2013 Volume 29 Issue 12
In this paper, the recent developments in measurement methods of solid-state circular dichroism (CD) spectroscopy were summarized and discussed, especially the effects of concentration on solid-state CD spectral distortions. By reinspection and introspection of the solid-state CD spectra of four reported compounds, concentration gradient measurements were proved to be necessary for appropriate concentrations, which are greatly related to the chiroptical properties. The thin film solid-state CD measurements of the inherently chiral atropisomer (S)-1,1'-bi-2-naphthol (S-BINOL) were carried out with concentration gradient measurements. Using this film-state technique for the first time, the results show some subtle correlations between the CD curves and the special concentrations.
Hollow Fe2O3 nanorods were prepared using a hydrothermal method, and were then combined with Al nanoparticles to form superthermite Al/Fe2O3 by ultrasonic mixing. Fe2O3 and Al/Fe2O3 were characterized using X-ray powder diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS). The effects of Al/Fe2O3, Al, and nano-Fe2O3 powders on the thermal decomposition of cyclotrimethylene trinitramine (RDX) were investigated using differential scanning calorimetry (DSC). The results show that the superthermite Al/Fe2O3 affects the thermal decomposition of RDX and greatly enhances its secondary gas-phase reaction. The shapes of the main RDX decomposition peaks changed with increasing superthermite content. The main influences of superthermite Al/Fe2O3, Al nanopowders, and Fe2O3 nanorods on the thermal decomposition of RDX are that the secondary decomposition peaks become distinct and the peak temperature decreases.
Solvent-free solid-state foaming technology was used to fabricate microcellular polylactic acid (PLA) scaffold materials with cell sizes from 350 to 20 μm at saturation pressures of 2.5, 3.5, 4.0, and 5.0 MPa in carbon dioxide. The corresponding thermodynamic parameters were measured, including the decomposition temperature and rate, storage/loss modulus, and loss factor, using thermogravimetric analysis, dynamic thermal mechanical analysis, and scanning electron microscopy. The Kissinger, Ozawa-Doyle, and Vyazovkin equations were used to calculate the thermal decomposition kinetics for PLA foams of different cell sizes; their lifetimes in nitrogen were also obtained. It was observed that PLA foams with larger cell sizes, lower average activation energies, and better flexibilities could be fabricated at lower saturation pressures, resulting in reduced decomposition times.
Membranes produced from modified polyacrylonitrile (PAN) nanofibers with different diameters were prepared by electrospinning and amidoximation. They were then used as ligands to coordinate with Fe3+ for preparing modified PAN nano-fibrous membrane Fe complexes. The coordination kinetics of three modified PAN nano-fibrous membranes with Fe3+ were studied, and the effects of temperature and the Fe3+ initial concentration on the coordination kinetics were also examined. Finally, the catalytic activities of the three modified PAN nano- fibrous membrane Fe complexes were evaluated as heterogeneous Fenton catalysts in the degradation of an organic dye. The effect of fiber diameter on the catalytic activity of the complexes was investigated. The results indicated that within the observed temperature and concentration ranges, the equilibrium data for the coordination of Fe3+ with the modified PAN nano-fibrous membranes correlated with the Langmuir and Freundlich isotherm equations, but the coordination kinetics showed better agreement with the Lagergren second-order equation. Modified PAN nanofibrous membranes with small diameters showed higher Fe- coordinating capacities and reaction rate constants under the same conditions, indicating that they reacted with Fe3+ more easily than the others did. Better catalytic activities for dye degradation were found for the three modified PAN nanofibrous membrane Fe complexes in the dark, and these were further improved by light irradiation. The catalytic activities of the complexes were significantly affected by the nanofiber diameter. The complex prepared using a modified PAN nanofibrous membrane with fibers of an appropriate diameter exhibited the best catalytic activity.
Integration of a skeletal polycyclic aromatic hydrocarbon (PAH) model with a toluene reference fuel (TRF) oxidation model was used to develop a skeletal TRF-PAH model. A phenomenological soot model, coupled with the new TRF-PAH model, was modified based on the experimental observation that fuels with different molecular structures produce PAHs and soot in different ways. The new TRF-PAH model was validated against experimental data for the relevant PAHs for the oxidation/pyrolysis of toluene in a jet-stirred reactor, flow reactor, and shock tube. The results show that the PAH model can reproduce the experimental data for the major species concentrations. The predicted benzene concentration in the oxidation of alkanes and aromatic hydrocarbons indicates that the molecular structure of the fuel significantly affects the PAH formation pathway. The improved soot model was validated against measured soot yields from the pyrolysis of toluene, toluene/n-heptane mixtures, and toluene/isooctane mixtures in a shock tube, as well as toluene oxidation. The results show that the predicted soot yields obtained using the new soot model are in reasonable agreement with the experimental data over a wide operating range. Finally, the soot model was used to predict the soot emissions from a diesel engine fueled with TRF20. The results indicate that the TRF-PAH combustion model and the new soot model can reproduce the combustion and emission characteristics well.
The electronic structures and optical properties of 4-N,N-dimethylamino-4'-N'-methylstilbazolium tosylate (DAST) and 4-N,N-dimethylamino-4'-N'-methylstilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS) were investigated using density functional theory based on the plane wave basis set. The results indicated that the two compounds showed similar band structures, and the top of the valence band and the bottom of the conductive band mainly originated from the N 2p states of dimethylamino and methylpyridine, respectively. In terms of the linear optical properties, the birefringence indexes, Δn, of the two compounds were very large (Δn>0.5), and they exhibited od light transmission in the mid-and far-infrared regions. With regard to second-order nonlinear optical characteristics, the DAST and DSTMS crystals showed strong second harmonic generation (SHG) responses, and the corresponding SHG coefficients (d11) were about 150 pm·V-1. Analysis of the band structures showed that the SHG responses of the two compounds were closely related to charge transfers between electron-donating and electron-withdrawing groups. Ethylene bridging also played an important role in the charge transfer process.
The geometries, polarizabilities (αs), and first hyperpolarizabilities (βtot) of a series of green fluorescent protein chromophore coupled diradicals and their corresponding optical isomers were investigated using density functional theory (DFT). The results show that the introductions of the electron donor/acceptor significantly enhance the polarizabilities and have a different influence on the first hyperpolarizabilities. For trans isomers, the βtot values of the studied compounds increase with increasing strength of the electron-withdrawing ability of the substituent, whereas the βtot values decrease significantly with increasing strength of the electron-donating ability of the substituent. For cis isomers, the trends in the changes in the βtot values are the opposite of those for trans isomers on introduction of a donor/acceptor. Significantly, photoisomerization can lead to the different βtot values. The βtot values of cis isomers are smaller than those of trans isomers when electron acceptors are introduced. For example, the βtot value of the cis isomer with the strongest electron acceptor, i.e., ―NO2, is about 1/6 that of the corresponding trans isomer. However, the βtot values of trans isomers are smaller than those of cis isomers when electron donors are introduced. For example, the βtot value of the trans isomer with the strongest electron donor, i.e., ―NH2, is about six times smaller than that of the corresponding cis isomer. As a result, photoisomerization can modulate the molecular nonlinear optical (NLO) responses effectively.
A detailed understanding of how nucleobases interact with protein peptides will allow us to gain valuable insights into how these interesting biological molecules could be used to construct complex nanostructures and materials. In this work, the optimal structures and binding energies of 20 hydrogenbonded complexes, which contained the nucleic acid base adenine, N-methylacetamide, a glycine dipeptide, and an alanine dipeptide, were obtained. The site preferences of adenine hydrogen bonding to peptide amides were explored. The calculation results show that adenine can use two binding sites (site A1 and site A2) to form N―H…N or N―H…O=C hydrogen-bonded complexes with N-methylacetamide; the N―H…N hydrogen-bonded complexes formed at site A1 of adenine are more stable. The calculation results also show that the glycine dipeptide can use either site Gly7 or site Gly5, and the alanine dipeptide can use either site Ala7 or site Ala5 to form hydrogen-bonded complexes with adenine; the hydrogenbonded complexes formed at site Gly7 of the glycine dipeptide and at site Ala7 of the alanine dipeptide are more stable. The hydrogen-bonded complexes formed by adenine and a dipeptide have larger negative binding energies than the complexes formed by adenine and N-methylacetamide, indicating that the interaction between adenine and the peptide is preferred to that between adenine and N-methylacetamide. The nature of the hydrogen bonding in these complexes was further explored based on the atoms in molecules calculations and the natural bond orbital analysis.
Electrolytic manganese dioxide (EMD) was prepared using a gas diffusion electrode (GDE) instead of a traditional hydrogen evolution cathode. The stability, lifetime, and failure behavior of the GDE were studied in a strongly acidic MnSO4-H2SO4 electrolysis system. The results show that the GDE has od reproducibility and stability, and its lifetime is up to 400 h in a MnSO4-H2SO4 electrolysis system. Parallel experiments indicate that the major reason for the first increase in the anode cell voltage is the deposition on the anode of a certain thickness of EMD. When the current density is 100 A·m-2, the cathode reaction rate is controlled by a mixture of oxygen ionization and oxygen diffusion before failure of the GDE, and the cathode reaction process consists of two simultaneous reactions after failure of the GDE, i.e., oxygen depolarization and hydrogen depolarization. Hydrogen depolarization is the main controlling process after GDE failure. One of the reasons for electrode failure is destruction of the polytetrafluoroethylene (PTFE) network structure in the catalyst layer and dissolution of the nickel mesh layer. Platinum agglomeration reduces the electrocatalytic activity of the GDE, and this is the main reason for electrode failure. Cathode failure is the main reason for the second increase in the anode cell voltage.
2-Mercaptobenzothiazole (MBT) is a highly efficient inhibitor of Cu. However, the inhibition mechanism is still unclear. In this paper, the anticorrosive effect of MBT on a Cu surface at the macroscopic level was evaluated using a polarization curve technique. The potential-dependent adsorption geometries of MBT at the molecular level were investigated using electrochemical surface-enhanced infrared reflection absorption spectroscopy in attenuated total reflection mode, together with theoretical calculations. The results indicated that the MBT molecules were adsorbed on the Cu surface vertically, in a thiolate form, through exocyclic S atoms at a potential negative of 0 V (vs saturated calomel electrode (SCE)). At a potential positive of 0 V (vs SCE), electrons were transferred between MBT and the Cu substrate, meaning that MBT molecules can interact with the Cu surface via exocyclic S and endocyclic N atoms to form a polymer film, resulting in the formation of a compact protecting layer to prevent Cu dissolution.
Self-crosslinked poly(phthalazinone ether ketone) anion-exchange membranes (AEMs) were successfully fabricated from chloromethylated poly(phthalazinone ether ketone) (CMPPEK) by amination, membrane casting, and OH-exchange reaction steps. Triethylamine (TEA) was used as an ammonium agent, and diethylenetriamine (DETA) and diethylamine (DEA) were used as self-crosslinking agents in the quaternary reaction of CMPPEK, resulting in DETA-QPPEK-OH and DEA-QPPEK-OH AEMs, respectively. The chemical structures of DETA-QPPEK-OH and DEA-QPPEK-OH were characterized using Fourier transform infrared (FTIR) spectroscopy. The physicochemical properties of these AEMs were investigated including ion-exchange capacity (IEC), swelling ratios, water uptake, and ionic conductivities at 30 ℃. The results showed that the swelling ratio of the DETA-crosslinked AEM was lower than that of the DEAcrosslinked AEM. This could be attributed to multi-crosslinking of multi-amino groups in the DETA structure. The temperature dependences of the ionic conductivities of the AEMs were measured from 30 to 80 ℃. The ionic conductivities of the DEA-crosslinked and DETA-crosslinked AEMs were 0.060 and 0.028 S·cm-1 at 80 ℃, respectively. The thermal stabilities of the resulting DETA-QPPEK-OH and DEAQPPEK-OH membranes were investigated using thermogravimetric analysis (TGA), under a nitrogen atmosphere. The obtained membranes have high dimensional stabilities and are very promising for potential applications in anion-exchange membrane fuel cells (AEMFCs).
The co-deposition and electrocrystallization of Cu-Sn alloy in a weak acidic citrate bath were studied by linear sweep voltammetry (LSV), cyclic voltammetry (CV), and chronoamperometry. The Scharifker- Hill (SH) theory model and Heerman-Tarallo (HT) theory model were applied to analyze the chronoamperometry data. The results show that the Cu-Sn alloy co-deposited on copper electrode, following instantaneous nucleation with three-dimensional (3D) growth under diffusion control. The kinetic parameters were obtained using the HT model. As the step potential shifted from -0.80 to -0.85 V, the nucleation rate constant (A) increased from 20.19 to 177.67 s-1, the density of active nucleation sites (N0) increased from 6.10×105 to 1.42×106 cm-2, and the diffusion coefficient (D) was (6.13±0.62)×10-6 cm2·s-1.
SmBaCo2O5+δ (SBCO) was synthesized as a cathode material for intermediate temperature solid oxide fuel cells (IT-SOFC) via the EDTA-glycine process. The structure and properties of the material were measured by thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), four-probe DC method, and AC impedance spectroscopy. The results indicated that a stable perovskite phase was formed after the initial powder was calcined at 850 ℃ for 5 h. The obtained powders revealed fine particles with od dispersion and homogeneous size distribution. SBCO had excellent high temperature chemical compatibility with Sm0.2Ce0.8O1.9 (SDC) electrolyte. The electrical conductivities of the SBCO reached 668-382 S·cm-1 in the temperature range 500-800 ℃. A symmetric half cell with SDC as electrolyte and SBCO as electrode was characterized by od three-phase interface bonding and high cathode catalytic activity. A polarization resistance of 0.0688 Ω·cm2 was achieved at 750 ℃ for the SBCO, far below that of SBCO synthesized by solid state reaction method (SSR), with an activation energy (Ea) of 122.21 kJ·mol-1.
Polymers used in porous membrane manufacture are highly susceptible to adsorption of organic foulants. In this study, a new method for in situ preparation of a poly(vinylidene fluoride) (PVDF) based hybrid membrane is reported. The strategy in this method is to combine an ion-exchange process with a traditional immersion precipitation process. A hydrous ZrO2 sol was synthesized by the addition of anion-exchange resin to N,N-dimethylformamide (DMF) containing zirconyl chloride. A homogeneous ZrO2/PVDF casting solution was then obtained by dissolving PVDF in the ZrO2 sol. The presence and dispersion states of ZrO2 nanoparticles in the resultant membrane matrix were determined using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The results indicate that the ZrO2 nanoparticles were well dispersed throughout the PVDF matrix, and the size of the formed nanoparticles was about 10-20 nm. The membrane formation mechanism was investigated based on the viscosity, precipitation kinetics, and membrane morphology. The results indicate that the introduction of ZrO2 nanoparticles accelerates phase inversion of the casting solution. The membrane hydrophilicity was determined using contact angle measurements. The antifouling properties were examined using antifouling experiments. The results confirm that the presence of ZrO2 nanoparticles improves the membrane hydrophilicity and reduces protein adsorption on the membrane. This method for in situ preparation of ZrO2/PVDF hybrid membranes by combining an ion-exchange process with a traditional immersion precipitation process is valuable in the fabrication and applications of organic-inorganic hybrid membranes.
Amonolayer film of thiosalicylic acid (TSA) adsorbed on activated ld electrodes was investigated by using in situ electrochemical surface-enhanced Raman scattering (EC-SERS). In the SERS spectra of selfassembled monolayers in solutions with different pH values, two peaks with Raman intensities that decreased with increasing pH were observed. The optimum EC-SERS signals were obtained at 0.7 V and 70 s, and it was found that the intensities became weaker, and the peaks eventually disappeared, when the potential was negatively shifted. This showed that the alignments of TSA assembled on the ld surface changed in response to changes in the external conditions. The absorption mechanism of the TSA monolayer was investigated by calculating the distribution fraction of TSA at different pH values and the enhancement factor (EF) at different potentials, using a combination of SERS and EC-SERS. As a result of different electrochemical absorption orientations of TSA and its reduction/desorption behavior at high negative potentials, the Raman enhanced effect of TSA on ld was significantly reduced and the SERS activity was irreversibly lost.
Three-dimensional (3D)-NiO/Bi7.47Ni0.53O11.73 (BiNiO) microspheres were synthesized by a mixed solvothermal process in the presence of urea. The catalysts were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), and photodegradation of methyl orange (MO). The results show that the composite catalysts are composed of NiO nanosheets and 3D-NiO/Bi7.47Ni0.53O11.73 microspheres. The sample BiNiO-300, which was prepared by heating the precursor at 300 ℃ for 2 h, had the best photocatalytic activity: after visible-light irradiation for 3 h, the decolorization of an MO solution was 98%.
Polystyrene latex (PS) spheres and EO20PO70O20 (P123) were used as dual template agents, with TiO2 as the matrix, to prepare a three-dimensionally ordered macroporous (3DOM) composite Bi2O3/TiO2, using a sol-gel method and post-processing calcination. The phase structures, chemical composition, morphology, and surface physicochemical properties were characterized using X-ray diffraction (XRD), Fourier-transform infrared (FT-IR), ultraviolet-visible diffuse reflectance (UV-Vis DRS) and X-ray photoelectron spectroscopies (XPS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), scanning electron microscopy (SEM), and N2 adsorption-desorption measurements. The results show that the composite is well crystallized and has a highly ordered porous structure with mesoporous walls; it is a 3DOM material. The light absorption of 3DOM-Bi2O3/TiO2 is red-shifted by about 60 nm to the visible region compared with TiO2. In the photocatalytic degradation of crystal violet using various methods, namely ultraviolet, visible-light, and microwave-assisted irradiation, the activity of 3DOM-Bi2O3/TiO2 is significantly higher than those of P25, Bi2O3, and Bi2O3/TiO2. The 3DOM-Bi2O3/TiO2 composite also shows od photocatalytic activity in the degradations of various dyes under ultraviolet irradiation. The 3DOM-Bi2O3/TiO2 activity is well retained after three cycles.
Anew type of organic visible-blind ultraviolet (UV) photodetector based on tri(dibenzoylmethane)(4, 7-biphenyl-1,10-phenanthroline)europium (Ⅲ) [Eu(DBM)3BPhen] as an electron donor and [6,6]-phenyl-C-61-butyric acid methyl ester ([60]PCBM) as an electron acceptor was fabricated. A peak response of 26 mA·W-1 and external quantum efficiency of 9.1% were obtained under illumination with 360 nm UV light at 2.1 mW·cm-2. This was because of the high UV absorption of Eu(DBM)3BPhen and the long lifetime, 300 μs, of Eu3+ ions, resulting in high exciton dissociation efficiency. Distinct photoluminescence quenching and photoconductivity of Eu(DBM)3BPhen were obtained by doping with [60]PCBM. A strong persistent photoconductivity was observed, which could be attributed to low charge carrier transportation and slow release of trapped exciton states in the blend films after the UV light is turned off.
Amyloid β (Aβ) peptides and metal ions have been suggested to be associated with the pathogenesis of Alzheimer′s disease. Understanding the interactions between Aβ and metal ions at the molecular level is a key step in investigating the role of metal ions in the aggregation of Aβ to form neurotoxic oli mers. In this paper, dihedral dynamics analyses were used, which combine the potential of mean force (PMF) to calculate the free energies of individual dihedral angles of Zn2+-bound Aβ40 (Aβ40-Zn2+) and Aβ42 (Aβ42-Zn2+) using a coarse-grained model, dihedral principle component analysis to characterize the free energy landscapes of Aβ40-Zn2+ and Aβ42-Zn2+, and Markov state models to show the dynamic misfolding network of Aβ40-Zn2+ and Aβ42-Zn2+. Our results show that the dihedral free energies of Zn2+-bound Aβ40 and Aβ42 are similar, with significant difference being observed for the dihedral consisting of Val24, Gly25, Ser26, and Asn27 residues. Both free energy landscapes are less rugged, indicating that no high energy barrier has to be crossed for conformational transitions of Aβ. Furthermore, the Markov state model suggests that each microstate containing a number of similar structures serves as a hub in the network, and multiple alternative misfolding pathways are available if that node is blocked, indicating the kinetic feasibility of conformational transitions of Zn2+- bound Aβ. In particular, the role of the β-strand structure in the kinetic network is negligible, consistent with the experimental result that little β-strand structure was identified in Zn2+-bound Aβ.
The binding isotherms of the interaction between bovine serum albumin (BSA) and sodium dodecyl sulfate (SDS) were obtained using electromotive force measurements. Changes in the microenvironmental polarity of aromatic amino acid residues during the interaction were studied using fourth-derivative ultraviolet spectroscopy and fluorescence spectroscopy. The average number (v) of SDS molecules bound to BSA increased with increasing SDS concentration. The polarity of tryptophan (Trp) residues decreased gradually and then remained almost constant. The polarity of tyrosine residues increased significantly and then decreased a little. The polarity of phenylalanine residues increased very slightly. The results show that SDS molecules bind to BSA in the vicinity of Trp-213 when v gradually increases from 0 to 14. BSA unfolds from domain ⅡA, induced by SDS aggregates formed near Trp-213. The v value then increases rapidly as a result of positive cooperative binding. When the v value reaches about 302, saturation binding is achieved and the BSA conformation remains almost unchanged.
The mechanism of the interaction between Chrysin (CHR) and human serum albumin (HSA) was investigated using various spectroscopic techniques. It was found that CHR can induce HSA fluorescence emission quenching by static process. Additionally, HSA caused a significant red shift in the ultraviolet absorption of CHR. This indicated that binding with a protein can result in dissociation of the phenolic hydroxyl in CHR. HSA can also cause CHR fluorescence emission. The binding constants of CHR and HAS were calculated based on the fluorescence quenching and emission modes. The results obtained using these two methods were consistent. The binding constant (KA) values at pH 7.4 were (9.97±0.24)×104 and (9.75±0.11)×104 L·mol-1, respectively; and the ratio of combination was 1:1. The binding constants decreased gradually with decreasing the pH value. This is related to conformational changes in the protein. The protein is partly denatured at pH 3.5, with the site Ⅱ in the HSA opening chain. It was found that CHR was located at site I, which is in subdomain ⅡA of HAS. Based on molecular modeling, the mechanism of the interaction between CHR and HAS was investigated.
Nanocrystalline BiOBr-TiO2 composite has been prepared using a microemulsion-like chemical precipitation method. The key to this method is the dual role of Br- in the synthetic process. The Br- of cetyl trimethyl ammonium bromide is able to link the cetyltrimethyl ammonium cation with anatase TiO2 to form a water-in-oil microemulsion-like system. Meanwhile, Br- is also a bromine source favorable for the fabrication of a nanoheterostructure between BiOBr and TiO2. Compared with pure TiO2 and BiOBr-TiO2 composite obtained using a traditional aqueous system, the as-obtained BiOBr-TiO2 displays high photogenerated charge separation, responsible for excellent photocatalytic activity for degrading liquid-phase phenol solution and gas-phase acetaldehyde. This result is ascribed to its effective heterostructure.
β-FeSe is typically prepared under vacuum at high temperatures exceeding 800 ℃. Here we develop a new LiCl/NaCl/KCl flux method to successfully synthesize β-FeSe under air atmosphere. The synthetic procedure is simple and without evacuation pretreatment. The flux effectively decreases the synthetic temperature and protects the reactants and products from air. X-ray diffraction data and Rietveld analysis show that the product has high purity. Magnetic and electrical measurements confirm that all samples obtained show superconductivity below 8 K.
According to the SCI data, articles in this list are the most frequently cited ones among those published in Acta Physico-Chimica Sinica in 2010.
一年来(2012 年11 月21 日-2013 年11 月20 日), 有918 位老师(名单按姓名拼音字母排序)非常认真细致、无偿而且及时(初审平均19 天、复审平均8 天)地完成了审稿, 提出了很多客观、中肯的意见和建议. 他们的辛勤劳动和无私奉献使得《物理化学学报》能够高质量、快速(网络版平均出版周期为77 天, 印刷版为154 天)地发表作者的优秀研究成果, 促进了学术交流. 谨向他们致以衷心的谢忱和崇高的敬意!