Xylariphilone: a new azaphilone derivative from the seagrass-derived fungus Xylariales sp. PSU-ES163

One new azaphilone derivative, named xylariphilone (1), along with 10 known compounds was isolated from the seagrass-derived fungus Xylariales sp. PSU-ES163. Their structures were elucidated on the basis of extensive spectroscopic analysis. The absolute and relative configurations of 1 were determined by circular dichroism spectroscopy and NOEDIFF data. The antimicrobial and cytotoxic activities of the isolated compounds were evaluated.     

Novel bioactive breviane spiroditerpenoids from Penicillium brevicompactum Dierckx

The structures of four new, naturally occurring bioactive spiroditerpenoids, (+)-breviones B, C, D, and E, potential allelopathic agents, have been determined from extracts of semisolid fermented Penicillium brevicompactum Dierckx. The structures display the novel breviane spiroditerpenoid skeleton. Structure elucidation was performed by chemical transformations and by homo- and heteronuclear 2D-NMR spectral data. On the basis of combined studies of the theoretical conformations and NOEDIFF data, their relative stereochemistry is proposed. A mixed biogenesis for this novel family of spiroditerpenoids is tendered. The levels of activity shown by breviones B, C, and E in the etiolated wheat coleoptiles bioassay, especially breviones E (100% inhibition) and C (80% inhibition) both at 10(-4) M, suggest them as lead compounds for new agrochemicals.     

Blennolide derivatives from the soil-derived fungus Trichoderma asperellum PSU-PSF14

Three new blennolide derivatives, blennolides L-N (1–3), together with five known metabolites were isolated from the soil-derived fungus Trichoderma asperellum PSU-PSF14. Their structures were determined by analysis of spectroscopic data. Their relative configurations were determined by analysis of NOEDIFF data and confirmed by X-ray crystallography for compound 1 whereas the absolute configurations were established by means of experimental and calculated TDDFT ECD data. Compound 1 displayed antifungal activity against Cryptococcus neoformans ATCC90112 and ATCC90113 flucytosine-resistant with the MIC values of 128 and 64?μg/mL, respectively, and was inactive against noncancerous Vero cell lines.     

Characterization and stereochemistry of alkyl 2-chloro-3-formylacrylates: Experimental NMR and theoretical DFT studies

The synthesis of alkyl 2-chloro-3-formylacrylates 1 from alkyl pyruvates was carried out using Vilsmeier reaction. The reaction is highly stereoselective and leads to a 95:5 mixture of Z and E stereoisomers. Both stereoisomers were characterized by ¹H and ¹³C NMR. In CDCl₃ solution, the NMR data, particularly the NOEDIFF experiments, show that the major species formed is the Z stereoisomer. Heating compound 1 in THF at reflux afforded the cyclic product 2 in 90 % yield. The interpretation of the experimental data were further supported by DFT/B3LYP calculations.     

Hydroacridines: Part 23. 1H and 13C NMR spectra of sym‐octahydroacridine,its 9‐(3‐pyridyl) and 9‐(4‐pyridyl) derivatives and the corresponding N(10)‐oxides. An experimental approach to the diamagnetic anisotropy of the pyridine nucleus

The complete ¹H NMR chemical shift assignments of 1,2,3,4,5,6,7,8‐octahydroacridine ( 1 ), 1,2,3,4,5,6,7,8‐octahydro‐9‐(3‐pyridyl)acridine ( 2 ), 1,2,3,4,5,6,7,8‐octahydro‐9‐(4‐pyridyl)acridine ( 3 ) and the corresponding N(10)‐oxides 1a , 2a and 3a , respectively, were achieved on the basis of 400 MHz ¹H NMR spectra and proton–proton decoupling, HMQC and NOEDIFF experiments. The spectral data for the above compounds provided the first experimental evidence of the difference in the anisotropy effect of the two non‐symmetrical moieties of the pyridine nucleus, and allowed us to ascertain that the shielding effect of the moiety defined by the C(2′)—N—C(6′) atoms is weaker than that of the C(3′)—C(4′)—C(5′) moiety. The ¹³C NMR spectra of 1 – 3 and 1a – 3a and the effect of N(10)‐oxidation on the ¹³C NMR chemical shifts are also discussed. The N‐oxidation of 2 and 3 with m‐chloroperbenzoic acid occurred regiospecifically, affording the N(10)‐oxides 2a and 3a free of N(1′)‐oxide isomers. Copyright © 2002 John Wiley & Sons, Ltd.     

Isotope Effects on Chemical Shifts in the Study of Hydrogen Bonds in Small Molecules

This review is giving a short introduction to the techniques used to investigate isotope effects on NMR chemical shifts. The review is discussing how isotope effects on chemical shifts can be used to elucidate the importance of either intra- or intermolecular hydrogen bonding in ionic liquids, of ammonium ions in a confined space, how isotope effects can help define dimers, trimers, etc., how isotope effects can lead to structural parameters such as distances and give information about ion pairing. Tautomerism is by advantage investigated by isotope effects on chemical shifts both in symmetric and asymmetric systems. The relationship between hydrogen bond energies and two-bond deuterium isotope effects on chemical shifts is described. Finally, theoretical calculations to obtain isotope effects on chemical shifts are looked into.     

Isotope Effects in Organic Chemistry and Biochemistry

The present article shows the extent to which isotope effects are likely to be encountered in the use of isotope techniques and what problems are studied with primary and secondary isotope effects. By way of example, the results of studies on E2 reactions, particularly in the Hofmann degradation, are discussed, followed by a discussion of some “analytical isotope effects”. Finally, the problems encountered and the information that can be obtained from isotope effects studies on enzyme reactions, and the advantages and disadvantages of competitive and non-competitive techniques are described. In addition to a survey of isotope effects in dehydrogenase reactions, new isotope effects encountered in the dehydrogenation of T-labeled alcohols are reported.     

Anti-oxidative action of resveratrol: Implications for human health

Resveratrol, the red-wine polyphenol, is intensively studied polyphenols for its pleiotropic biological effects. A plethora of health beneficial effects of this stilbene has been reported including cardio-protective, neuro-protective, anti-cancer, anti-diabetic and interesting anti-aging. Though it has been proposed that these effects of resveratrol arise from its capacity to interact with multiple molecular targets involved in diverse intracellular pathways including activation of sirtuins, the antioxidant property of this compound is the most described one to attribute its diverse health beneficial effects. In the present review we have explained the biological activities of resveratrol with the latest laboratory evidences towards its antioxidant effects.     

Substituent Effect on the C–NO2 and N–NO2 Bond Dissociation Energies of Nitroaromatic Molecules

Six density function theory methods (B3LYP, B3P86, MPWB1K1, MPWPW91, PBEPBE, TPSS1KCIS3) were used to calculate bond dissociation enthalpies of nitro compounds, where the B3P86 method was found to give the most accurate predictions. Using the B3P86 method meta‐ and para‐substituted nitroaromatics were systematically studied for the first time. The remote substituent effects, Hammett relationships, and the origin of the substituent effects were discussed on the basis of the calculated results. Both meta‐ and para‐substituted nitromethyl‐benzenes showed significant substituent effects and a fair correlation against substituent constants σ_p⁺ The ground state effects were found to play the major role in determining the overall substituent effects. Meanwhile, nitroamino‐ benzenes showed irregular substituent effects and a poorer Hammett correlation, where both ground and radical state effects contributed to the overall substituent effects.     

Matrix effects demystified: Strategies for resolving challenges in analytical separations of complex samples

Matrix effects can significantly impede the accuracy, sensitivity, and reliability of separation techniques presenting a formidable challenge to the analytical process. It is crucial to address matrix effects to achieve accurate and precise measurements in complex matrices. The multifaceted nature of matrix effects which can be influenced by factors such as target analyte, sample preparation protocol, composition, and choice of instrument necessitates a pragmatic approach when analyzing complex matrices. This review aims to highlight common challenges associated with matrix effects throughout the entire analytical process with emphasis on gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry, and sample preparation techniques. These techniques are susceptible to matrix effects that could lead to ion suppression/enhancement or impact the analyte signal at various stages of the analytical workflow. The assessment, quantification, and mitigation of matrix effects are necessary in developing any analytical method. Strategies can be implemented to reduce or eliminate the matrix effect by changing the type of ionization, improving extraction and clean-up methods, optimization of chromatography conditions, and corrective calibration methods. While development of an effective strategy to completely mitigate matrix effects remains elusive, an integrated approach that combines sample preparation, analytical extraction, and effective instrumental analysis remains the most promising avenue for identifying and resolving matrix effects.     

Kinetic Isotope Effects in Asymmetric Reactions

Kinetic isotope effects are exquisitely sensitive probes of transition structure. As such, kinetic isotope effects offer a uniquely useful probe for the symmetry‐breaking process that is inherent to stereoselective reactions. In this Concept article, we explore the role of steric and electronic effects in stereocontrol, and we relate these concepts to recent studies carried out in our laboratory. We also explore the way in which kinetic isotope effects serve as useful points of contact with computational models of transition structures. Finally, we discuss future opportunities for kinetic isotope effects to play a role in asymmetric catalyst development.     

河水中兽药多残留分析时亲水亲脂平衡柱的基质效应和保留效果

基质效应是液相色谱-质谱联用(LC-MS)定量分析中的重要干扰因素。以反渗透水为空白对照进行LC-MS/MS检测,在500倍浓缩条件下考察了33种兽药分别经Waters、Supelco和CNW等3种亲水亲脂平衡(hydrophilic-lipophilic balance, HLB)固相萃取柱富集后的基质效应及其保留效果。结果表明,以反渗透水为基质时3种HLB柱均表现出外源性基质效应,对大部分喹诺酮类和四环素类兽药呈现促进效应,有两种HLB柱对雌激素类兽药等呈现抑制效应,对磺胺类兽药的基质效应不显著,有一种HLB柱对氯霉素类兽药呈现抑制效应;以河水为基质时,由于外源性杂质与内源性杂质共同作用,对大部分喹诺酮类和四环素类兽药呈现促进效应,对氯霉素类和雌激素类兽药呈现抑制效应,对磺胺类兽药基质效应不显著。与外标法相比较,基质匹配标准校正法可有效消除基质效应对检测结果的影响。在50 ng/L和200 ng/L两个加标水平下,Waters、Supelco和CNW 3种HLB柱对河水中33种目标兽药的校正后的回收率分别为40.3%~146.0%、37.8%~104.2%和52.9%~150.1%; RSD(n=4)为0.2%~14.6%。相同实验条件下3种HLB柱的外源性基质效应不容忽视。而采用基质匹配标准校正法克服目标物基质效应,保留效果无显著差异,富集效果良好,为河水样品中兽药多残留分析方法中固相萃取柱的选择提供了科学依据。     

Some symmetry-induced isotope effects in the kinetics of recombination reactions

Symmetry-induced isotope effects in recombination and collision-induced dissociation reactions are discussed. Progress on understanding the anomalous isotope effects in ozone is reviewed. Then, calculations are performed for the simpler reaction xNe+yNe+H<-->xNeyNe+H, where x and y label either identical or different isotopes. The atomic masses in the model are chosen so that symmetry is the only difference between the systems. Starting from a single potential energy surface, the properties of the bound, quasibound, and continuum states of the neon dimer are calculated. Then, the vibration rotation infinite order sudden approximation is used to calculate cross sections for all possible inelastic and dissociative processes. A rate constant matrix that exactly satisfies detailed balance is constructed. It allows recombination to occur both via direct three-body collisions and via tunneling into the quasibound states of the energy transfer mechanism. The eigenvalue rate coefficients are determined. Significant isotope effects are clearly found, and their behavior depends on the pressure, temperature, and mechanism of the reaction. Both spin statistics and symmetry breaking produce isotope effects. Under most conditions the breaking of symmetry enhances the rates, but a wide spectrum of effects is observed; they range from isotope effects with a normal mass dependence to huge, mass-independent isotope effects to cancellation and even to reversal of the isotope effects. This is the first calculation of symmetry-induced isotope effects in recombination rates from first principles. The relevance of the present effects to ozone recombination is discussed.     

Effects of liquid crystal states on photovoltaic effects of chlorophyll-a

The photovoltaic effects of chlorophyll-a(chla) and the effects of stearic acid, egg phosphatide and cholesterol on those were investigated by means of measuring the photoinduced potentials of SnO2/chla electrodes. Because of the formation of liquid crystal states, appropriate concentrations of stearic acid and egg phosphatide added in a certain system could increase the photovoltaic effects of chla. Cholesterol always decreased the photovoltaic effects of chla because there was no liquid crystal state formed with it.     

共混聚合物辐射效应研究的进展

本文综述了近十几年来国内外共混聚合物辐射效应研究的进展情况.内容包括辐射交联理论在共混聚合物体系中的适用性、共混体系的相容性、相态结构对辐射效应的影响及共混组份间的辐射敏化及保护效应等.     

Large primary kinetic isotope effects in the abstraction of hydrogen from organic compounds by a fluorinated radical in water

Isotope effects have been measured for the abstraction of hydrogen from a series of organic substrates by the perfluoro radical, Na+ -O3SCF2CF2OCF2CF2*, in water. Both primary and secondary deuterium isotope effects were measured, with the primary isotope effects ranging in value from 4.5 for isopropanol to 19.6 for acetic acid. The values for the alpha- and beta-secondary deuterium isotope effects were 1.06 and 1.035, respectively. It was concluded that tunneling contributes significantly to the production of the observed, large primary kinetic isotope effects in these C-H abstraction reactions.     

Nuclear quantum effects at aqueous metal interfaces captured by molecular dynamics simulations

In this review, we summarize the recent development in modeling nuclear quantum effects at aqueous metal interfaces. First, we review the nuclear quantum effects on the water-metal interface at ultrahigh vacuum. Then, we illustrate the nuclear quantum effects at the potential of zero charge conditions. At last, we give some outlook for the perspective work in modeling the nuclear quantum effects at electrochemical interfaces and some practical simulation strategies.     

大豆蛋白动态超高压微射流均质中机械力化学效应

以大豆蛋白为对象, 研究大豆蛋白在动态超高压均质过程中存在的机械力化学效应, 同时探究机械力化学效应对大豆蛋白热稳定性的影响. 结果表明, 在动态超高压微射流均质的机械力作用下, 蛋白颗粒粒度变小, 粒度分布范围变窄, 蛋白内部的二硫键和疏水基团被破坏, 致使巯基和疏水基团暴露, 并随着工作压力的增大破坏作用力增强. 同时经过机械力化学效应改性的大豆蛋白热稳定性增强, 并随着工作压力的增加改善效果增强.     

Length and substituent-scrambling energies of parent and halogen-substituted conjugated polyynes

Conjugated polyynes are a class of species of diverse and increasing interest. Length-scrambling and substituent scrambling reaction energies were examined using ab initio quantum chemistry calculations to investigate issues concerning the energetic effects of the molecular ends (substituent communication). Computations were performed for the parent, monohalogenated, and dihalogenated (F, Cl, Br, I) polyynes of up to 60 carbon atoms. A study of resonance effects using natural resonance theory and bond lengths demonstrates lone-pair-donating effects that increase in the series F < Cl < Br < I, but run counter to the halogen inductive effects which decrease in this series and dominate energetic effects.     

Specific-ion effects in non-aqueous systems

It is widely acknowledged that specific-ion effects are ubiquitous in aqueous systems and undoubtedly are essential to the fundamental processes of life, although a deep fundamental understanding of specific-ion effects remains an important challenge. Specific-ion effects in non-aqueous solvents are known but have attracted far less attention, yet knowledge of specific-ion effects in non-aqueous systems is likely to provide important information for guiding, evaluating and testing our theories of specific-ion effects. Here, the literature on specific-ion effects in non-aqueous solvents is surveyed with a view to determining if the Hofmeister series or lyotropic series so universally observed in aqueous systems is widely evident in non-aqueous systems. Particular attention has been applied to experiments on non-aqueous systems that are known to exhibit Hofmeister series in aqueous systems with the aim of determining if a consistent ion ordering in the strength of specific-ion effects is observed in other solvents. We find that specific-ion effects are ubiquitous in non-aqueous solvents, that both Hofmeister and lyotropic series are widely observed, although not necessarily for the same class of experiment. Moreover, we find that Hofmeister and lyotropic series are observed in non-aqueous solvents even for experiments in which these series are not observed for water. Additionally, series reversal is seen for a given experiment when the solvent is changed. All this poses significant challenges for our understanding of specific-ion effects in aqueous and non-aqueous systems and also provides guideposts for future investigations.