient catalyst for the synthesis of pyrimido[4,5-b]quinolines and indeno fused pyrido[2,3-d]pyrimidines in water. The desired products were obtained in excellent yields. Fe3O4@SiO2-SO3H was readily recovered using an external magnet and could be reused several times without significant loss of reactivity.
The magnetic nanoparticles supported silica sulfuric acid was used as an efficient catalyst for the synthesis of pyrimido[4,5-b]quinolines and indeno fused pyrido[2,3-d]pyrimidines in water. The desired products were obtained in excellent yields. Fe3O4@SiO2-SO3H was readily recovered using an external magnet and could be reused several times without significant loss of reactivity.
2013, 24(05): 373-375
Abstract:
A novel photooxidative system for degrading toxic organic pollutants is reported. A new complex of Fe2L3(L = bis[2-hydroxybenzaldehyde]hydrazone) synthesized can efficiently activate hydrogen peroxide (H2O2) to oxidize and mineralize the target complexes rhodamine B (RhB) and methyl orange (MO) in aqueous media under ambient temperature and normal pressure and with visible light irradiation.
A novel photooxidative system for degrading toxic organic pollutants is reported. A new complex of Fe2L3(L = bis[2-hydroxybenzaldehyde]hydrazone) synthesized can efficiently activate hydrogen peroxide (H2O2) to oxidize and mineralize the target complexes rhodamine B (RhB) and methyl orange (MO) in aqueous media under ambient temperature and normal pressure and with visible light irradiation.
2013, 24(05): 376-378
Abstract:
A series of substituted 1,4-oxathiane-3-thione derivatives were synthesized via one-pot multicomponent reactions of nitromethane, carbon disulfide and oxiranes in the presence of Et3N in water as the solvent under microwave irradiation. Particularly valuable features of this method include high yields of products, broad substrate scope, short reaction time and straightforward procedure.
A series of substituted 1,4-oxathiane-3-thione derivatives were synthesized via one-pot multicomponent reactions of nitromethane, carbon disulfide and oxiranes in the presence of Et3N in water as the solvent under microwave irradiation. Particularly valuable features of this method include high yields of products, broad substrate scope, short reaction time and straightforward procedure.
2013, 24(05): 379-382
Abstract:
In this paper, we report a total synthesis of a naturally occurring pyrrolo[2,3-d]pyrimidine nucleoside, mycalisine A. Our synthetic strategy uses D-xylose as the startingmaterial and Vorbrüggen glycosylation as the key step. Mycalisine A was synthesized in 11 steps with a 15% overall yield.
In this paper, we report a total synthesis of a naturally occurring pyrrolo[2,3-d]pyrimidine nucleoside, mycalisine A. Our synthetic strategy uses D-xylose as the startingmaterial and Vorbrüggen glycosylation as the key step. Mycalisine A was synthesized in 11 steps with a 15% overall yield.
2013, 24(05): 383-385
Abstract:
A new spongy adsorbent (PU-DTC) was prepared with a polyurethane (PU) adsorbent for removal of EDTA-Cu(Ⅱ) and EDTA-Ni(Ⅱ) from water. This new spongy adsorbent was characterized by using SEM and 13C NMR and FT-IR spectroscopy. Adsorption kinetic curve indicated that this new spongy adsorbent could quickly remove EDTA-Cu(Ⅱ) and EDTA-Ni(Ⅱ) from water, and adsorption isotherm also indicated that PU-DTC had high equilibrium adsorption capacity for EDTA-Cu(Ⅱ) and EDTA-Ni(Ⅱ).
A new spongy adsorbent (PU-DTC) was prepared with a polyurethane (PU) adsorbent for removal of EDTA-Cu(Ⅱ) and EDTA-Ni(Ⅱ) from water. This new spongy adsorbent was characterized by using SEM and 13C NMR and FT-IR spectroscopy. Adsorption kinetic curve indicated that this new spongy adsorbent could quickly remove EDTA-Cu(Ⅱ) and EDTA-Ni(Ⅱ) from water, and adsorption isotherm also indicated that PU-DTC had high equilibrium adsorption capacity for EDTA-Cu(Ⅱ) and EDTA-Ni(Ⅱ).
2013, 24(05): 386-388
Abstract:
A series of novel diaryl ureas containing 4-[(2-amino-6-trifluromethyl)pyrimidine-4-yl]piperazine-1-yl group were synthesized and evaluated for their cytotoxic activities in a panel of human cancer cell lines. Compared with the reference drug Sorafenib, some compounds showed more potent and a broader spectrum of anti-cancer activities. Among them, compound 2p demonstrated significant inhibitory activities against MDA-MB-231, HT-29 and MCF-7 cell lines with IC50 values of 0.016, 0.63, 0.001 mmol/L, respectively.
A series of novel diaryl ureas containing 4-[(2-amino-6-trifluromethyl)pyrimidine-4-yl]piperazine-1-yl group were synthesized and evaluated for their cytotoxic activities in a panel of human cancer cell lines. Compared with the reference drug Sorafenib, some compounds showed more potent and a broader spectrum of anti-cancer activities. Among them, compound 2p demonstrated significant inhibitory activities against MDA-MB-231, HT-29 and MCF-7 cell lines with IC50 values of 0.016, 0.63, 0.001 mmol/L, respectively.
2013, 24(05): 389-391
Abstract:
A catalytic multi-component reaction involving aromatic amine, aromatic aldehydes, mercapto acid as substrates and Bi(SCH2COOH)3 as catalyst under solvent free conditions, afforded thiazolidin-4-one in good yields. The efficiency of the catalyst was proved with a variety of substrates, ranging from electrondeficient to electron-rich aldehydes.
A catalytic multi-component reaction involving aromatic amine, aromatic aldehydes, mercapto acid as substrates and Bi(SCH2COOH)3 as catalyst under solvent free conditions, afforded thiazolidin-4-one in good yields. The efficiency of the catalyst was proved with a variety of substrates, ranging from electrondeficient to electron-rich aldehydes.
2013, 24(05): 392-396
Abstract:
In order to expand the application of poly(p-dioxanone) or PPDO in biomedical area, a series of novel copolymers were synthesized successfully by one-step, melted copolymerization of p-dioxanone (PDO) and L-phenylalanine N-carboxyanhydride (L-Phe-NCA) monomers. With the in-feedmolar ratio of L-Phe-NCA/PDO equal to 1/20, the conversions of the two kinds of monomers were calculated from 1H NMR. The average molecular weight and polydispersity of the copolymer increase with the increasing reaction time and catalyst concentration. However, the conversions of the two kinds of monomers did not change with the reaction conditions. A three-step mechanism is presented and proved by high resolution 1H NMR and IR spectrums.
In order to expand the application of poly(p-dioxanone) or PPDO in biomedical area, a series of novel copolymers were synthesized successfully by one-step, melted copolymerization of p-dioxanone (PDO) and L-phenylalanine N-carboxyanhydride (L-Phe-NCA) monomers. With the in-feedmolar ratio of L-Phe-NCA/PDO equal to 1/20, the conversions of the two kinds of monomers were calculated from 1H NMR. The average molecular weight and polydispersity of the copolymer increase with the increasing reaction time and catalyst concentration. However, the conversions of the two kinds of monomers did not change with the reaction conditions. A three-step mechanism is presented and proved by high resolution 1H NMR and IR spectrums.
2013, 24(05): 397-400
Abstract:
Based on an analysis of the 1H NMR, FT-IR, UV-vis spectra, a chiral trimeric phenylene vinylene derivative (ChTPV) synthesized by a Wittig reaction was determined to have a trans-cis configuration, and it could be isomerized to the trans-trans isomer when treated with iodine. The melting point of ChTPV with a trans-trans configuration increased by 162.1℃ compared to the trans-cis isomer, and the ChTPV with trans-trans configuration exhibited the typical liquid-crystalline texture of the smectic A in the heating process. The results indicated that the molecular configuration can influence the formation of the liquid crystalline phase of ChTPV.
Based on an analysis of the 1H NMR, FT-IR, UV-vis spectra, a chiral trimeric phenylene vinylene derivative (ChTPV) synthesized by a Wittig reaction was determined to have a trans-cis configuration, and it could be isomerized to the trans-trans isomer when treated with iodine. The melting point of ChTPV with a trans-trans configuration increased by 162.1℃ compared to the trans-cis isomer, and the ChTPV with trans-trans configuration exhibited the typical liquid-crystalline texture of the smectic A in the heating process. The results indicated that the molecular configuration can influence the formation of the liquid crystalline phase of ChTPV.
2013, 24(05): 401-403
Abstract:
An efficient diketene ring-opening synthesis of polyhydroquinoline derivatives using SBA-15 sulfonic acid modified mesoporous substrates a green and reusable catalyst in a single-pot four-component coupling reaction of diketene, alcohol, enamine, and aldehydes is reported. Dihydropyridine derivatives based on neat adduct of diketene, alcohols and aldehydes using SBA-15/SO3H nanoreactor as catalyst via a four-component reactions are also synthesized. The advantages of the present method include the use of a small amount catalyst, simple procedure with an easy filterable work-up, waste-free, green and direct synthetic method with an excellent yield of products with efficient use of catalyst and a short reaction time.
An efficient diketene ring-opening synthesis of polyhydroquinoline derivatives using SBA-15 sulfonic acid modified mesoporous substrates a green and reusable catalyst in a single-pot four-component coupling reaction of diketene, alcohol, enamine, and aldehydes is reported. Dihydropyridine derivatives based on neat adduct of diketene, alcohols and aldehydes using SBA-15/SO3H nanoreactor as catalyst via a four-component reactions are also synthesized. The advantages of the present method include the use of a small amount catalyst, simple procedure with an easy filterable work-up, waste-free, green and direct synthetic method with an excellent yield of products with efficient use of catalyst and a short reaction time.
2013, 24(05): 404-406
Abstract:
A facile and highly efficient protocol for the synthesis of 1,8-dioxo-octahydroxanthene derivatives was achieved through cascade Knoevenagel-Michael condensations and cyclo-dehydration reaction utilizing tetrachlorosilane (TCS) as catalyst under mild conditions. Reaction of the titled compounds with TCS-NaN3 to give novel functionalized pyrano[3,2-c]tetrazolo[1,5-a]azepine derivatives is also described.
A facile and highly efficient protocol for the synthesis of 1,8-dioxo-octahydroxanthene derivatives was achieved through cascade Knoevenagel-Michael condensations and cyclo-dehydration reaction utilizing tetrachlorosilane (TCS) as catalyst under mild conditions. Reaction of the titled compounds with TCS-NaN3 to give novel functionalized pyrano[3,2-c]tetrazolo[1,5-a]azepine derivatives is also described.
2013, 24(05): 407-410
Abstract:
Microwave-assisted tandem reaction of (Z)-arylvinyl bromides involving an elimination and homocoupling in the presence of DBU and CuI in DMF affords a variety of symmetrical 1,3-diynes in good to excellent yields. This tandem process, eliminating the need of volatile and savory terminal alkynes, provides an alternative to the conventional homocoupling methods for the synthesis of symmetrical 1,3-diynes.
Microwave-assisted tandem reaction of (Z)-arylvinyl bromides involving an elimination and homocoupling in the presence of DBU and CuI in DMF affords a variety of symmetrical 1,3-diynes in good to excellent yields. This tandem process, eliminating the need of volatile and savory terminal alkynes, provides an alternative to the conventional homocoupling methods for the synthesis of symmetrical 1,3-diynes.
2013, 24(05): 411-414
Abstract:
Saccharose was applied as an efficient and homogenous catalyst for a one-pot, three-component Mannich reaction for the formation of β-aminoketones from aromatic aldehydes, anilines, and acetophenone at ambient temperature in excellent yields. This protocol has the following advantages: mild conditions, high yields, clean reaction profiles, operational simplicity, and environmentally benign and simple work-up procedures.
Saccharose was applied as an efficient and homogenous catalyst for a one-pot, three-component Mannich reaction for the formation of β-aminoketones from aromatic aldehydes, anilines, and acetophenone at ambient temperature in excellent yields. This protocol has the following advantages: mild conditions, high yields, clean reaction profiles, operational simplicity, and environmentally benign and simple work-up procedures.
2013, 24(05): 415-418
Abstract:
Novel furoxan-based nitric oxide-releasing derivatives 6a-p of hydroxylcinnamic acids were synthesized by coupling the carboxyl group of hydroxylcinnamic acids with furoxan through various alkylol amines. Compounds 6a, e-i and m-p displayed more potent anti-tumor activities superior to control 5-fluorouracil (5-FU) in most cancer cells tested. Furthermore, 6f could selectively inhibit tumor cells, but not non-tumor cell proliferation. This inhibition was attributed to high levels of NO released in cancer cells and potentially synergistic effect of NO donor moieties and the bioactivity of hydroxylcinnamic acids.
Novel furoxan-based nitric oxide-releasing derivatives 6a-p of hydroxylcinnamic acids were synthesized by coupling the carboxyl group of hydroxylcinnamic acids with furoxan through various alkylol amines. Compounds 6a, e-i and m-p displayed more potent anti-tumor activities superior to control 5-fluorouracil (5-FU) in most cancer cells tested. Furthermore, 6f could selectively inhibit tumor cells, but not non-tumor cell proliferation. This inhibition was attributed to high levels of NO released in cancer cells and potentially synergistic effect of NO donor moieties and the bioactivity of hydroxylcinnamic acids.
2013, 24(05): 419-421
Abstract:
In this work, a new type of hydrophobic stationary phase that provide electrostatic interactions with analytes was developed by bonding β-phenylethylamine as a functional ligand to silica. This stationary phase can separate proteins with similar hydrophobicity that traditional hydrophobic resins cannot. Hen egg white was separated to examine the selectivity. The results show that the introduced electrostatic interactions are an important factor for the resolution enhancement and the new resin could have important applications in separation and purification of biological macromolecules.
In this work, a new type of hydrophobic stationary phase that provide electrostatic interactions with analytes was developed by bonding β-phenylethylamine as a functional ligand to silica. This stationary phase can separate proteins with similar hydrophobicity that traditional hydrophobic resins cannot. Hen egg white was separated to examine the selectivity. The results show that the introduced electrostatic interactions are an important factor for the resolution enhancement and the new resin could have important applications in separation and purification of biological macromolecules.
2013, 24(05): 422-424
Abstract:
An efficient protocol was developed for the synthesis of 3-aminoalkylated indoles using 3-chlorophenylboronic acid as a catalyst under ambient temperature conditions. The three-component reaction of indoles, aromatic aldehydes and N-methyl aniline offered corresponding 3-aminoalkylated indoles in excellent yields. This protocol presents some remarkable features such as mild reaction conditions, simple workup procedure and excellent yields.
An efficient protocol was developed for the synthesis of 3-aminoalkylated indoles using 3-chlorophenylboronic acid as a catalyst under ambient temperature conditions. The three-component reaction of indoles, aromatic aldehydes and N-methyl aniline offered corresponding 3-aminoalkylated indoles in excellent yields. This protocol presents some remarkable features such as mild reaction conditions, simple workup procedure and excellent yields.
2013, 24(05): 425-428
Abstract:
In this study, N,N'-di-(2-methylphenyl)malonamide was synthesized and reacted with polyphosphoric acid to afford 8-methyl-4-hydroxyl-2-quinolone. Eight novel azo disperse dyes were then synthesized by linking diazotized p-substituted aniline derivatives with 8-methyl-4-hydroxyl-2-quinolone. The solvatochromism of these azo dyes in various solvents was evaluated. All the compounds were then evaluated for their antibacterial activity against four bacteria, namely, Bacillus subtilis, Micrococcus luteus, Salmonella enterica, and Pseudomonas aeruginosa. The results showed that some of these compounds have high levels of antibacterial activity.
In this study, N,N'-di-(2-methylphenyl)malonamide was synthesized and reacted with polyphosphoric acid to afford 8-methyl-4-hydroxyl-2-quinolone. Eight novel azo disperse dyes were then synthesized by linking diazotized p-substituted aniline derivatives with 8-methyl-4-hydroxyl-2-quinolone. The solvatochromism of these azo dyes in various solvents was evaluated. All the compounds were then evaluated for their antibacterial activity against four bacteria, namely, Bacillus subtilis, Micrococcus luteus, Salmonella enterica, and Pseudomonas aeruginosa. The results showed that some of these compounds have high levels of antibacterial activity.
2013, 24(05): 429-432
Abstract:
Seven cyclohexane-bearing C-glucoside derivatives (7, 9, 12, 13 and 17-19) were designed and synthesized as SGLT2 inhibitors starting from a potent SGLT2 inhibitor we discovered in earlier work, (1S)-1-deoxy-1-[4-methoxy-3-(trans-n-propylcyclohexyl)methylphenyl]-D-glucose (1). The in vitro and in vivo biological activities were evaluated by hSGLT2/hSGLT1 inhibition and urinary glucose excretion (UGE), respectively. Among the synthesized compounds 12, the 6-deoxy derivative of 1 was the most active and selective SGLT2 inhibitor (IC50 = 1.4 nmol/L against hSGLT2; selectivity = 1576). Compound 12 was a potent SGLT2 inhibitor, which could induce more urinary glucose than 1 and dapagliflozin in UGE.
Seven cyclohexane-bearing C-glucoside derivatives (7, 9, 12, 13 and 17-19) were designed and synthesized as SGLT2 inhibitors starting from a potent SGLT2 inhibitor we discovered in earlier work, (1S)-1-deoxy-1-[4-methoxy-3-(trans-n-propylcyclohexyl)methylphenyl]-D-glucose (1). The in vitro and in vivo biological activities were evaluated by hSGLT2/hSGLT1 inhibition and urinary glucose excretion (UGE), respectively. Among the synthesized compounds 12, the 6-deoxy derivative of 1 was the most active and selective SGLT2 inhibitor (IC50 = 1.4 nmol/L against hSGLT2; selectivity = 1576). Compound 12 was a potent SGLT2 inhibitor, which could induce more urinary glucose than 1 and dapagliflozin in UGE.
2013, 24(05): 433-436
Abstract:
The system, Pd(OAc)2/imidazolium salts (L2), was found as an efficient catalyst in the Heck coupling reaction of olefins with aryl halides and Suzuki reactions of various aryl halides with aryl boronic acids under aerobic condition. This catalytic system demonstrates great tolerance to a wide range of groups on all substrates of aryl halides, alkenes and aryl boronic acids.
The system, Pd(OAc)2/imidazolium salts (L2), was found as an efficient catalyst in the Heck coupling reaction of olefins with aryl halides and Suzuki reactions of various aryl halides with aryl boronic acids under aerobic condition. This catalytic system demonstrates great tolerance to a wide range of groups on all substrates of aryl halides, alkenes and aryl boronic acids.
