A chemical kinetic model containing 46 species and 167 reactions was developed for the auto-ignition and combustion of n-decane. On the basis of a significant reduction of the mechanism proposed by Peters (118 species and 527 reactions)—where the reduction was achieved using reaction path analysis and a sensitivity analysis—the newly developed mechanism was obtained by correcting and improving some elementary reactions important for auto-ignition at lower temperatures and laminar flame speeds. When compared with experimental results, not only did the mechanism contain fewer species and reactions than other models, it could also predict the auto-ignition delay time at lower and higher temperatures and laminar flame speeds more precisely. The development of this model represents a significant step toward a global model that could be coupled with computational fluid dynamics.

Solidification processes of liquid Fe with embedded homogeneous solid nanoparticle whose radius ranges from 0.4 to 1.8 nm have been studied by molecular dynamics simulation adopting the Sutton-Chen potential. It was found that the particles whose radii exceed 0.82 nm can obviously decrease the critical undercooling (ΔT^*) and induce solidification. The microstructural evolution during the solidification process is traced through the atom definition with cluster-type index method (CTIM-2). Results revealed that when the embedded particle induced solidification, the growth process of nucleus would proceed as a cross-nucleation between hcp and fcc structures, a little similar to the eutectic crystallization process. Moreover, the heredity effect attributed by embedded solid nanoparticle is clearly observed during the microstructural evolution.

First-principles calculations were applied to design and study the electron transport behavior of a biomolecular sensor with graphene-based electrodes. It is shown that the designed biosensor is capable of distinguishing different nucleotide molecules such as cytosine, methylcytosine, and hydroxymethylcytosine. The current was seen to change by nearly one order of magnitude, while molecules passed through the device individually. The resolution capacity of the present device was primarily determined by the interactions and specific configurations of two adjacent single-stranded desoxyribonucleic acid (DNA) molecules and their specific configurations. This graphene-based biosensor was proved to be effective and efficient in detecting and distinguishing different DNA molecules, which provides a new potential method to pinpoint exactly varietal base molecules in DNAchains for the genetic information.

Taking dye D5 molecules as the prototype, different types and different elemental quantities of conjugate π bridge was used to design D-π-A organic molecules. Density functional theory (DFT) and timedependent density functional theory (TDDFT) were adopted to simulate the geometric structures, molecular orbital energy levels, and UV-Vis absorption spectra of the molecules, with the aim of finding conjugate π bridge in the sensitizer molecules for dye-sensitized solar cells (DSSCs). The absorption spectra of the molecules using “methenyl chains”,“furan rings” or “thiophene rings”,“methenyl chains and furan rings”, or “methenyl chains and thiophene rings” as conjugate π bridge showed a gradually increasing red-shifting trend. With increases in the number of conjugate π bridge elements, the absorption spectrum showed an intense red-shift, which weakened gradually; under the same conditions, the lowest unoccupied molecular orbital (LUMO) energy level of the molecules gradually decreased, and the highest occupied molecular orbital (HOMO) energy level gradually increased. The HOMO energy levels of the molecules with three“methenyl chain and furan ring”or“methenyl chain and thiophene ring”elements as conjugate π bridge were higher than the energy level of the redox electrolyte; in polar solutions, the HOMO energy levels of the molecules adopting two “methenyl chain and furan ring” or “methenyl chain and thiophene ring” elements as conjugate π bridge were higher than the energy level of the redox electrolyte. The absorption spectra of the organic sensitizer molecules with several “methenyl chain and furan ring” or “methenyl chain and thiophene ring” elements as conjugate π bridge showed an intense red-shift. These results showed that for DSSCs sensitizer molecules, it is not necessary to have many conjugate π bridge elements; one to two elements is typically enough.

The interaction of methanethiol (CH₃SH) molecules with the Cu(111) surface was investigated using a first-principles method based on density functional theory, and a slab model. A series of possible adsorption configurations constructed using S atoms on different sites with different tilt angles were studied. It was found for the first time that the non-dissociative molecular adsorption of CH₃SH on the Cu(111) surface with the S atom sitting on the top site belongs to the weak chemisorption, and the adsorption energy is 0.39 eV. After the dissociation of the S―H bond, the S atom is located at the bridge site, with a small shift toward the hollow site. The dissociative adsorption structure is thermodynamically more stable than the intact one, and the adsorption energy is 0.75-0.77 eV. Two reaction pathways have been studied for the transition from non-dissociative adsorption to dissociative adsorption, and the activation energy barrier along the minimum energy path is 0.57 eV. The results of the calculations indicated that the released H atom prefers to form a bond with the copper surface, rather than desorbing in the H₂ molecular form. Comparing the local density of states of S atoms in the single CH₃SH, CH₃SH/Cu(111), and CH₃S/Cu(111) structures, we found that the bonding between the S atoms and the substrate is much stronger in the dissociated adsorption states.

Using density functional theory, the adsorption behaviors of HF at α-AlF₃(0001) surfaces with different coverages of 3F, 2F, 1F, and Al terminations were studied systematically. The electronic interactions between HF and the α-AlF₃(0001) surfaces were also analyzed. Our results indicated that physisorption occurs when HF adsorbs at the 3F-terminated surface. Strong chemisorption occurs, and Al-F and FHF structures form when HF adsorbs at surfaces with 2F and 1F terminations. Under these conditions, the HF molecule is activated, and might take part in the subsequent fluorination reactions. Dissociated adsorption occurs, and Al-F and Al-H bonds form when HF is adsorbed on the Al-terminated surface. The unsaturated coordination numbers for surface Al with 3F, 2F, 1F, and Al-terminated surfaces are 0, 1, 2, and 3, respectively. The coordination number of the AlF2 surface is saturated when one HF molecule adsorbs; then, only physical adsorption occurs for any subsequently adsorbed HF molecules. However, it can still chemisorb at the 1F and Al-terminated surfaces. It is therefore reasonable to deduce that the higher the unsaturated coordination number of the surface, the higher the amount of activated HF, and possibly the higher the catalytic activities in the fluorination reactions. Charge density difference and density of states indicated that weak interactions occur between the HF and the 3F-terminated surface, while strong interactions occur between the HF and the 2F, 1F, Al-terminated surfaces.

The reaction mechanisms of ethylene hydrogenation catalyzed by Au(I) complexes AuX (X=F, Cl, Br, I) and AuPR₃⁺ (R = F, Cl, Br, I, H, Me, Ph) were investigated using density functional theory at the B3LYP level. The calculated results indicated that Au(I) complexes were effective catalysts in the hydrogenation of ethylene. AuPR₃⁺ showed higher catalytic activity than AuX and the effect of changing the electron donating or withdrawing ability of the ligand on catalytic activity was large. Natural bond orbital analysis indicated that the interactions between the Au(I) complex and H₂/C₂H₄ not only weakened the H― H/C＝C bond strength, but also decreased the energy of the σ_H―H^*、π_C＝C^* orbital level. As a result, the energy differences of π_C＝C-σ_H―H^*/σ_H―H-π_C＝C^* decreased, and ethylene hydrogenation was facilitated. A linear correlation was observed between the activation energies and π_C＝C-σ_H―H^*/σ_H―H-π_C＝C^*. The more an Au(I) complex affected the σ_H―H^*/π_C＝C^* orbital levels, the higher its catalytic activity.

Nano-WO₃-modified carbon nanotube supported Pt nanoparticles (Pt-WO₃/CNT) with uniform dimensions were prepared by adsorption and decomposition of ammonium meta-tungstate (AMT) on the surface of CNTs pretreated with HNO₃, and H₂PtCl₆ as the Pt precursor. The samples were characterized by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). The Pt nanoparticles had a face-centered cubic crystal structure, and were well dispersed on the external walls and ports of the WO₃/ CNTs. The electrocatalytic activity of the samples towards the oxidation of methanol was investigated using cyclic voltammetry and chronoamperometry. The results indicated that the Pt-WO₃/CNT catalysts exhibited higher electrocatalytic activity, better anti-poisoning ability, and od stability during methanol oxidation compared with Pt/CNTs used for acid oxidation treatments.

Transition metal oxides, especially manganese monoxide (MnO), are being intensively studied as candidate anode materials for next generation lithium-ion batteries in high efficiency energy storage applications such as portable electronics, electric vehicles, and stationary electricity storage. In this paper, the MnC₂O₄·2H₂O precursor, prepared fromKMnO4 and ascorbic acid, was heat-treated to synthesize nano MnO by a solid-state reaction approach. X-ray diffraction (XRD) showed that the so-obtained MnO had a rock-salt structure with od crystallinity, and scanning electron microscopy (SEM) indicated that the primary particle size was about 50-100 nm, while the secondary particle size was about 400-600 nm. As an active material for lithium-ion batteries, the nano MnO material delivered a reversible capacity of 679.7 mAh·g^-1 with an initial columbic efficiency of 68.9% at a current density of 46.3 mA·g^-1. The specific discharge capacity slightly decreased from 584.5 to 581.5 mAh·g^-1 with a retention of 99.5% after 50 cycles at a current density of 141.1 mA·g^-1. Moreover, the material was able to release a capacity of 290 mAh·g^-1 at current densities as high as 494.7 mA·g^-1 (corresponding to ~2C), which demonstrates reasonable rate performance and moderately fast charge/discharge capabilities. All of the above characteristics make nano MnO promising anode materials for developing high-capacity, long-life, low-cost, and environmentally-friendly lithium-ion batteries.

Electrochemical capacitors (ECs) are attractive energy storage systems for applications with high power requirements. Porous carbons are the materials that are most frequently used for the electrodes in ECs, because of their large surface area, high conductivity, chemical inertness, low cost, and tunable pore structure. Here, novel hierarchically micro-meso-structured porous carbons were synthesized, using microporous rod-like hydroxyapatite nanoparticles as a template and sucrose as a carbon source. The morphology and surface properties of the as-prepared porous carbons were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller surface analysis. The electrochemical capacitive performances were evaluated in an aqueous solution of 1 mol·L^-1 H₂SO₄ using cyclic voltammetry, electrochemical impedance spectroscopy, and constant current charge/discharge tests. The resultant carbons showed a high surface area of more than 719.7 m²·g^-1, large pore volumes of more than 1.32 cm³·g^-1, and a disordered pore structure composed of randomly distributed micropores, collapsed mesopores, and interweaving rod-like mesopores that took the shape of the template. As the carbonization temperature was increased, the density of micropores and rod-like mesopores decreased, and a tri-modal pore size distribution appeared for the carbon sample carbonized at 900 ° C. Because of these unique characteristics, the electrode material originated from the porous carbon carbonized at 900℃ exhibited od electrochemical capacitive performances.

We used electrochemical exfoliation to construct graphite nanosheet (GNS) arrays, in which the varying number of nanosheet layers were parallel to each other and perpendicular to the carbon substrate. Hydrous ruthenium oxide (RuO₂·xH₂O) was then loaded directly on the surface of nanosheets using cathodic reduction electrodeposition, resulting in the formation of RuO₂·xH₂O/GNS composite array electrodes. Electrochemical measurements showed that the composite array electrodes exhibited excellent capacitive behaviors, and achieved specific capacitance values as high as 4226 F·m^-2 in the potential window up to 0.9 V, with a scan rate of 5 mV·s^-1 in 0.5 mol·L^-1 H₂SO₄ solution. The RuO₂·xH₂O/GNS composite array electrodes showed od cycling abilities, and maintained 94.18% of their maximum performance after 20000 cycles.

Powders of La_0.90Sr_0.10Al_0.97Mg_0.03O_3-δ (LSAM) were synthesized by the glycine-nitrate process, and then sintered at 1500 °C for 5 h. Impedance spectroscopy at 900 °C in air revealed that the conductivity of LSAM was 1.11×10^-2 S·cm^-1. The chemical compatibility of LSAM with anode materials NiO-Ce_0.9Gd_0.1O_1.95 (Ni-GDC), Sr_0.88Y_0.08TiO₃ (SYT) and La_0.75Sr_0.25Cr_0.5Mn_0.5O₃ (LSCM) was characterized by X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy and AC impedance spectroscopy. The results indicated that SYT and LSCM had poor chemical compatibility with LSAM because Sr²⁺, Ti⁴⁺, Mn³⁺, and Cr³⁺ diffused readily into the LSAM lattice. The interdiffusion of cations between LSAM and Ni- GDC at 1300 °C was limited, implying excellent chemical compatibility. The electrochemical performance of symmetrical cells of the anode materials was measured under hydrogen atmosphere. The area-specific polarization resistance of Ni-GDC was 5.12 Ω·cm² at 800 ° C. An open-circuit voltage of 0.925 V and a power density of 19.5 mW·cm^-2 were obtained at 800 °C for a 550 μm thick LSAM electrolyte-supported single cell (Ni-GDC/GDC/LSAM/GDC/La0.75Sr0.25FeO3).

In this work, the stability and reversible aggregation properties of zwitterion-modified Au nanoparticles (Au NPs) were studied under acidic and alkaline conditions. The UV-Vis spectra of the Au colloids were measured under different conditions, and the stability and reversible aggregation properties of the Au colloids were revealed through the spectral changes. The results showed that the modification with zwitterionic ligands largely improved the stability of the Au NPs under both acidic and alkaline conditions. Under strongly acidic conditions, the modified Au NP colloids lost stability and aggregated, but the aggregated colloids could be redispersed once the pH of the colloids was returned to an appropriate value. By exploiting their pH-dependent reversible aggregation properties, dilute Au NP colloids were concentrated to give concentrated Au NP colloids or solid Au NP aggregates; these systems could be preserved for long periods of time, and if needed, could be recovered to give well-dispersed dilute dispersions simply by adding water.

The photosensitive amphiphilic copolymer poly-(styrene-alt-maleic anhydride)-co-poly (7-(4-vinylbenzyloxyl)-4-methylcoumarin-alt-maleic anhydride) (PSMVM) micelles with various degrees of swelling were used as polymeric micellar emulsifiers to stabilize toluene-in-water emulsions. This paper focuses on the influence of the degree of photo-crosslinking on the micellar structure and the emulsification performance of the micelles. The research results indicated that the degree of photo-crosslinking, the degree of swelling, and the charge on the micelles played an important role in the micellar structure and the emulsifying performance of the micelles.

Styrene monomer (St) and dimethylaminoethyl methacrylate monomer (DMAEMA) were used to synthesize the amphiphilic random copolymer P(St-co-DM) via free radical copolymerization. The polymer structure was characterized by Fourier transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance (¹H NMR) spectroscopy, gel permeation in chromatography (GPC), and differential scanning calorimetry (DSC). We investigated the influence on the microstructure of the P(St-co-DM) nanoscale micelles by self-assembly in three common solvents (co-solvent), and also investigated the effect of micelle structure on the emulsion properties. The morphologies and size distributions of the P(St-co-DM) colloid particles were studied by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The results show that the more critical water content, the higher hydrophilic and the bigger hydrodynamic radius of the micelles are observed when tetrahydrofuran (THF) is used as cosolvent. When dioxane or THF is used as co-solvent, the P(St-co-DM) self-assembles into spherical micelles with a relatively loose outer layer and a compact inner layer. In the case of N,N-dimethylformamide (DMF), particles are distributed uniformly inside the spherical micelles. The hydrophilic properties of the micelles were characterized by recording the contact angle for the toluene/water interface. The contact angles of all the micelles are less than 90°. The O/W type (oil-in-water type) emulsions were obtained for three co-solvents. The type of emulsions was determined by drop test. The emulsifier experiment shows that the solid particulate emulsifiers have excellent emulsifying properties for dioxane and THF as co-solvents.

The extraordinary properties of amphiphilic polymers originate from their unique skeleton structures and the aggregation behavior of the polymer chains. In the present work, we introduced different amounts of NaCl into AMPS-AMC₁₂S brush-like amphiphilic polymers synthesized via the statistical polymerization of 2-(acrylamido)-dodecanesulfonic acid (AMC₁₂S) with 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS), and investigated the effects of the NaCl on the aggregation behavior of the polymers, using steady-state fluorescence, dynamic light scattering, and transmission electron microscopy. The results showed that the effects of the salt were more intense for polymers with fewer side chains. As the NaCl concentration increased, the polymer chains associated at a lower critical concentration. The polymers tended to aggregate in an intrapolymer configuration, in preference to an interpolymer configuration; this resulted in the formation of smaller unimers, rather than giant multipolymer aggregates. The results described here provide an efficient approach for controlling the aggregation behavior of amphiphilic polymers, and have significance in advancing the design and control of functional aqueous systems, as well as in promoting the development and application of novel polymers.

Water-based cypermethrin microemulsions were prepared by adding oil to emulsified water, with ethyl butyrate as the solvent, TritonX-100 (TX-100) and sodium dodecyl benzene sulfonate (SDBS) as surfactants, and n-butyl alcohol (n-C₄H₉OH) as a co-surfactant. The structure and properties of the microemulsions were investigated by determining the phase diagram, and using negative-staining transmission electron microscopy, and conductivity, surface tension, dynamic light scattering, and contact angle measurements. The spreading kinetics of the microemulsions on the leaf surface of Youngfu wheat was also studied. The results showed that the cypermethrin microemulsions followed the oil-in-water model, and had a strong solubilizing effect on cypermethrin. The microemulsions showed a low contact angle, and low surface tension, and the droplet radius was about 45 nm. The kinetics for the spreading of the microemulsions on the leaf surface of Youngfu wheat fitted a second-order kinetic equation. The kinetic rate constants were 0.1090 (°)^-1·min^-1 (20℃) and 0.1572 (°)^-1·min^-1 (30℃), and the activation energy was 27.03 kJ·mol^-1.

The dynamic surface adsorption properties of aqueous sodium dodecyl sulfate (SDS) solutions were investigated at different concentrations of NaCl using bubble pressure tensiometry MPTC. In the case of ionic surfactants, the existence of a diffuse electric double layer on the surface adsorption layer and around the micelle produces a surface charge. Here, we discuss the influence of the surface charge on the dynamic surface diffusion processes and the micelle properties. It was found that the SDS adsorption process occurred in the presence of a 5.5 kJ·mol^-1 adsorption barrier (E_a) that was generated by the surface charge; this barrier significantly decreased the effective diffusion coefficient (D_eff) of the dodecyl sulfate ions (DS^-). The ratio of the effective diffusion coefficient to the monomer self-diffusion coefficient (D) (D_eff/D) was only 0.013. This indicated that at the beginning, the adsorption of SDS followed the mixed kinetic-diffusion controlled model; this is different from the behavior observed for nonionic surfactants. The adsorption barrier was reduced when NaCl was added. E_a was less than 0.3 kJ·mol^-1 after the addition of 80 mmol·L^-1 of NaCl. This resulted in values of between 0.8 and 1.2 for D_eff/D, which was consistent with the diffusion-controlled model that describes the behavior of nonionic surfactants. The characteristic constants for the micelle dissociation rate (k₂) were determined from the dynamic surface tension of the SDS micelle solutions. The calculated k values decreased as the NaCl concentration was increased, which demonstrated the existence of surface charge on the SDS micelles; this surface charge increased the repulsive forces between the dodecyl sulfate ions, and promoted the dispersion of the micelles.

The effects of Na⁺ in dilution steam and coke deposition on the physicochemical properties andcatalytic performance of ZSM-5 catalysts for the methanol-to-propylene (MTP) reaction were investigated.The deactivated and regenerated catalysts were characterized by means of X-ray diffraction (XRD),scanning electron microscopy (SEM), X-ray fluorescence (XRF) spectrum, nitrogen adsorption/desorption,temperature-programmed desorption of ammonia (NH₃-TPD), and thermogravimetry (TG). Their catalyticperformance for MTP reaction was tested in a continuous flow fixed-bed micro-reactor at 470℃, 101325Pa, and with methanol weight hourly space velocity (WHSV) in the range of 1.0-3.0 h^-1. The resultsindicated that the catalyst crystal structure and morphology was not significantly altered after 970 h onstream. In the MTP reaction, Na⁺ in the dilution steam can easily enter the pore channels of the catalyst,and partially replace H protons, thereby gradually decreasing the amount of acidity and acid strength of thecatalyst, which eventually causes deactivation. In addition, coke deposits on the catalyst surface blocking its micropores are the main reason for deactivation of the MTP catalyst. Coke deposits are mostlyeliminated through the burning charcoal regeneration process. The effect of framework dealumination fromthe catalyst by steam in the MTP process is slow but more serious. Through regeneration and ionexchange process, the catalytic activity of the deactivated catalyst can be fully restored. The conversion ofmethanol is consistently above 99%, and propylene selectivity is greater than 46% even after 470 h onstream. With increasing reaction time, the propylene selectivity gradually increases, while ethyleneselectivity gradually decreases.

The effects of oxygen atom coverage on the dissociation of O₂ molecules at the Nb(110) surface were investigated using density functional theory (DFT) methods. The dissociation of O₂ molecules is facile at low O coverages [Θ≤0.50 monolayer (ML)] because of the strong electronic interaction between O₂ molecules and the Nb substrate. At a coverage of 0.75 ML, O₂ molecules next to unoccupied distorted four-fold (H_4d) sites only dissociate with severe lattice distortions. However, the inward diffusion of O atoms is the rate limiting step for the dissociation of O₂ molecules after adsorption of 1.00 ML O atoms. Overall, our theoretical study provides a rationale for the experimental result that the dissociation of O₂ molecules decreases markedly after rapid adsorption of 1.00 ML O atoms on the low index Nb surfaces.

In this study, mesoporous nano CuAl₂O₄ was synthesized through a coprecipitation method using simple mixed templates consisting of butylamine and dodecanol. The sample was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and nitrogen adsorptiondesorption techniques. The absorption of butyl and octyl xanthate from aqueous solution onto the synthesized mesoporous CuAl₂O₄ solid surfaces was studied by a continuous, online, in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) technique. The CuAl₂O₄ membrane used in the adsorption experiments was prepared on a germanium internal reflection element using the chemical bath deposition method. During the adsorption process, the characteristic peak height of xanthate at 1200 and 1040 cm^-1 emerged and gradually increased. By monitoring changes in the peak height at 1200 cm^-1, which was assigned to the stretching vibration caused by C-O-C of the adsorbed xanthate molecules, the adsorption kinetics were studied. The adsorption results show that mesoporous CuAl₂O₄ has a high chemisorption capacity for xanthate, which reaches 236 and 300 mg·g^-1 for butyl and octyl xanthate, respectively, within 100 min. The adsorption kinetics can be described by a pseudo-second-order reaction model.

Adsorption of nicotine from aqueous solution by activated carbons with different pore sizes and chemical properties was studied. Activated carbons were prepared from Chinese fir sawdust by chemical activation with zinc chloride (called AC-Z) or physical activation with steam (called AC-H). The properties of the samples were compared with those of a commercial coconut-based activated carbon, named AC-C. The surface area and pore structure of the samples were determined by a surface area and porosity analyzer, and surface oxygen groups were characterized by Boehm titration. Adsorption experiments were performed under varying contact time, initial concentration, and temperature. The experimental data suggested that micropores, acidic groups, and the metal atoms play important roles in adsorption of nicotine. The different effects of temperature on the three samples also explain the role of the activated sites. The amount of nicotine adsorbed by AC-Z, which contained more activated sites than the other samples, first increased and then decreased with increasing temperature. This is because increased temperature accelerated the decomposition of nicotine molecules and their conjugation with activated sites, but if it became too high, the probability and strength of molecular collisions increased, causing adsorbed molecules to dissociate from activated sites. AC-H and AC-C, which both contained micropores and activated sites, showed different performance. Nicotine was physically adsorbed first: the surface oxygen groups bonded to nicotine molecules, which blocked the micropores of the adsorbents. Pseudofirst order, pseudo-second order, and intraparticle diffusion kinetic models were used to interpret the adsorption mechanism. Kinetic studies showed adsorption of nicotine was rapid and followed a pseudosecond order model. Thermodynamic parameters ΔG⁰, ΔH⁰ and ΔS⁰ were also calculated to predict the nature of adsorption, and indicated that adsorption was endothermic and spontaneous. The low ΔH⁰ values of AC-Z and AC-H show that nicotine molecules interacted strongly with activated sites, so they require less isosteric heat to adsorb the same amount of nicotine as AC-C, and also indicate that the activated sites play a role in adsorption.

Globally, NO_x is one of the most widespread pollutants. It is generated mainly from the burning of fossil fuels, and NO is very difficult to remove because of its capacity to be dissolved in water. The catalytic oxidation method can be used to convert NO to NO₂, which is soluble in water and can be removed using desulfurization devices. Here, a series of TiO₂-supported Mn-Co composite oxide catalysts were prepared using the impregnation method. The results of catalytic activity tests showed that the addition of Mn enhanced the efficiency of NO oxidation. Significantly, with 6% doping amounts, Mn (0.3)-Co(0.7)/TiO₂ showed the best activity of 88% NO conversion at 300 ° C. X-ray diffraction (XRD), N₂ adsorption/desorption, hydrogen temperature-programmed reduction (H₂-TPR), oxygen temperatureprogrammed desorption (O₂-TPD), and in-situ diffuse reflectance Fourier transform infrared (in-situ DRFTIR) spectroscopy were used to characterize the catalysts. The results indicated that when the doping amount was 6%, the Mn enhanced the specific surface areas and pore volumes, which improved the dispersion of the active component over the TiO₂ support. The co-doping of manganese into the Co/TiO₂ also enhanced the oxygen desorption capabilities of the catalysts, which improved their reduction abilities. In addition, bridge NO₃^-, the key intermediate, was converted into NO₂; this conversion was also enhanced by the presence of Mn on the Co/TiO₂ catalyst. All of the above reasons account for the high NO catalytic oxidation activity of the supported Mn-Co composite oxide catalysts.

CeO₂, Cr2O₃, and CeO₂-CrO_x mixed oxides with molar ratios of Ce to Cr of 9/1, 4/1, 2/1, 1/1, 1/2, 1/4, and 1/8 were prepared by coprecipitation. The catalytic performance of 1,2-dichloroethane (DCE) decomposition was evaluated on all the catalysts. The results indicate that CeO₂-CrO_x mixed oxides with different Ce/Cr molar ratios showed higher performance for the removal of DCE compared with pure CeO₂. The CeO₂-CrO_x mixed oxide with Ce/Cr molar ratio of 2/1 exhibited the highest catalytic activity of the samples, generating only small amounts of chlorinated by-products during the decomposition of DCE. The selectivity for HCl decreased as the molar ratio of Ce to Cr decreased. The catalysts were characterized by N₂ adsorption/desorption, X-ray diffraction (XRD), UV-Raman spectroscopy, hydrogen temperatureprogrammed reduction (H₂-TPR), and ammonia temperature-programmed desorption (NH₃-TPD) to study the effect of the Ce/Cr molar ratio on the physicochemical performance of the catalysts. An appropriate molar ratio of Ce to Cr formed a more stable Ce-Cr-O solid solution, which increased the mobility of reactive oxygen species, oxidative ability, surface acid content and the ratio of strong acidity, promoting the adsorption, activation and deep oxidation of DCE.

The reduction of carbon dioxide to methane in the presence of water was used to evaluate the photocatalytic activity of a prepared strontium metaborate catalyst. The strontium metaborate (SrB₂O₄) was prepared by a simple sol-gel method, and was shown to exhibit better photocatalytic performance than TiO₂ (P25) under UV-light irradiation. The structure, morphology, and energy levels of the photocatalysts were studied by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy, and UV-Vis diffuse reflectance absorption spectroscopy. It was revealed that the SrB₂O₄ valence band (VB) was located at 2.07 V (vs normal hydrogen electrode, NHE), which is more positive than E_redox^o (H₂O/H⁺) (0.82 V (vs NHE)); the conduction band was estimated to be -1.47 V (vs NHE)), which is more negative than E_redox^o (CO₂/CH₄) (-0.24 V (vs NHE)). Therefore, it is clear that strontium metaborate is capable of transforming CO₂ into CH₄. Moreover, the potential at the bottom of the conduction band for SrB₂O₄ is more negative than that for TiO₂(P25), leading to a higher deoxidization capacity, which also favors CH₄ formation. Thus, SrB₂O₄ exhibits a higher photocatalytic activity than TiO₂(P25).

In this work, graphene oxide ( ) was prepared from natural flake graphite by the modified Hummers method. A series of composites consisting of rutile TiO₂ and graphene (r -TiO₂) were synthesized via a one-step hydrothermal reaction of graphene oxide and titanium isopropylate. The influence of the amount of graphene oxide on the photocatalytic activity of the r -TiO₂ composites was studied. The photocatalysts were characterized by Brunauer-Emmett-Teller sorption (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, UV-Vis absorbance spectroscopy, and photoluminescence (PL) spectroscopy. The as-formed TiO₂ was formed in the rutile phase with a needle-cluster structure, and dispersed uniformly on the surface of graphene sheets. The composites possess higher specific areas than pure rutile TiO₂. The photo-degradation performance of Rhodamine B and methyl orange by the r -TiO₂ composites under ultraviolet and visible light was studied. The results indicated that r -TiO₂ composites prepared with 0.5 mg·mL^-1 of graphene oxide had the greatest photocatalytic activity.

Bismuth titanate (Bi₄Ti₃O₁₂, BIT) particles with different morphologies were synthesized by a one-step hydrothermal process and their optical and photocatalytic properties were investigated. The crystal structure and microstructures were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). XRD patterns demonstrate that the as-prepared BIT samples have layered perovskite structure. FESEM shows that BIT crystals can be fabricated in different morphologies by simply manipulating the reaction parameters of the hydrothermal process. The UV-visible diffuse reflectance spectra (UV-Vis DRS) reveal that the band gaps of the BIT photocatalysts are about 2.88-2.93 eV. The as-prepared BIT photocatalysts exhibit higher photocatalytic activities toward the degradation of methyl orange (MO) under visible light irradiation (λ>420 nm) when compared with traditional N-doped TiO₂ (N-TiO₂). The influence of morphology on the photocatalytic properties of BIT was also studied. BIT nanobelt structures displayed the highest photocatalytic activity. Up to 95.0% MO was decolorized after visible light irradiation for 360 min.

Bis(2-propyloxy)calix[4]crown-6 (BPC6) is an effective separation agent for the removal of cesium from high-level liquid wastes, because of its high selectivity and coordination capacity toward cesium ions. BPC6 will be exposed to ionizing radiation generated by radionuclides during the treatment of high-level liquid nuclear wastes, so it is necessary to investigate the radiolysis mechanism of BPC6 under γ-irradiation conditions. In this work, the radiolysis products including the gaseous and solid products of BPC6 solid were systematically assessed using gas chromatography (GC), micro Fourier transform infrared (Micro-FTIR) spectroscopy, and nuclear magnetic resonance spectroscopy. The radiolysis ratio for BPC6 in an O₂ atmosphere (approximately 10.4%) was significantly higher than that in an N₂ atmosphere (approximately 2.5%). The main radiolytic gas products of BPC6 under O₂ were H₂, CH₄, CO, and CO₂, while those under N₂ were H₂, CH₄, CO, CO₂, C₂H₄, C₂H₆, C₃H₆, and C₃H₈. Finally, a mechanism for the radiolysis of BPC6 under different atmospheres was suggested, in terms of the gas and solid radiolytic products. This work will be of significant help in understanding the degradation mechanism of the BPC6 extraction system.

We performed molecular dynamics simulations on complexes of ABL to investigate the binding of imatinib, P16 (binding at the ATP pocket), and STJ, MS7, MS9, 3YY, and MYR (binding at the myristoyl pocket). The calculated binding energies were then decomposed to determine the ligand-residue pair interactions, using the generalized Born surface area (GBSA) method. The results showed that the binding energies are almost the same for STJ, MS7, and MS9, and their absolute values are larger than those of 3YY and MYR. The decomposition of the binding energy revealed that three residues (ILE502, VAL506, and LEU510) contribute significantly to hold the αI-helix in a bent conformation in the STJ-ABL and MYR-ABL complexes. The root mean square deviation (RMSD) values for the residues forming myristoyl pocket showed that the inhibitors in this pocket decrease the flexibility of the corresponding residues.

The three-dimensional quantitative structure-activity relationships (3D-QSAR) were established for 38 five-membered heterocyclopyrimidine thymidylate synthase inhibitors by using comparative molecular field analysis (CoMFA) and comparative similarity indices analysis (CoMSIA) techniques. With the CoMFA model, the cross-validated value (q²) was 0.662, the non-cross-validated value (R²) was 0.921, and the external cross-validated value (Q_ext²) was 0.85. And with the CoMSIA model, the corresponding q², R², and Q_ext² values were 0.672, 0.884, and 0.81, respectively. The mode of action obtained by molecular docking was in agreement with the 3D-QSAR results. The results revealed that both models have od predictive capability to guide the design and structural modification of homologic compounds. Furthermore, these results also establish a base level for further research and development of new thymidylate synthase inhibitors.

Based on the three-dimensional (3D) structure of trypsin, 2-nitrophenyl-β-D-glucopyranoside was selected from the ZINC database to be a candidate affinity ligand for trypsin. The affinity between trypsin and the ligand was analyzed. It is found that the interactions between the ligand and the protein are dominated by van der Waals interactions and hydrogen bonding. Molecular dynamics (MD) simulations were used to verify the affinity between the ligand and trypsin; the simulations indicate that the complex remains stable, and the distance between the ligand and the target protein changes only a little. It is found that one water molecule acts as a bridge between the ligand and the protein pocket via hydrogen bonding. Finally, the ligand was coupled to Sepharose CL-6B gel, and was used to immobilize trypsin in an oriented fashion. It is found that the enzyme activity and specific activity of the oriented immobilized trypsin are 340.8 U·g^-1 and 300.3 U·mg^-1, respectively. These values are 10 and 5 times that of the free enzyme. The results of this work indicate that the combination of docking and MD simulations are promising for the rational design of ligands for oriented immobilization.