Thermodynamic studies of monuron

Monuron (C₉H₁₁ClN₂O; N,N-dimethyl-N′-(4-chlorophenyl) urea, CAS 150-68-5) was synthesized and the heat capacities of the compound were measured in the temperature range from 79 to 385 K with a high precision automated adiabatic calorimeter. No phase transition or thermal anomaly was observed in this range. The enthalpy and entropy data of the compound relative to the reference temperature 298.15 K were derived based on the heat capacity data. The thermodynamic properties of the compound were further investigated through DSC and TG analysis. The melting point, the molar enthalpy, and entropy of fusion were determined to be 447.6±0.1 K, 29.3±0.2 kJ mol⁻¹, and 65.4 J K⁻¹ mol⁻¹, respectively.     

2-(苯并噻唑-2-基)-5-(N,N-二乙基氨基)苯酚衍生物的合成及其对H2S的识别

以4-N,N-二乙基氨基水杨醛为原料,制备了2-(苯并噻唑-2-基)-5-(N,N-二乙基氨基)苯酚衍生物(探针L),并对其结构进行了表征。在DMSO/PBS(体积比3∶7,pH=7.4)溶液中,探针L具有高选择性并可荧光"关-开"识别H_2S,在365nm紫外灯照射下,由无荧光变成蓝色荧光。实验表明,探针L识别H_2S的检测限为2.05×10~(-6)mol/L,pH适用范围为6～9,可用于检测实际水样中的H_2S。     

Self-assembling of helical poly(phenylacetylene) carrying L-valine pendants in solution, on mica substrate, and on water surface

In the present work, we investigated self-assembling of a poly(phenylacetylene) carrying L-valine pendants (PPA-Val) in a water/methanol solution, upon evaporation of the solution on mica, and on the water surface. With intercalation of a fluorescence probe of Ru(phen)2(dppx)2+ (phen = 1,10-phenanthroline, dppx=7,8-dimethyldipyridophenazine) into the hydrophobic cavities associated by the PPA-Val chains, their helical structures were directly detected in solution with an in situ fluorescence microscope. Helical aggregates were observed with AFM upon evaporation of the solvents, suggesting that the helical structures in the solution are the building blocks of the helical aggregates. Self-assembling structures of PPA-Val on the water surface were, however, very different from that formed upon evaporation of its THF solution on the mica surface. The polymer chains associated into a monolayer of extended fibers on the water surface, whereas superhelical fibers formed on the mica surface. Water molecules play a critical role in inducing the polymer to form diverse morphological structures in its bulk solution and on its surface. In solution, the isotropic hydrophobic effect drove the polymer chains to form superhelical aggregates, while on the water surface, the hydrophobic effect concentrated mainly on the lateral part of the polymer, thus giving a monolayer of extended fibers.     

Remarkably enhanced capacitance of ordered polyaniline nanowires tailored by stepwise electrochemical deposition

A stepwise deposition method was employed to create ordered polyaniline (PANI) nanowires with remarkably enhanced capacitance. Cyclic voltammetry, AC impedance, and galvanostatic charge/discharge cycling were employed to investigate the electrochemical performance of the PANI electrodes. The PANI-deposited electrode exhibits much higher capacitance than those prepared by one-step deposition method, which were mainly contributed from the unique nano structure of PANI and the increased biological, economical, and technical surface areas. The superior capacitive behaviors of the nano PANI electrodes show great potential in preparation of high efficient electrochemical capacitors or rechargeable batteries.     

Simultaneous Determination of Four Flavonoids in Pigeonpea [Cajanus cajan (L.) Millsp.] Leaves Using RP-LC-DAD

A simple and accurate RP-HPLC method using photodiode array detection (PAD) was developed for the simultaneous determination of four flavonoids, namely quercetin (QU),luteolin(LU),apigenin(AP) and isorhamnetin (IS) in pigeonpea leaves.Extract samples were separated on HIQ SIL C₁₈V column using methanol-acetonitrile-water(31:10:59, v/v/v) as mobile phase.The flavonoids were detected at 254.5 nm for QU and IS, and at 345 nm for LU and AP.Contents were determined with satisfactory repeatability (R. S. D. < 2.2%) and recovery (97.27 – 99.98%). The developed method was found to be simple and efficient.     

Time‐Resolved Synchrotron Radiation Excited Optical Luminescence: Light‐Emission Properties of Silicon‐Based Nanostructures

The recent advances in the study of light emission from matter induced by synchrotron radiation: X‐ray excited optical luminescence (XEOL) in the energy domain and time‐resolved X‐ray excited optical luminescence (TRXEOL) are described. The development of these element (absorption edge) selective, synchrotron X‐ray photons in, optical photons out techniques with time gating coincide with advances in third‐generation, insertion device based, synchrotron light sources. Electron bunches circulating in a storage ring emit very bright, widely energy tunable, short light pulses (<100 ps), which are used as the excitation source for investigation of light‐emitting materials. Luminescence from silicon nanostructures (porous silicon, silicon nanowires, and Si–CdSe heterostructures) is used to illustrate the applicability of these techniques and their great potential in future applications.     

CO(υ)高振动激发态向C2H2的振动传能研究

用时间分辨富里叶红外发射谱研究了高振动激发态ＣＯ向Ｃ２Ｈ２的传能，得到了ＣＯ（ｖ＝１－３）各振动态布居及其随时间的变化。利用微分法解出弛豫微分方程组，获得ＣＯ（ｖ＝１－３）向Ｃ２Ｈ２的传能速率常数分别为：２．０±０．１，６．０±０．２和９．４±０．８（１０＾－１３ｃｍ＾３·ｍｏｌｅｃｕｌｅ＾－１·ｓ＾－１）。传能速率随着振动量子数的增加而迅速增加。ＣＯ的振动能应向Ｃ２Ｈ２的对称伸缩模ｖ２近共振Ｖ－     

Two-color resonantly enhanced multiphoton ionization and zero-kinetic-energy photoelectron spectroscopy of jet-cooled indan

We report studies of supersonically cooled indan using two-color resonantly enhanced multiphoton ionization and two-color zero-kinetic-energy photoelectron spectroscopy. With the aid of ab initio and density-functional calculations, vibrational modes of the first electronically excited state of the neutral species and those of the cation have been assigned, and the adiabatic ionization energy has been determined to be 68458 +/- 5 cm(-1). Similar to the ground state and the first electronically excited state of the neutral molecule, the ground state of the cation is also proven to be nonplanar, with an estimated barrier of 213 cm(-1) and a puckering angle of 15.0 degrees. These conclusions will be discussed in comparison with a previous study of an indan derivative 1,3-benzodioxole.     

Direct synthesis, characterization of Cu-SBA-15 and its high catalytic activity in hydroxylation of phenol by H2O2

Transition metal copper substituted mesoporous silica (Cu-SBA-15) was synthesized using triblock copolymers surfactant as template agent under acidic condition. The result Cu-SBA-15 was characterized with XRD, ICP-AES, FT-IR and N₂ adsorption–desorption measurements, which prove that Cu(II) was mainly incorporated into the framework of Cu-SBA-15. Its catalytic activity was studied for phenol hydroxylation using H₂O₂ (30%). The substituting element (Cu²⁺) is incorporated into the framework position forming a new type of active site which raises the phenol conversion to 62.4% and the diphenol (the mixture of catechol (CAT) and hydroquinone (HQ)) selectivity to 97%. The Cu-SBA-15 has very high selectivity for catechol (about 71% selectivity), which is completely different from that of the microporous titanium silicalite zeolites (47.1% phenol conversion and about 50% selectivity to CAT under same reaction conditions). The results obtained indicate that the selective oxidation of phenol with H₂O₂ by a radical substitution mechanism.     

Effects of cell-wall acetate,xylan backbone,and lignin on enzymatic hydrolysis of aspen wood

Aspen wood substrates with varying degrees of deacetylation, xylan, and lignin removal have been prepared and submitted to enzymatic hydrolysis with a cellulase/hemicellulase preparation for an extended constant period of hydrolysis. Controlled deacetylation has been achieved by treating wood with various alkali metal hydroxide solutions, at various alkali/wood ratios. It has been found that samples with the same extent of deacetylation produce the same sugar yields upon enzymatic hydrolysis. Increased degree of deacetylation increases the yield of sugars obtained from enzymatic hydrolysis, all other compositional parameters held constant. The acetyl group removal is proportional to the stoichiometric relation between added base and wood acetyl content, i.e., the same number of milliequivalents of base/weight of wood remove the same extent of acetyl groups, regardless of the concentration of the base solution. No cation effects are found among Li, Na, and K alkali hydroxide solutions, suggesting that swelling is not as important a parameter as is the removal of the acetyl groups from the xylan backbone in determining the extent of hydrolyzability of the resulting sample.