棒状纳米纤维素仿生矿化及光谱分析

以棒状纳米纤维素为模板,采用仿生矿化的方法制备纳米纤维素/纳米羟基磷灰石复合材料。并利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜能谱分析(SEM-EDAX)对仿生矿化前后纳米纤维素中碳、氧、钙、磷元素的变化情况及分布状态进行了表征,并探讨了纳米羟基磷灰石的生长机理。结果表明纳米纤维素表面形成了纳米羟基磷灰石;纳米纤维素的碳氧比为1.81,仿生矿化后下降为1.54;仿生矿化后纳米纤维素的钙磷比nCa/nP=1.70;纳米羟基磷灰石成核是在纳米纤维素的羟基上,并且纳米纤维素表面羟基和纳米羟基磷灰石的钙离子之间发生了配位作用。纳米羟基磷灰石较为均一的形成在纳米纤维素的基体中。通过原子力显微镜(AFM)图片可以看出,直径为20nm左右的羟基磷灰石生长在纳米纤维素的表面。     

Molecular dynamics of polycrystalline cellobiose studied by solid-state NMR

Molecular motions of polycrystalline cellobiose have been investigated by measuring proton spin–lattice relaxation times, T₁ and T_1ρ, and the second moment, M₂, in both protonated and D₂O exchanged forms over the temperature range 120–380 K. T₁ relaxation is dominated by the motions of hydroxyl groups between 150 and 380 K, characterised by an activation energy of about 8.74 kJ/mol, whereas T_1ρ relaxation is driven by the motions of the same groups between 120 and 300 K. T_1ρ results suggest that hydroxyl groups have a distribution of dynamics. Motion of methylene groups was detected in the second-moment experiments at about 350 K, characterised by activation energy of about 40 kJ/mol. Consideration of the calculated and observed rigid-lattice second moments suggests that the reported X-ray data are incorrect for the inter-proton distance on C6′. ¹³C CPMAS spectra of both protonated and deuterated cellobiose have also been measured. Spectra of the deuterated material showed the existence of a second crystalline form in addition to the normal form.     

Rotational spectra, nuclear quadrupole hyperfine tensors, and conformational structures of the mustard gas simulent 2-chloroethyl ethyl sulfide

Rotational spectra have been recorded for both the ³⁵Cl and ³⁷Cl isotopic forms of two structural conformations of 2-chloroethyl ethyl sulfide (CEES). The rotational constants of the ³⁵Cl and ³⁷Cl isotopomers were used to identify the conformational isomers. A total of 236 hyperfine transitions have been assigned for 47 rotational transitions of the ³⁵Cl isotope of a GGT conformer, and 146 hyperfine have been assigned for 37 rotational transitions of the ³⁷Cl isotopomer. For the second conformer, a total of 128 (110) hyperfine and 30 (28) rotational transitions have also been assigned to the ³⁵Cl (³⁷Cl) isotopes of a TGT conformation. The extensive hyperfine splitting data, measured to high resolution with a compact Fourier transform microwave spectrometer, were used to determine both the diagonal and off-diagonal elements of the ³⁵Cl and ³⁷Cl nuclear quadrupole coupling tensors in the inertial tensor principal axis system. The experimental rotational constant data, as well as the ³⁵Cl and ³⁷Cl nuclear quadrupole coupling tensors, were compared to the results from 27 optimized ab initio (HF/6-311++G^∗∗ and MP2/6-311++G^∗∗) model structures.     

酸性离子液体催化合成对硝基苯甲酸乙酯的研究

在酸性离子液体([(CH2)3SO3Hmin]HSO4)催化剂存在下, 以对硝基苯甲酸和乙醇为原料合成对硝基苯甲酸乙酯. 对影响产率的诸多因素进行了考察, 其最佳反应条件为: 酸醇摩尔比1:15, 酸与离子液体摩尔比1:1.5, 反应温度85℃, 反应时间2h, 产品收率可达85.10%. 离子液体重复使用5次后, 其催化活性基本不变.     

Zur Empfindlichkeit von Festkörperspurdetektoren

Es werden verschiedene Festkörperspurdetektor-Materialien hinsichtlich ihrer Empfindlichkeit gegenüber Bestrahlung mit α-Teilchen und zum Teil auch gegenüber Protonen und Deuteronen verglichen. Die speziell für den Einsutz als Festkörperspurdetektor hergestellten Zellulosenitrat-Folien wurden als empfindlichste Detektoren ermittelt.     

DFT study and quantitative detection by surface‐enhanced Raman scattering (SERS) of ethyl carbamate

Ethyl carbamate (EC), a potentially toxic compound, is found in alcoholic beverages and fermented foodstuff. A combined experimental and theoretical study of Raman on EC is reported in this work for the first time. The Raman bands observed for EC in solid phase are characteristic for the carbonyl group, C―C, C―H and N―H stretching and deformation vibrations. These spectral features coupled with a pKa study allowed establishing the neutral species of EC present in the aqueous solutions experimentally tested at different concentrations. In addition, by performing a density functional theory study in the gas phase, the calculated geometry, the harmonic vibrational modes, and the Raman scattering activities of EC were found to be in good agreement with our experimental data and helped establish the surface‐enhanced Raman scattering (SERS) behavior and EC adsorption geometry on the silver surfaces. The Raman peak at 1006 cm⁻¹, assigned to the υ_s(CC) + ω(CH) modes, the strongest and best reproducible peak in the SERS spectra, was used for a quantitative evaluation of EC. The limit of detection, which corresponds to a signal‐to‐noise ratio equal to 3, was found to be 2 × 10⁻⁷ M (17.8 µg l⁻¹). SERS spectra obtained by using hydroxylamine hydrochloride‐reduced silver nanoparticles provide a fast and reproducible qualitative and quantitative determination of EC in aqueous solution. Copyright © 2013 John Wiley & Sons, Ltd.     

On the Effects of UV Radiation on the Release Ability of Glucose Embedded in Hydroxypropyl Cellulose Films

New drug delivery systems based on hydroxypropyl cellulose (HPC) and different percents of glucose were prepared and characterized to check their suitability as UV resistant patches. The spectral absorption properties of the HPC and HPC-glucose blends before and after UV irradiation were analyzed. The surface polarity and hydrophilicity were correlated with the morphology of the films and analyzed with respect to the UV exposure time and the embedded amount of glucose. The effects of UV radiation on in vitro evaluation of glucose release from the HPC films are reported. The mechanism involved in the drug release process, evaluated using the Korsmeyer-Peppas equation, was dependent on the introduced amount of glucose and less on the UV exposure time. A more polar, smoother, and less dense surface releases the glucose over larger periods of time, making the system with lower percents of glucose more adequate for the pursued purpose.     

Expansion,injection and micro-explosion phenomena during the full combustion cycle of mixed fuel droplets of ethyl alcohol and biodiesel

In this study, mixed fuel droplets of ethyl alcohol and biodiesel with different volumes or ratios were prepared and the related expansion, injection and micro-explosion phenomena were investigated. During the tests, a mixed-fuel droplet was hung on a high-temperature-resistant Cr-Ni wire, which was transported to the preheating piston for heating and then was ignited automatically. Micro-needles and an infusion set also were employed to prepare mixed droplets with identical ratios but different volumes. Using a single-lens-reflex (SLR) camera, colour videos that captured the combustion process of the mixed droplets were taken and were processed into colour images using Adobe Premiere Pro CC. The colour image series were analysed to determine the ignition delay time, the burnout time and the flame characteristics during combustion of mixed droplets with different ratios. Instantaneous grey images were obtained by means of high-speed photography during combustion of the mixed droplets with different volumes and different ratios, and of droplets of E40 (in which the volume ratio of ethyl alcohol was 40%). Using Image pro plus and Origin software, the variation of normalised mean droplet diameter with time over the whole combustion cycle was calculated and the underlying reasons for various combustion phenomena were analysed.     

Synthesis of Novel 1,2,3,4-Tetrahydrocarbazole Derivatives of Biological Interest

2-Cyano-N-(tetrahydrocarbazole)acetamide (1) was utilized for the synthesis of several new arylazocarbazole derivatives (2a–e). Compound (1) reacted with phenyl isothiocyanate to yield the corresponding non-isolable intermediate (3), which gave, upon treatment with dilute hydrochloric acid, thiocarbamoyl derivative (4). Compound (3) reacted with chloroacetone, chloroacetic acid, chloroacetyl chloride, ethyl bromoacetate, and phenacyl bromide to afford thiazolone derivatives (6), (8), and (10), respectively. Compound (1) was heated in the presence of pyridine and/or hydrazine hydrate and/or isatine to give the corresponding tetrahydrocarbazole derivatives (13), (14), and (18), respectively.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

One‐Pot,High‐Yielding Synthesis of Novel Dihydrothiazolo[3,2‐a]pyrimidinones

Reaction between 6‐(un)substituted‐2‐thiouracils and E‐ethyl 4‐bromocrotonate under basic conditions at room temperature is an easy, mild, high‐yielding, and regioselective method for the preparation of 7‐(un)substituted dihydrothiazolo[3,2‐a]pyrimidinone derivatives.