Two new layered lanthanide sulfates, [C₁₀H₁₀N₂][Pr₂(SO₄)₄(H₂O)₂](1) and [H₅O₂][Sm(SO₄)₂(H₂O)₃](2) were synthesized via solvothermal reaction and structurally characterized by single-crystal X-ray diffraction(XRD), infrared(IR) spectroscopy, thermal analysis, fluorescent spectra and inductively coupled plasma(ICP). Crystal data for compound 1, triclinic, P-1 space group, a=0.8052(4) nm, b=0.9438(4) nm, c=1.4990(7) nm, α=79.450(5)°, β=83.703(5)°, γ=74.048(5)°, V=1.0746(9) nm³, Z=2; for compound 2, monoclinic, P2(1)/c space group, a=0.6599(11) nm, b=1.8940(3) nm, c=0.8765(14) nm, β=96.596(2)°, V=1.0883(3) nm³, Z=4. Structure analysis indicates that both the compounds exhibit a 2D corrugated layer structure, with protonated 4,4′-bipyridine cations and water dimmers (H₅O₂)⁺ located between the inorganic layers of compounds 1 and 2, respectively. Luminescent properties of compounds 1 and 2 were further investigated.

Hierarchical tin oxide(SnO₂) architectures were synthesized with a facile hydrothermal method. In the hydrothermal synthesis, sodium dodecyl benzene sulfonate(SDBS) surfactant plays an important role as structure-directing reagent. The synthesized samples were characterized by powder X-ray diffraction(XRD), field emission scanning electron microscopy(FESEM), transmission electron microscopy(TEM) and high-resolution transmission electron microscopy(HRTEM). The results clearly reveal that the hierarchical architectures of SnO₂ were composed of aggregated nanosheets with a thickness of about 100 nm. A possible mechanism for the formation of the SnO₂ hierarchical architectures was proposed. In addition, the gas sensing properties of the as-prepared products were investigated and it was found that the sensor based on the special SnO₂ hierarchical architectures exhibited a high response and good selectivity to NO₂ at the optimal working temperature of 160 °C.

GdOHCO₃ rhombic microcrystals were synthesized by hydrothermal method with urea used as the precipitator. Experimental parameters, such as the molar ratio of the starting reagents, reaction temperature and reaction time were examined. The as-obtained product was characterized by powder X-ray diffraction(XRD), field-emission scanning electron microscopy(FESEM), X-ray photoelectron spectroscopy(XPS), Fourier transform infrared spectroscopy(FTIR) and spectrofluorometry. The main reactions to form GdOHCO₃ were proposed. In addition, the photoluminescence(PL) properties of GdOHCO₃ rhombic microcrystals were discussed. The broad band located between 350 nm and 600 nm in the emission spectrum can be attributed to the self-trapped exciton luminescence.

A new “off-on” switch for sensitive and selective fluorescence detection of biothiols[glutathione(GSH), cysteine(Cys) and homocysteine(Hcy)] was developed based on an anionic conjugated polyelectrolyte(CPE), pyridyl-functionalized poly(phenylene ethynylene)(P1). The fluorescence of P1 can be significantly quenched by Ag⁺ due to complexation-mediated interpolymer aggregation. Furthermore, biothiols can efficiently recover the fluorescence intensity of P1 as a result of the stronger binding between thiol group and Ag⁺, which dissociates P1 from the P1/Ag⁺ complex and disrupts interpolymer aggregation. Under optimum conditions, a good linear relationship in a range of 100–4200 nmol/L is obtained for GSH with a detection limit of 80 nmol/L(S/N=3). As a result of specific interaction between the thiol group and Ag⁺, the proposed method shows a high selectivity for biothiols. In addition, the CPE-based fluorescence “off-on” switch has been used to quantitatively detect total biothiols in cell lysates.

An electrophoretic method was developed for the determination of several important catecholamine markers, namely norepinephrine, epinephrine, dopamine, metanephrine, vanillylmandelic acid and homovanillic acid in urine samples. Under the optimum conditions, the six marker compounds could be well separated with the major coexisting interference compound uric acid within 24 min at a separation voltage of 16 kV in a borate running buffer(80 mmol/L, pH=9.48). Highly linear response can be obtained over three orders of magnitude for the above markers with the low limits of detection ranging from 1.0 ng/mL to 5.0 ng/mL(S/N=3). The proposed capillary electrophoresis with amperometric detection(CE-AD) method has been used to simultaneously determine the six catecholamine markers in urine samples of healthy volunteers and patients suffering from different diseases avoiding redundant measurements and high assay cost; and the electrochemical profiles can suggest more diagnostic information of multiple diseases, which provides a promising and convenient entry into primary diagnoses of several clinical diseases.

Three (2E)-3-(4′-halophenyl)prop-2-enoyl sulfachlorpyridazine sodium salts(XPSCA) were synthesized. Their chemical structures were confirmed by ¹H NMR and ¹³C NMR, electrospray ionization mass spectrometry (ESI-MS), and infrared(IR) spectroscopy. The interactions between XPSCA and bovine serum albumin(BSA) were investigated under imitated physiological condition by fluorescence quenching technique and UV-Vis absorption spectroscopy according to the Stern-Volmer equation. The results from the emission quenching at different temperatures indicate that the quenching mechanism of serum albumin by XPSCA was static quenching mechanism at low XPSCA concentrations or a combined quenching(static and dynamic) mechanism at higher XPSCA concentrations. At different temperatures, the binding constant and the binding sites of XPSCA with BSA were investigated, and the distances were evaluated according to Förster non-radiative resonance energy transfer theory. The thermodynamic parameters were calculated according to van’t Hoff equation, which implies that both van der Waals interaction and hydrogen bond played major roles in stabilizing the XPSCA-BSA complexes, whereas hydrophobic interactions were secondary. Moreover, the conformational changes in BSA were analyzed by synchronous fluorescence spectra.

We described the preparation of copper oxide composite nanofibers doped with carbon nanotubes (CuO/C-NFs) or nickel oxide(CuO/NiO-NFs) by electrospinning for direct glucose determination. The interest in exploring practical CuO/C-NFs and CuO/NiO-NFs electrode materials for sensor application was fascinated by the possibility of promoting electron transfer for kinetically unfavorable glucose oxidation reactions at a lower overpotential and thus improving the selectivity of the electrode for glucose in electroanalysis. The morphologies of CuO/C-NFs and CuO/NiO-NFs were characterized by scanning electron microscopy(SEM) and X-ray powder diffraction(XRD). The electrocatalytic performances of glucose were evaluated in detail by cyclic voltammetry(CV) and chronoamperometry. Facile charge transport, enhanced current response(at a lower overpotential of +0.35 V), improved stability and selectivity, as well as excellent resistance towards electrode fouling were observed at CuO/C-NFs electrode in direct glucose electroanalysis. These merits are attributed to the highly porous three-dimensional network film structure of CuO/C-NFs electrode materials and the potential synergic catalytic effect of CuO and carbon nanotubes in composite nanofibers. This study may provide a new insight into metal oxide-based composite nanofibers obtained via electrospinning for fabricating novel and high performance sensors and devices.

A novel colorimetric aptasensor was developed for thrombin detection with high sensitivity and specificity. The assay takes the advantage of Au nanoparticles-DNAzyme as a dual catalytic system for signal amplification. Au nanparticles were modified with peroxidase mimicking DNAzyme sequence as well as thrombin binding aptamer. And then the thrombin binding aptamer hybridized with its complementary sequence which was immobilized on the surface of the magnetic nanoparticles to construct the colorimetric aptasensor. In the presence of thrombin, the target-induced displacement takes place, resulting in the dissociation of the aptasensor. The DNAzyme functioned Au NPs are released due to the combine ability of thrombin binding aptamer with thrombin. The released Au NPs are capable of catalyzing the colorless 2,2′-azino-bis(3-ethylbenzothiazoline)-6-sulfonic acid(ABTS) conversion into a blue-green product by H₂O₂-mediated oxidation, thus can amplify the colorimetric readout signals of thrombin detection. Such a device can serve as a novel selectivity sensor for thrombin with a detection limit of 0.6 nmol/L.

The calix[4]arene-based podands which incorporates two terpyridinyl functional groups derived from the alkylation reactions of 4-(ω-chloroalkoxyphenyl)-2,2′:6′,2″-terpyridine in 1,3-alternate position at lower rim have been prepared in moderate yields. The structures of four pyridyl compounds were determined by X-ray single crystal diffraction method. The complexing properties of bis-terpyridinyl-calix[4]arenes for transition metal ions were investigated by fluorescence spectra. Bis-terpyridinyl-calix[4]arenes gave a more efficient fluorescent sensing ability to Zn²⁺.

A facile and efficient protocol for the synthesis of 3,4-dihydropyrimidones via one-pot Biginelli reaction in PEG₁₀₀₀-DAIL/toluene system was developed. PEG₁₀₀₀-DAIL/toluene mixture is a temperature-driven reversible biphasic system, which promises the fully display of catalytic activity and simple recycle of PEG₁₀₀₀-DAIL. As a result, PEG₁₀₀₀-DAIL/toluene mixture showed catalyst-medium double-duty in the Biginelli reaction and afforded corresponding 3,4-dihydropyrimidones in excellent yields of 80%–95% for 20 examples. No obvious loss of catalytic activity was observed even after 10 recycling runs.

Two new natural methoxyflavonoids and two known methoxyflavonoids were isolated from the ethanol fraction of the leaves of Murraya paniculata (L.) Jack. The two new natural methoxyflavonoids were elucidated as 2′-hydroxy-3,4,5,3′,4′,6′-hexamethoxychalcone(1) and 6,7,8,3′,4′-pentamethoxyflavanone(2) on the basis of ¹³C NMR and mass spectra. The two known methoxyflavonoids were identified as 3′-hydroxy-5,7,4′-trimethoxyflavone(3) and 2′-hydroxy-3, 4, 4′, 6′-tetramethoxychalcone(4).

A new series of physostigmine analogues 3a—3j with modifications at the C3a and C5 positions was designed and synthesized. Bioassay of the synthetic analogues 3a—3j, along with the previous synthesized C3a-ethyl-C5-triazole physostigmine analogues 1a—1g and 2a—2j was performed, which indicates that the replacement of the carbamoyl moiety of C3a-ethyl-C5-triazole analogues 1 and 2 with a triazole moiety decreased acetylcholinesterase(AchE) inhibitory activity, whereas the introduction of heterocycles into the triazole ring increased both AChE and butyrylcholinesterase(BchE) inhibitory activities. Structure-activity relationship(SAR) studies of C3a-methyl-C5-triazole analogues 3 reveal the C3a-methyl substituent is important for AChE and BChE inhibition and the introduction of a second ionizable N center improved the binding of the synthetic analogues to both AChE and BChE.

Chiral alcohols(3, 5) were synthesized in optically pure forms from easily available rosin acid in short-steps. A comprehensive protocol for the enantiomeric excess assays of mono-or di-functional-grouped chiral secondary amine or alcohol has been established with them used as chiral auxiliary for chiral phosphorus derivatizing agents(CPDAs) in ³¹P NMR tests. Chemical shift difference(Δδ _P) values ranging from 4.5 to 0.15 between two diastereoisomers of the CPDAs and the aryl substrates were obtained. Positive Δδ _R-S was observed for all the tested alcohol P(III) and P(V) derivatives, while negative Δδ _R-S was observed for all the amines.

A series of novel 1-substituted phenyl or glycosyl 1,2,3-triazoles was designed and synthesized by azide-alkyne 1,3-dipolar cycloaddition between 4,6-dimethoxy-2-[4-prop-2-ynyl)piperazin-1-yl] pyrimidine and each of different azides catalysed by in situ generated Cu(I). The O-acyl protecting groups on glycosyl 1,2,3-triazoles were removed by triethylamine in wet methanol. Their chemical structures were established on the basis of corresponding ¹H NMR, ¹³C NMR, MS and elemental analysis. The fungicidal activities of target compounds were evaluated in vitro against Fusarium omysporum, Physalospora piricola, Alternaria solani, Phytophthora capsici, Cercospora arachidicola and Gibberella zeae at 50 μg/mL. The bioassay results indicate that some of the compounds exhibited moderate but promising fungicidal activities. In particular, acetylated glucopyranosyl triazole displayed a good fungicidal activity against Physalospora piricola, which is equal to that of the positive control compound chlorothalonil.

A novel series of first procaspase activating compound(PAC-1) analogues was designed, synthesized and evaluated for antitumor activity towards two cell lines[human promyelocytic leukemia cell line(HL60) and human embryonic lung fibroblast cell line(HLF)] by the MTT[3-(4,5)-dimethylthiahiazo(-z-y1)-3,5-di-phenytetrazo-liumromide]_method in vitro. The structures of all the compounds were confirmed by ¹H NMR, MS and elemental analysis. Among the compounds synthesized,(E)-2-[(3-{[4-(tert-butyl)benzyl](methyl)amino}propyl)(methyl)amino]-N′-[4-(diethylamino)-2-hydroxybenzylidene]acetohydrazide(compound 6n) exhibits a good anti-proliferative activity to the majority of tumor cells tested, and selectively cleaves cancer cells. Thus, compound 6n was identified as promising lead compound for further structural modification.

The androgen receptor(AR) signaling activated by dihydrotestosterone(DHT) plays critical roles in prostate cancer development and progression. Phytoestrogens, which are diphenolic compounds with estrogen and antiestrogen effects, can bind to estrogen receptors. However, their function on AR signaling has not been fully elucidated. In this study, dual-luciferase reporter assay, immunobloting, docking system test, MTT assay, immunofluorescence and chromatin immunoprecipitation(ChIP) assays were employed to examine the potential effects of three phytoestrogens(genistein, daidzein, flavone) on DHT-activated prostate specific antigen(PSA) activation, cell proliferation and AR transactivation in lymph node carcinoma of prostate(LNCaP) cells. Phytoestrogens were detected to down-regulate DHT-activated AR-mediated PSA promoter transactivation by dual-luciferase reporter system. Furthermore, three phytoestrogens, especially genistein, were demonstrated to significantly decrease AR-activated PSA protein expression by Western blotting analysis. MTT experiment proves that phytoestrogens, especially genistein, remarkably inhibits the DHT-induced cell proliferation in LNCaP cells. To provide reasonable explanations for experimental phenomena mentioned above, we did docking system test and detected phytoestrogens to share the same AR-binding site with DHT. To further prove the competition between phytoestrogen and DHT on AR binding, we examined the effects of phytoestrogens on DHT-activated AR nuclear translocation and immunofluorescence analysis which confirms that phytoestrogens, especially genistein, inhibit DHT-activated androgen receptor nuclear translocation. Results from ChIP show that phytoestrogens down-regulate DHT-induces AR binding to the androgen response elements(AREs, including AREI, AREII, and AREIII) in PSA promoter. Genistein remarkably down-regulates AR, binding to the AREI located in −250— −39 bp and AREIII in −4170— −3978 bp in the presence of DHT. In general, three phytoestrogens were identified to inhibit DHT-AR binding by competitively binding to AR and inhibit AR-mediated transactivation. And genistein shows the strongest effects among three phytoestrogens. Our findings confirm that phytoestrogens are AR antagonist in the regulation of AR-related PSA activation and cell proliferation, which provides valuable insights into the treatment of prostate cancer.

Two thermostable glucoamylases were produced from Aspergillus niger B-30 by submerged fermentation. The two glucoamylases GAM-1 and GAM-2 were purified by ammonium sulfate precipitation, diethylaminoethyl-cellulose fast flow(DEAE FF) and Superdex G-75 gel filtration columns. The molecular weights of GAM-1 and GAM-2 were determined as 9.72×10⁴ and 7.83×10⁴ by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), while the molecular weights of GAM-1 and GAM-2 were determined to be 8.05×10⁴ and 7.04×10⁴ by matrix assisted laser desorption ionizationtime-of-flight(MALDI-TOF) mass spectrometry, respectively. Both the enzymes were glycosylated, with 10.4% and 11.4% carbohydrate content, respectively. The optimal pH and temperature were 4.0–4.6 and 70 °C for both. The two glucoamylases were maintained 100% relative activity after incubation at 60 °C for 120 min. After the hydrolysis of starch for 120 min, glucose was the only product, confirming that the two enzymes were of high efficiency towards starch. The GAM-2 exhibited higher catalytic activity towards oligosaccharides such as maltose than GAM-1, and the kinetic analysis shows that the affinity of GAM-2 to starch was lower than that of GAM-1. The high thermostability and effectiveness make the two glucoamylases potentially attractive for biotechnological application.

Biochemical techniques including ion-exchange chromatography, gel filtration chromatography and reversed-phase high-performance liquid chromatography(RP-HPLC) were used to isolate and purify the natural polypeptide from velvet antler(nVAP) of Cervus elaphus (C. elaphus), which has a molecular weight of 3215.8 and the primary structure of VLSAADKSNVKAAWGKVGGNAPAFGAEALLRM. The homology of the protein sequence in nVAP with known protein sequence is less than 50%, suggesting that nVAP appears to be a new bioactive substance. At a level of 0.4–50 μg/mL, nVAP promotes mitosis in epidermal cells, chondrocytes and NIH3T3 fibroblasts primarily cultured in a significant way. Given that a yield of high-purity nVAP isolated from C. elaphus is 0.001%, nVAP is artificially synthesized to prepare synthetic velvet antler polypeptide(sVAP) according to its primary structure. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis(SDS-PAGE) of sVAP shows a single band, and its HPLC spectrum displays a single peak. The matrix-assisted laser desorption ionization time-of-flight mass spectrometry(MALDI-TOF-MS) was used to identify sVAP to be of a molecular weight of 3200 and the consistency between primary structures of sVAP and nVAP. Bioactivity test shows that at a dose of 5–40 μg/mL, sVAP promotes the proliferation of primarily cultured epidermal cells and NIH3T3 cell line. From the traditional Chinese medicine theory, velvet antler from Cervus nippon (C. nippon) and velvet antler from C. elaphus are considered as the same medicine, but differences between biochemical base and pharmacological effect of these two velvet antlers have been observed. We compared the total polypeptide mapping of the two velvet antlers, discovering that nVAP is active polypeptide and only exists in the velvet antler of C. elaphus. sVAP is similar to nVAP in physicochemical property and biological activity. These studies extend the possible utility of sVAP to be the promising compound to prepare velvet antler polypeptide of C. elaphus.

The assembly of gold nanorods(GNRs) into different liquid crystalline structures can be controlled by tuning their surface electric potential. After mildly removing excess surfactants in the GNRs solution, the electrostatic interaction between GNRs can be tuned by adjusting counter ion concentration. Specifically, nematic and smectic structures formed after solvent evaporation at low and high bromide concentrations, respectively. These results could be helpful for fabricating anisotropy enabled devices composed of metal and semiconductor nanorods.

This research reveals the phylogenetic history and structural information of the hemagglutinin(HA) and neuraminidase(NA) from novel avian influenza virus A/Hangzhou/1/2013(H7N9_2013) strain from human infected in China. Strains closely related to the H7N9_2013 strain were obtained from Nation Center for Biotechnology Information(USA)-basic local alignment search tool(NCBI-BLAST) searching, and the phylogenetic trees were constructed. The 3D structures of HA and NA from H7N9_2013 strain were built by homology modeling technology, and molecular dynamics(MD) simulations were performed on the high-performance computer cluster. Characteristic amino acid sites were then screened from multiple sequence alignment(MSA) via home-made Python script and mapped onto the 3D structures. The thermodynamic characteristic root-mean-square-fluctuation (RMSF) of these sites in the structure was also analyzed with MD trajectories. The HA of H7N9_2013 strain is closely related to the A/duck/Zhejiang/12/2011 strain isolated in China, while the NA of H7N9_2013 strain is mostly related to the A/mallard/Czech Republic/13438-29K/2010 strain isolated in Europe. The 3D structures of HA and NA from H7N9_2013 stain are mostly identical to the existing structure of H7 and N9. A total of 11 and 14 characteristic amino acid sites were identified in HA and NA, respectively, in H7N9_2013. Structural analysis indicates that certain sites in the top region of HA are important, at which the mutation of some amino acids can impact the receptor binding that may be related to its infection of human beings.

Cylindrical coconut activated carbon(CCAC) support was graphitized at a high temperature(1900 °C) in argon, then oxidized with an O₂-N₂-H₂O mixture, and treated with nitric acid. Pretreatment of carbon support on its mechanical strength, physical structure, chemical composition and surface properties of cylindrical CCAC support was investigated by X-ray diffraction(XRD), surface area analysis, scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), thermogravimetric-differential thermogravimetric(TG-DTG) analysis and temperature programmed desorption-mass spectrometry(TPD-MS), and the effect of CCAC support on the catalytic activities was also studied. The results show that the degree of graphitization, the purity(phosphorus, sulphur), pore structure(micropore, mesopore) and oxygen-containing functional groups(—COOH, —OH, —COOR) of carbon supports are obviously different, which have a great influence on the performance of Ru-based catalysts. After a series of pretreatments, the surface physical and chemical properties of the commercial CCAC are modified and improved, and the activity of as-prepared Ru/AC catalyst is increased significantly.

A method was developed to treat the result from an antioxidant trapping radicals including 2,2′-azinobis (3-ethylbenzothiazoline-6-sulfonate) cationic radical(ABTS^+·), 2,2′-diphenyl-1-picrylhydrazyl radical(DPPH), and galvinoxyl radical. In the presence of a certain concentration of an antioxidant, the decrease of the concentration of a kind of radicals follows the second order exponential function with the increase of the reaction time(t), viz., [radical]=Ae^−t/a+Be^−t/b+C, the derivation operation of which obtains the differential style, −d[radical]/dt= (A/a)e^−t/a+(B/b)e^−t/b, revealing the relationship between the reaction rate(r=-d[radical]/dt) and the reaction time(t). Thus, the reaction rate at the beginning of the reaction(r ₀) can be calculated by assigning t=0 in the equation of -d[radical]/dt-t. Based on the concept of the reaction rate, r=k[radical][antioxidant], the rate constant(k) can be calculated based on r ₀ and the initial concentrations of radical and antioxidant, k=r ₀/([radical]₀[antioxidant]₀). The k means the rate of a fresh antioxidant molecule to trap a fresh radical. This method was used to treat the interactions of ABTS^+·, DPPH, and galvinoxyl radicals with three homoisoflavonoids, four pyrazoles, and three ferrocenyl Schiff bases. It was found that ferrocenyl group is beneficial for antioxidants to reduce ABTS^+·, and ortho-hydroxyl group is beneficial for antioxidants to donate hydrogen atom in phenolic hydroxyl group to DPPH and galvinoxyl radicals.

A series of PdNi/Al₂O₃ catalysts with different compositions was prepared by co-reduction method. The influence of Ni amount on the catalytic combustion of methane was studied. X-ray diffractometry and X-ray photo-electron spectroscopy were employed to characterize the dispersion and electronic state of the active phase. Temperature-programmed oxidation was carried out to study the thermal stability affected by Ni doping. It has been demonstrated that Ni addition changed particle size and oxidation state of PdO _x. The results indicate that the promotion of Ni to the Pd/Al₂O₃ resulted from both size effect and electronic effect. In addition, the thermal stability of the Ni-doped catalysts were enhanced.

Theoretical studies of stereodynamics for reaction LiH(ν=0, j=0)+H→Li+H₂ have been carried out with quasiclassical trajectory method on two potential energy surfaces(PESs) structured as W-PES and P-PES. The main difference of the two PESs is at fixed angle of Li-H-H from 110° to 180°. In this angle range, there is an early-staged energy barrier on the P-PES, but there is no barrier on the W-PES. Some studies have been done to explore the influence of the early-staged energy barrier on this exothermic reaction. Integral cross sections, differential cross sections and product rotational angular momentum of the reaction have been calculated. When E _c<0.48 eV, the dominant influence of barrier is to restrain reacting. However, when E _c>0.48 eV, the dominant influence of barrier is to promote reacting. The angular distribution of the product H₂ is extremely forward on both the PESs, because the lifetime of most complexes is short. Totally, the lifetime on the P-PES is longer than that on W-PES for the existence of the barrier. With the collision energy increasing, on the both PESs, the distribution of the direction of the product H₂ angular momentum changed, and there is a trend that peak at (90°,270°) gets weaker and peak at (90°,90°) gets stronger. The energy barrier weakens the degree of the rotation alignment of the H₂.

Theoretical study about the magnetic properties of conjugated organic molecules containing borepin with π current density was carried out. 1-(2,4,6-Trimethylphenyl)borepin moiety is the center and other different groups are situated on the both β sides, which are named molecules 1–12 as theoretical model in order to establish the relationship between aromaticity and geometry variation of borepin. The optimized molecular structures of molecules 1–12 are almost keeping planar and the C2–C3 bond length of borepin turns longer from molecule 1 to molecule 12. Different borepin-annulated ring could change the conjugated effect of π-electron between borepin and these bore-pin-annulated rings. Moreover, the molecule presents antiaromaticity, in other words, the molecule became unstable when the C2–C3 bond length of borepin extended more than ca. 0.1417 nm. But the β position fragment and substituent groups of borepin are not affected in this case, they are still steady. However, the central borepin ring current is counteracted by symmetrical overlap of it with affiliated borepin-annulated ring current. Hence, the central borepin ring breaking would be liable to occur. These molecules have higher vertical ionization potentials(VIPs) and lower vertical electron affinities(VEAs), which suggests that these molecules could easily exist in anionic form.

Butterfly-like calcium carbonate(CaCO₃) particles were successfully prepared via a facile precipitation reaction of Na₂CO₃ with CaCl₂ in the presence of sodium polyacrylate(PAAS). The as-prepared samples were characterized with field emission scanning electron microscopy(FESEM), X-ray diffraction(XRD) and Fourier transform infrared spectroscopy(FTIR). Butterfly-like CaCO₃ particles composed of three segment rods were obtained. Rod aggregates would act as the template for butterfly-like CaCO₃ crystals consisted of regular shaped crystallites with 150–200 nm in diameter. The influences of reaction temperature, the amount of PAAS and reaction time on the nucleation and growth of CaCO₃ crystals were investigated. The possible growth mechanism of CaCO₃ crystals was discussed. This research can not only make us further understand the general principles of the reaction, but also open up a new avenue of industrial production of CaCO₃ particles with exquisite and unique morphologies.

We studied the excitation energies of zinc porphyrin(ZnP) and zinc porphyrin analogues(ZnP-R) with long-range corrected(LC) density functional theory. We compared three recent LC functionals, wB97XD, CAM-B3LYP, LC-wPBE and functionals B3LYP with the experiments. It was found that the low energy excitation is well predicted for ZnP with the LC-wPBE functional based on 6-31G(d) basis set. Excited-state geometry optimizations for all the compounds were carried out. It was shown that upon the photo-excitation nearly 1 e transferred to the acceptor unit[dodecafluorosubphthalocyanine, SubPc(F)₁₂] and a highly polarized state formed in compound 5. But after the relaxation of the first excited state, the electron on the acceptor went back to the ZnP a little and then shifted from ZnP to the donor segment[bis(4-hexylphenyl)amino] partially. The computed excited-state radiative lifetime(τ) for compound 5 is 943 μs, which shows a reasonable agreement with the experimental observation. According to the long-lived exciton in strong push-pull compound 5, we proposed that electron injection to semiconductor might occur after vibrational relaxation of excited state.

We analyzed the excited-state structures and emission spectra of firefly emitter, the anionic keto form of firefly oxyluciferin(keto-1), determined by the time dependent-density functional theory(TD-DFT) approach. The analysis is based on a direct comparison with the highly correlated CASSCF(MS-CASPT2) ab initio approach. 49 DFT functionals were considered and applied to the study. Among the tested functionals, mPW3PBE, B3PW91 and B3P86 give the best performance for ground-state geometry, absorption spectrum, excite-state geometry and emission spectrum.

Direct transformation of ethanol to ethyl acetate was investigated on a series of Cu(ZrO₂)/SiO₂ catalysts. Inductively coupled plasma(ICP), surface area analysis, X-ray diffraction(XRD), H₂-temperature programmed reduction(H₂-TPR), X-ray photoelectron spectroscopy(XPS), NH₃-temperature programmed desorption(NH3-TPD) and Fourier transform-infrared spectroscopy(FTIR) techniques were used to characterize the catalysts. The results reveal that ZrO₂ can improve the dispersion of copper species and increase the acidity of the Cu(ZrO₂)/SiO₂ catalysts. The Cu₀ is responsible for ethanol dehydrogenation to acetaldehyde, and both the Lewis acid and Brønsted acid sites were in favor of the selectivity to ethyl acetate. The synergistic effect of Cu₀ and an appropriate amount of acidic sites played an important role in the production of ethyl acetate.

The authors made the electrochemical studies on the electrode processes during copper electrodeposition with ionic liquids-reline as an electrolytic medium. Reline is a commercial name for a eutectic mixture of choline chloride and urea(1:2, molar ratio). This new proposed method of copper deposition is an ecological one because the ionic liquids are recyclable, non-volatile and non-toxic. Cyclic voltammetry investigations were conducted at 343 and 353 K in choline chloride-urea(Reline) deep eutectic solvent with single salt CuCl(generally in 0.05–0.38 mol/L concentration range). Electrochemical impedance spectroscopy investigations were conducted in choline chlorideurea ionic liquid with CuCl(0.05 mol/L). We investigated both cathodic and anodic processes of Cu⁺ ions at different sweep rates in this new electrolytic system based on choline chloride. We have proposed by this an alternative to the classical copper electrodeposition. Coefficient of diffusion, D ₀, for the system Reline-CuCl is presented and the value of D ₀ is 1.22×10⁻⁸ cm²/s.

Nanocrystal N-Zn-Ag/TiO₂ powders were prepared with N-Zn/TiO₂ by photo deposition method. A series of pure polymers P3HT[poly(3-hexylthiophene)], P3OT[poly(3-octylthiophene)], P3DT[poly(3-decylthiophene)] and P3DDT[poly(3-dodecylthiophene)], was synthesized, which were used to synthesize p-n type semiconductor materials P3HT/N-Zn-Ag-TiO₂, P3OT/N-Zn-Ag-TiO₂, P3DT/N-Zn-Ag-TiO₂ and P3DDT/N-Zn-Ag-TiO₂ by in situ chemical method. X-Ray diffraction(XRD) and infrared(IR) spectroscopy showed the structure of the polymers and complexes. Ultraviolet-visible(UV-Vis) spectra and cyclic voltammograms(CV) showed the optical and electronic performance of the polymers and complexes. Two new single and double organic thin film heterojunction solar cells were prepared with the above mentioned synthesized powders as raw materials. Current-voltage(I–V) measurements indicate that the conversion efficiency of the single organic thin film heterojunction solar cell is higher than that of the double organic thin film heterojunction solar cells. Single organic thin film heterojunction solar cells based on P3DT/N-Zn-Ag-TiO₂ can get a photoelectric conversion efficiency of 0.0408%. The performance of electronic transform between electron donor and acceptor on organic thin film solar cells was researched.

Novel poly(lactide-co-glycolide acid)(PLGA) microspheres were developed for sustained delivery of antisense oligonucleotide(ASO). First, a new cationic agent, polyethylenimine(PEI) conjugated to linoleic acid(LA)(PEI-LA) was synthesized by reacting PEI(M _w=800) with linoleoyl chloride. Then, PEI-LA was combined with LOR-2501 to form electrostatic complexes at moderate nitrogen-to-phosphate(N/P) molar ratios which were then encapsulated into poly(lactide-co-glycolide) microspheres by a multiple emulsion-solvent evaporation technique. With an increase in ASO/PEI-LA concentration from 5% to 10%, encapsulation efficiency of ASO in the microspheres reduced from 72.14% to 57.62%, and the particle size of microspheres increased from 28.58 μm to 34.76 μm. In vitro studies show that the release profile of ASO from microspheres prepared at 7.5% ASO-PEI-LA lasted for 14 d. The novel microspheres have a potential use as a sustained release vehicle for ASO.

The authors prepared large area surface-enhanced Raman scattering(SERS) active substrates with tunable enhancement. First the large area gratings were fabricated by scanning a photoresist with two-beam laser interference and subsequently they were coated with silver nano islands via vacuum evaporation. SERS active metal island grating substrates with four different periods(300, 400, 515 and 600 nm) and Ag nano islands uniformly coated on an area of 2.5 cm×0.5 cm were obtained. The measured SERS spectra reveal the tuning effect of the period on the Raman signals period. The highest enhancement(ca. 10⁵) for Rhodamine 6G(R6G) as probing molecule is associated with a period of 515 nm due to the perfect matching of surface plasmons and Raman excitation line. A good reproducibility of SERS signals with almost the same SERS intensity at different spots was observed on all the larger area Ag island grating substrates.

Polyacrylonitrile(PAN)-based activated carbon fiber(PACF) supporting nano-ZnO(PACF/nano-ZnO) was prepared by spin, pretreatment, carbonization, and KOH chemical activation at an activation temperature of 950 °C for 40 min. Nano-ZnO content, distribution and antibacterial properties of the PACF/nano-ZnO were studied. The pore structure and surface properties of the PACF/nano-ZnO were studied by Brunauer-Emmett-Teller(BET), N₂/77 K isothermal adsorption. The specific surface area increased markedly after the activation process and it was several hundred times greater than that before the process. The PACF/nano-ZnO shows a strong adsorption for Staphylococcus aureus(S. aureus) and Escherichia coli(E. coli) and antibacterial activity against them. As an experimental result, antibacterial properties of PACF/nano-ZnO increased with increasing the concentration of nano-ZnO particles, which suggests it is a promising antibacterial material.

Point mutations on membrane proteins may lead to small structural variations. Prediction of such structural variations can help to further understand the related bio-activities of membrane proteins. We constructed fifteen hybrid energy functions on the basis of Chemistry at Harvard Macromolecular Mechanics(CHARMM) force field, hydrogen bonding potential and distance-scaled, finite ideal-gas reference(DFIRE)-like statistical energies, and evaluated their performance on a representative dataset of homologous membrane proteins via a newly developed all-atom replica exchange Monte Carlo algorithm. The energy function composed of CHARMM and hydrogen bonding potential has the best performance, and the original DFIRE potential shows much better performance than the DFIRE-like potentials constructed from membrane proteins. We can conclude that more membrane protein structures with high resolution are necessary for the construction of robust prediction method of mutation induced membrane protein structure variations.

Temperature dependence of chain conformation and local rigidity of two soluble isomerized polyimides (PIs), poly(hexafluorodianhydride/3,3′-dimethylbenzidine)[poly(6FDA/3,3′-DMB)] and poly(hexafluorodianhy-dride/2,2′-dimethylbenzidine)[poly(6FDA/2,2′-DMB)] were investigated by dilute solution viscosity, size exclusion chromatography(SEC) coupled with multi-angle laser light scattering, viscometer, and refractive index detector in dimethylformamide(DMF) with either 0.1 mol/L LiBr or 3.1 mmol/L tetrabutylammonium bromide(TBAB) in the temperature range of 30 to 50 °C. The scaling relationships of [η]=K _η M ^α and R _g=K _g M ^ν obtained are employed to investigate the temperature dependence of chain conformation for the two polyimides. The values of α and ν are in the range of 0.66–0.69 and 0.53–0.56, respectively, for poly(6FDA/3,3′-DMB), meanwhile they are in the range of 0.64–0.68 and 0.53–0.56, respectively, for poly(6FDA/2,2′-DMB). These results reveal that random coil conformations for both PIs are not affected visibly with increasing temperature from 30 °C to 50 °C. However, values of more exact intrinsic viscosity from dilute solution measurement indicate there is only tiny coil extension or shrinkage for both PIs with temperature rising. Parameters related to chain flexibility of polymer, including persistence length l _p, shift factor M _L(relative molecular weight per unit contour length) and backbone diameter d are estimated from the relationship between intrinsic viscosity and molecular weight for the continuous wormlike cylinder model, which indicates that two samples are flexible chains, only the chain of poly(6FDA/3,3′-DMB) is stiffer than that of poly(6FDA/2,2′-DMB) slightly.