Growth of Carbon Nanotubes over Ni Nano-particles Prepared in Situ by Reduction of La2NiO4 Oxides

Carbonnanotubes(CNTs),theallotropeofcarbon,haveattractedmuchspeculationfortheirextraordinarypropertiesandpotentialapplicationssincetheywerediscoveredl.NowthesynthesisofCNTsisoneofthechallengingissuesinthenewcarbonmaterialsfield.ThecatalyticproductionofCNTsissimplerandmorereproduciblethanothermethods2*3.Inthepresentwork,weobtainedgroWthofCNTsbycatalyticdisproportionationofCOoverNinano-particlespreparedbyreducingLa2NiO..Therareearthoxidescanpreventtransitionmetalfromagglomefatingandpromo…     

Liquid Phase Hydrogenolysis of Biomass‐derived Lactate to 1,2‐Propanediol over Silica Supported Cobalt Nanocatalyst

Liquid phase hydrogenolysis of ethyl lactate to 1,2‐propanediol was performed over silica supporting cobalt catalysts prepared by two different methods: precipitation‐gel (PG) technique and deposition‐precipitation (DP) procedure. The cobalt species (Co₃O₄/cobalt phyllosilicate) present in the corresponding calcined PG and DP catalysts were different as a consequence of the preparation methods, and Co OH Co olation and Si O Co oxolation molecular mechanisms were employed to elucidate the chemical phenomena during the different preparation procedures. In addition, the texture (BET), reduction behavior (TPR and in‐situ XRD), surface dispersion and state of cobalt species (XPS), and catalytic performance differ greatly between the samples. Because of small particle size, high dispersion of cobalt species and facile reducibility, the Co/SiO₂ catalyst prepared by precipitation‐gel method presented a much higher activity than the catalyst prepared by deposition‐precipitation method. Metallic cobalt is assumed to be the catalytically active site for the hydrogenolysis reaction according to the catalytic results of both cobalt samples reduced at different temperatures and the structure changes after reaction.     

Storage Stability of LiFePO4/C in Humid‐hot Air

Storage stabilities of LiFePO₄/C composite at different conditions are investigated in terms of structural and electrochemical evolutions. The results from different aging tests indicate that moisture and temperature are the key factors that have the most profound effects on the structure homogeneity which in turn influences the electrochemical performance of LiFePO₄/C. Although the storage in a humid‐hot environment, such as saturated humidity air at 50°C, does not greatly influence the discharging capacity of LiFePO₄/C, it does reduce the initial charging capacity, thus the amount of reversible Li⁺ ions in a practical LiFePO₄/graphite cell decreases. This impact is explained by the lithium extraction during the storage, forming olivine FePO₄ and associated Li₃PO₄. Elevated storage temperature also favors the delithiation process. The degree of delithiation increases from about 6% at 50°C to 18% at 80°C. It is also found that re‐calcination at 650°C effectively resolves the problem of the structural heterogeneity of the stored LiFePO₄/C. Therefore both the initial charging capacity and coulombic efficiency of the stored sample in the first cycle revert to the original value of the fresh one.     

Determination of adefovir in human plasma by liquid chromatography/tandem mass spectrometry: application to a pharmacokinetic study

A liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed and validated to determine the concentrations of adefovir [9-(2-phosphonylmethoxyethyl)adenine, PMEA] in human plasma. After one-step protein precipitation of plasma samples by methanol, adefovir was analyzed by LC/MS/MS using positive electrospray ionization. Chromatography was performed on a C18 column. The extraction recoveries of adefovir were found to be 85.1-89.3%. Adefovir was stable under routine laboratory conditions. A minimal matrix effect resulting in a slight ionization enhancement of adefovir (<10.9%) was observed, which did not markedly affect the behavior of the calibrations curves and accuracy and precision data. The method had a chromatographic run time of 7.8 min and a linear calibration curve over the concentration range 1.5-90 ng/mL for adefovir. The lower limit of quantification of the method was 1.5 ng/mL. The intra- and inter-day precision was less than 8.4%. These results indicated that this LC/MS/MS method has high selectivity and efficiency, and acceptable accuracy, precision and sensitivity. The validated LC/MS/MS method has been successfully used in a pharmacokinetic study in healthy volunteers treated with oral adefovir dipivoxil at 10 and 20 mg.     

Time-resolved resonance Raman and density functional theory study of the deprotonation reaction of the triplet state of p-hydroxyacetophenone in water solution

[reaction; see text] Picosecond and nanosecond time-resolved resonance Raman (TR(3)) spectroscopy was employed to investigate the deprotonation/ionization reaction of p-hydroxyacetophenone (HA) after ultraviolet photolysis in water solution. The TR(3) spectra in conjunction with density functional theory (DFT) calculations were used to characterize the structure and dynamics of the excited-state HA deprotonation to form HA anions in near neutral water solvent. DFT calculations based on a solute-solvent intermolecular H-bonded complex model containing up to three water molecules were used to evaluate the H-bond interactions and their influence on the deprotonation reaction and the structures of the intermediates. The deprotonation reaction was found to occur on the triplet manifold with a planar H-bonded HA triplet complex as the precursor species. The HA triplet species is generated within several picoseconds and then decays with a approximately 10 ns time constant to produce the HA triplet anion species after 267 nm photolysis of HA in water solution. The triplet anion species was observed to decay with a time constant of about 90 ns into the ground-state anion species that was found to have a lifetime of about 200 ns. The DFT calculations on the H-bonded complexes of the anion triplet and ground-states species suggest that these anion species are H-bonded complexes with planar quinonoidal structures containing two water molecules H-bonded, respectively, with oxygen lone pairs of the carbonyl and deprotonated hydroxyl moieties. A deactivation scheme of the photoexcited HA in regard to the deprotonation reaction in neutral water solutions was proposed. With the above dynamic and structural information available, we briefly discuss the possible implications of the model HA photochemistry in water solutions for the photodeprotection reactions of related p-HP phototrigger compounds in aqueous solutions.     

含均苯四甲酸二酰亚胺受体单元的共轭高分子的合成及其在有机太阳能电池上的应用

通过Stille反应合成了一系列含有均苯四甲酸二酰亚胺受体单元的共轭聚合物P1～P7.该系列聚合物在常见有机溶剂中溶解性良好,在370～600 nm范围内有较强吸收.通过循环伏安法测量其LUMO能级范围在-3.66～-3.90 eV之间,HOMO能级在-5.25～-6.17 eV之间,在同类分子中接近最低值.通过改变主链中噻吩单元的数量和给电子单元,可以调节分子的能隙,使其电化学能隙在2.45～1.55 eV范围内变化.将含均苯四甲酸二酰亚胺受体单元的P1～P7应用于有机太阳能电池中,作为给体材料与PC61BM共混制成本体异质结聚合物电池,器件开路电压普遍较高.其中基于均苯四甲酸二酰亚胺与二噻吩并噻咯的聚合物P7的器件,在AM 1.5 G,86 mW/cm2光照条件下,开路电压为0.72 V,短路电流为1.22 mA/cm2,能量转换效率为0.27%.     

First total synthesis of four natural prenylated flavonoids

A facile approach for the first total synthesis of prenylated flavonoids,(±)-abyssinone-Vl-4-O-methyl ether 1,(±)-abyssinoneIV -4’-O-methyl ether 2,(±)-abyssinone-V-4’-O-methyl ether 3 and(±)-sigmoidin E 4 has been described.The key intermediate 4-hydroxy-3,5-di-(3-methylbut-2-enyl)benzaldehyde 6 was also first synthesized that features regioselective prenylation of 4-hydroxybenzaldehyde and crystallizing with petroleum ether from the reaction mixture by freeze-out effect.     

氟代苯阳离子的理论研究

用B3LYP方法及6-311G(d,p)和6-311 G(d,p)基组,对十二种氟代苯阳离子做了理论研究,优化了它们的电子基态的结构,计算了对应分子的垂直电离势(VIP)和绝热电离势(AIP)．依据Jahn．Teller理论,计算确定了1,3,5-C6H3F^ 3和C6F^ 6离子分别具有C2v(2↑B)和D2h(2↑B2g)结构(对应分子分别为D3h和D6h结构)．其余十个离子的构型的对称点群与对应分子相同,但构型参数值有明显差别．自然布居分析计算表明这些离子的正电荷主要分布在与F原子相连的C原子和各H原子上．B3LYP／6-311 G(d,p)级别上计算的各氟代苯分子的VIP和AIP值和实验值符合得很好．     

Highly photoluminescent MoOx quantum dots: Facile synthesis and application in off-on Pi sensing in lake water samples

Molybdenum oxide (MoO_x) is a well-studied transition-metal semiconductor material, and has a wider band gap than MoS₂ which makes it become a promising versatile probe in a variety of fields, such as gas sensor, catalysis, energy storage ect. However, few MoO_x nanomaterials possessing photoluminescence have been reported until now, not to mention the application as photoluminescent probes. Herein, a one-pot method is developed for facile synthesis of highly photoluminescent MoO_x quantum dots (MoO_x QDs) in which commercial molybdenum disulfide powder and hydrogen peroxide (H₂O₂) are involved as the precursor and oxidant, respectively. Compared with current synthesis methods, the proposed one has the advantages of rapid, one-pot, easily prepared, environment friendly as well as strong photoluminescence. The obtained MoO_x QDs is further utilized as an efficient photoluminescent probe, and a new off-on sensor has been constructed for phosphate (Pi) determination in complicated lake water samples, attributed to the fact that the binding affinity of Eu³⁺ ions to the oxygen atoms from Pi is much higher than that from the surface of MoO_x QDs. Under the optimal conditions, a good linear relationship was found between the enhanced photoluminescence intensity and Pi concentration in the range of 0.1–160.0 μM with the detection limit of 56 nM (3σ/k). The first application of the photoluminescent MoO_x nanomaterials for ion photochemical sensing will open the gate of employing MoO_x nanomaterials as versatile probes in a variety of fields, such as chemi-/bio-sensor, cell imaging, biomedical and so on.     

浸没沉淀相转化法制备结晶性聚合物微孔膜的研究进展

综述了近期关于结晶性聚合物浸没沉淀相转化法制备微孔膜的成膜机理和实验研究工作.对制膜体系的热力学、相分离、成膜机理进行了分析和总结,并依此解析了结晶性聚合物膜中常见的结构形态,最后从热力学和动力学两个方面对影响膜结构形态的因素如聚合物的浓度、铸膜液的组成、凝固浴的组成等进行了详细的讨论.