抗坏血酸有机锗倍半氧化物的合成及抗癌活性研究

通过三氯锗仿与抗坏血酸分子的加成反应,合成了一种新型有机锗倍半氧化物,产物的结构通过元素分析、IR及UV光谱等方法进行了表征．生物活性实验表明合成物对小鼠S-180肿瘤生长具有显著的抑制作用．     

A Pyrazine‐Based Polymer for Fast‐Charge Batteries

The lack of high‐power and stable cathodes prohibits the development of rechargeable metal (Na, Mg, Al) batteries. Herein, poly(hexaazatrinaphthalene) (PHATN), an environmentally benign, abundant and sustainable polymer, is employed as a universal cathode material for these batteries. In Na‐ion batteries (NIBs), PHATN delivers a reversible capacity of 220 mAh g^?1 at 50 mA g^?1, corresponding to the energy density of 440 Wh kg^?1, and still retains 100 mAh g^?1 at 10 Ag^?1 after 50 000 cycles, which is among the best performances in NIBs. Such an exceptional performance is also observed in more challenging Mg and Al batteries. PHATN retains reversible capacities of 110 mAh g^?1 after 200 cycles in Mg batteries and 92 mAh g^?1 after 100 cycles in Al batteries. DFT calculations, X‐ray photoelectron spectroscopy, Raman, and FTIR show that the electron‐deficient pyrazine sites in PHATN are the redox centers to reversibly react with metal ions.     

Routine analysis by high precision gas chromatography/mass selective detector/isotope ratio mass spectrometry to 0.1 parts per mil

Stable isotope methods are potentially quite useful for validating natural or enhanced mineral degradation of contaminants. For this reason, a continuous flow gas chromatograph (GC), isotope ratio mass spectrometer (IRMS) has been coupled with a quadrupole mass selective detector (MSD) to allow simultaneous mass spectral and stable carbon isotope ratio data to be obtained from a single chromatographic analysis. This allows the target contaminant and any extra-cellular degradation intermediates to be both qualified and quantified. Previously acceptable limits of precision (0.3 parts per mil) are undesirable given the small fractionation observed during aerobic degradation. To further understand the fate of organic contaminants and to gain information about the metabolic degradative pathway employed by a microorganism, routine isotopic analyses on a range of analytes have been performed. Quantities of sample producing mass-44 ion beam signal (I(44)) of 2 x 10(-10) to 1 x 10(-8) A were analysed. When the IRMS was tuned for high sensitivity, ion source nonlinearities were overcome by peak height correction from an algorithm that was produced using known isotopic standards of varying concentrations. This led to sample accuracy of <0.01 per thousand and sample precision of 0.1 per thousand. Copyright 1999 John Wiley & Sons, Ltd.     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.     

The structure and magnetic properties of chromium(III) molybdate

Magnetic susceptibility measurements have shown that Cr₂(MoO₄)₃ orders magnetically at 42 K. Powder neutron diffraction experiments at 295 and 5 K indicate that Cr₂(MoO₄)₃ is chemically and magnetically isostructural with the L-type ferrimagnet Fe₂(MoO₄)₃, and has a magnetic moment of 2.5 ± 0.2 μ_B per cation at 5 K. The limitations imposed on powder neutron diffraction methods by particle-size effects are discussed.     

The nexus between alternatives assessment and green chemistry: supporting the development and adoption of safer chemicals

ABSTRACT

Alternatives assessment and green chemistry share a common goal of supporting the transition to safer, more sustainable chemicals, materials, and products. Yet the two fields, and their respective scientific communities, are not well integrated. To better understand the nexus between alternatives assessment and green chemistry as complementary approaches to support the development and adoption of safer, more sustainable chemicals for specific functional uses, this article discusses the foundations of the two fields and examines two case examples in which companies have utilized the tools and approaches of both disciplines in developing safer chemical solutions. This research demonstrates the importance and utility of the overlapping skillsets and tools of the two disciplines and the potential benefit of educational opportunities and collaborative spaces in jointly strengthening both fields. Additionally, the literature and case examples identify a number of research and practice needs that would bolster the application of both alternatives assessment and green chemistry in supporting the transition to safer, more sustainable chemistry, including: clearer definitions and criteria of what is ‘safer’; improved approaches to evaluate potential unintended consequences of chemical applications; and more effective tools to evaluate toxicity, consider inherent exposure trade-offs, and combine multiple attributes to make an informed decision.     

The metal complexes of some azo and azomethine dyestuffs : Determination of stability constants,and preparation of solid complexes

The stability constants of the complexes of 4-(2-pyridylazo)-resorcinol (I) with copper(II), cobalt-(II), zinc(Il), lead(ll), and uranium(VI) were determined by potentiometric titration in aqueous media, and were shown to have very high values, the stability constant of the copper(ll) complex approaching that of the copper(ll)-EDTA complex. The nickel(II) complex was shown to behave anomalously. The stability constants were also determined by this method in 1:1 dioxan/water, and the values obtained compared with those for the complexes of salicylidene-2-aminopyridine (II), 2-(o-hydroxy-phenyl-imino-methyl)-pyridine(III), and benzeneazoresorcino (IV). It is shown that chelation by (1) is terdentate, involving the pyridine nitrogen, the o-hydroxyl group and the azo nitrogen farthest from the heterocycle.The solid copper(II) complexes of these four ligands were prepared; in the solid complexes the azo nitrogen nearest the heterocycle plays a greater part than in the complexes in solution.     

Quantum theory for transition state absorption

A time-dependent quantum model involving two wave packets on two excited-state surfaces is presented to describe absorption (or emission) from the transition state of a chemical reaction. The connection between the quantum result and existing classical theories is shown. The model ia applied to the direct dissociation of ICN* and gives results in good agreement with experiment. The dissociation time - the time to half-maximal absorption - is almost invariant with the pulse width but is dependent on the probe wavelength. A lower absorption plateau and a longer dissociation time is predicted for probe energies above the asymptotic resonance energy.     

On the effect of donor and acceptor substituents on the behaviour of light-driven rotary molecular motors

Light-driven rotary molecular motors based on overcrowded alkenes can be substituted with electron-donating and electron-withdrawing substituents (R = OMe, Cl and CN) in direct conjugation with the central double bond (the axis of rotation) without having a significant influence on the rate-limiting, thermal isomerisation step of their rotary cycle. This indicates that in this system, it is predominantly steric factors that determine the barrier to the thermal helix inversion. In contrast, the quantum yield and photoequilibria in the photochemical step were found to be quite sensitive to the combination of substituent and solvent employed.