Fermentation characteristics and the dynamic trend of chemical components during fermentation of Massa Medicata Fermentata

As a representative of traditionally fermented Chinese medicine, Massa Medicata Fermentata (MMF) shows the functions of invigorating the spleen and stomach and promoting digestion, which plays an important role in the treatment of gastrointestinal diseases. The fermentation mechanism and the key factors that affect the quality of MMF have not been revealed yet, which has become an urgent issue that limits its clinical application. This article aims to systematically and comprehensively reveal the transformation of physical properties and the dynamic trend of chemical components including substrate components, volatile components, and lactic acid as anaerobic fermentation product during MMF fermentation. Along with obvious hyphae growth observed for MMF, the weight of MMF decreased, and the moisture and temperature increased. Through the quantified 14 components from substrate, ferulic acid increased from 45.53 ± 6.94 to 141.89 ± 78.40 μg/g, while glycosides and phenolic acids declined except caffeic acid. Also, within the 66 volatile components analyzed, alcohols and acids increased, while aldehydes and ketones decreased. Lactic acid was not detected in the fermentation substrate, but an apparent increase in lactic acid content was observed along with the increased fermentation days, resulting in 2.54 ± 0.15 mg/g on day 8. Based on the tested components, the fermentation process of MMF was discriminated into three distinct stages by principal component analysis, and an optimal fermentation time of four days was proposed. The results of this study will be of great significance to clarify the characteristics of fermentation and conduce to improving quality standards of MMF.     

On the Criteria of Instability for Electrochemical Systems

Both cyclic-voltammetry-based and impedance-based experimental criteria that have been developed recently for the oscillatory electrochemical systems are critically appraised with two typical categories of oscillators.Consistent conclusions can be drawn by the two criteria for the category of oscillators that involve the coupling of charge transfer mainly with surface steps(e.g.ad-and desorption)such as in the electrooxidation of C1 organic molecules.Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the coupling of charge transfer mainly with mass transfer(e.g.diffusion and convection) such as in the Fe(CN)6^3- reduction accompanying periodic hydrogen evolution.The reason is that the negative impedance cannot include the feedback information of convection mass transfer induced by the hydrogen evolution.However,both positive and negative nonlinear feedbacks,i.e., the diffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)6^3- surface concentration,that coexist between the bistability,i.e.,Fe(CN)6^3- reduction with and without hydrogen evolution at lower and higher potential sides respectively,are all reflected in the crossed cyclic voltammogram(CCV).It can be concluded that the voltammetry-based criterion(in time domain)is more intuitive,less time-consuming and has a wider range of applications than the impedancebased one (in frequency domain).     

吡咯和呋喃气相质子化过程的密度泛函理论研究

Density functional theory and ab initio calculations have been used to determine structures and stabilities of the protonated aromatics species AH^＋ and AH2^2＋ （A=pyrrole, furan）. Possible mechanisms and relative energetics for protonation of pyrrole and furan by H3O^＋ and AH^＋ in the gas phase have been explored. Calculations show that the Cα-protonated species was the most stable structure for AH^＋, and the protonated AH^＋ might accommodate the second proton to yield AH2^2＋ if the free proton was available. The gas-phase H3O^＋ could protonate pyrrole and furan with significant exothermiCity and almost without barrier. The proton transfer from AH4^＋ to pyrrole and furan has a barrier ranging from 33.5 to 39.3 kJ/mol in the gas phase.     

Theoretical study of endohedral metallofullerenes: Sc3−nLanN@C80 (n=0–3)

To provide theoretical insight into the structures and properties of Sc₃N@C₈₀, which has been isolated in high yield and purity as a new stable endohedral metallofullerene, density functional calculations are carried out for the Sc_3?nLa_nN@C₈₀ (n=0–3) series. Because of electron transfer from Sc₃N to C₈₀, the electronic structure of Sc₃N@C₈₀ is formally described as (Sc₃N)⁶⁺C$_{80}^{6-}$. The encapsulated Sc₃N cluster takes a planar structure with long Sc–Sc distances and is highly stabilized inside the I_h cage of C₈₀, which rotates rapidly. As the number of La atoms increases, the Sc_3?nLa_nN cluster is forced to maintain a pyramidal structure in Sc_3?nLa_nN@C₈₀. In addition, the C₈₀ cage takes an open‐shell electronic structure due to an increase in the number of electrons transferring from Sc_3?nLa_nN. These make the endohedral structure less stable and more reactive. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1353–1358, 2001     

Fourier transform IR spectrum and photoreactivity of the C3O2:HCl complex isolated in solid argon

IR spectroscopy was coupled with the matrix isolation technique to study the molecular complex formed between C₃O₂ and HCl and its photodissociation. The vibrational frequencies of the complex were compared with those of HCl and C₃O₂ monomers. For C₃O₂, a bent structure was characterized in the solid environment.

The vibrational frequencies were calculated in the 4000–400 cm⁻¹ range using an ab initio method at the MP2/6-31G** level for the most stable complex; these frequencies describe the hydrogen interaction with the central carbon atom of C₃O₂ (T complex). The measured shifts between the vibrational mode frequencies of the complex and monomers were in good agreement with the calculated values.

Broad-band UV irradiation ( > 230 nm) of the T complex leads preferentially to ketene chloride and carbon monoxide. Ketene chloride formation can be explained by the reaction between HCl and the carbene C₂O, which results from photo-dissociation at the C=CO bond of C₃O₂.     

Superoxes,high temperature universal phases in (GC)2

Most of the common classes of organic compounds chromatograph normally on Superoxes. There is no tailing or adverse effect from excessively different activity different activity coefficients. Superoxes are therefore universal phases for gas chromatography. This is also expressed by a wide useful temperature range from ～50° to ～300°. High MW Superox-4 has a MAOT about 20° higher than the lower MW Superox-0.1. Several applications illustrating the versatility of Superox phases in (GC)² are presented.     

Synthesis of New Ligand 1,2-Bis{di[（R,R）-1,3,2-oxzaphosphlidine]phosphino}ethane with C_2-symmetric Axis and Application in Rh-catalyzed Asymmetric Hydrogenation

New ligand 1,2-bis{di[（R,R）-1,3,2-oxzaphosphlidine]phosphino}ethane [（R,R）-BDOPPEs 1,2,3 and 4] with C2-symmetric axis and bearing nitrogen and oxygen were synthesized from readily available optically active amino alcohols.Rh complexes with these ligands were highly enantioselective catalysts for asymmetric hydrogenation of N-benzoyldehydroamino acid derivatives and α-functionalized ketones in 99%e.e.and 98%e.e.,respectively.This new class of（R,R）-BDOPPEs 1,2,3 and 4 gave much more effectivity and enantionselectivity than their corresponding non-C2-asymmetric aminophosphine phosphinite.     

金属四重键化合物M2X4(PMe3)4(M=Cr,Mo,W;X=F,Cl,Br,I)结构和电子光谱的密度泛函理论研究

采用密度泛函理论方法,在TZ2P-STO基组水平下,对金属四重键化合物M2Cl4(PMe3)4(M=Cr,Mo,W)和Mo2X4(PMe3)4(X=F,Cl,Br,I)的几何结构进行优化,分析了电子结构,并运用TDDFT方法对其低占据激发态进行了计算.考虑相对论效应的ZORA方法能够较好地重现M2X4(PMe3)4的几何结构.M2X4(PMe3)4的电子结构分析表明其d电子的组态为σ2π4δ2,前线轨道能级顺序为πlig<πd/σd<δd<δd*.金属原子和卤素配体的改变虽然使轨道能量发生变化,但没有影响轨道的排布顺序.TDDFT方法对M2X4(PMe3)4δd→δd*和πd→δd*跃迁能量的计算较为准确,对πlig→δd*(LMCT)跃迁能量的计算误差较大.金属原子、卤素配体以及相对论效应对激发能的影响可以根据分子轨道能级的变化给予解释.     

A new general-purpose isothermal microcalorimeter for use at temperatures up to 200 °C

The design and some properties of a new general-purpose isothermal microcalorimeter are reported. The instrument is a twin thermopile heat conduction calorimeter, which is designed for use up to 200 °C. The calorimetric units and surrounding heat sink are suspended inside a hollow aluminium construction, which is thermostated. Above that unit a second thermostated block is positioned and the whole assembly is suspended inside a Dewar vessel. When the instrument is used at room temperature and below, the thermostated units are cooled by use of an insertion Peltier effect cooler. The instrument can be used with a wide range of different reaction vessels (diameter 14 mm). Baseline experiments have been conducted in the temperature range 15-200 °C. Typical values obtained during 10 h periods at 200 °C are ±3 and ±10 nW for the baseline drift and baseline fluctuations, respectively. The heat detection limit, determined by release of electrical energy, is about 2 μJ. Preliminary stability measurements have been conducted at 100 °C on samples of stabilised and non-stabilised polyamide film.     

Zirconium bis(indenyl) sandwich complexes with an unprecedented indenyl coordination mode and their role in the reactivity of the parent bent-metallocenes: a detailed DFT mechanistic study

The mechanisms of three closely related reactions were studied in detail by means of DFT/B3 LYP calculations with a VDZP basis set. Those reactions correspond to 1) the reductive elimination of methane from [Zr(eta5-Ind)2(CH3)(H)] (Ind=C9H7-, indenyl), 2) the formation of the THF adduct, [Zr(eta5-Ind)(eta6-Ind)(thf)] and 3) the interconversion between the two indenyl ligands in the Zr sandwich complex, [Zr(eta5-Ind)(eta9-Ind)], which forms the link between the two former reactions. An analysis of the electronic structure of this species indicates a saturated 18-electron complex. A full understanding of the indenyl interchange process required the characterisation of several isomers of the Zr-bis(indenyl) species, corresponding to different spin states (S=0 and S=1), different coordination modes of the two indenyl ligands (eta5/eta9, eta5/eta5 and eta6/eta9), and three conformations for each isomer (syn, anti, and gauche). The fluxionality observed was found to occur in a mechanism involving bis(eta5-Ind) intermediates, and the calculated activation energy (11-14 kcal mol(-1)) compares very well with the experimental values. Two alternative mechanisms were explored for the reductive elimination of methane from the methyl/hydride complex. In the more favourable one, the initial complex, [Zr(eta5-Ind)2(CH3)(H)], yields [Zr(eta5-Ind)2] and methane in one crucial step, followed by a smooth transition of the Zr intermediate to the more stable eta5/eta9-species. The overall activation energy calculated (Ea=29 kcal mol(-1)) compares well with experimental values for related species. The formation of the THF adduct follows a one step mechanism from the appropriate conformer of the [Zr(eta5-Ind)(eta9-Ind)] complex, producing easily (Ea=6.5 kcal mol(-1)) the known product, [Zr(eta5-Ind)(eta6-Ind)(thf)], a species previously characterised by X-ray crystallography. This complex was found to be trapped in a potential well that prevents it from evolving to the 3.4 kcal mol(-1) more stable isomer, [Zr(eta5-Ind)2(thf)], with both indenyl ligands in a eta5-coordination mode and a spin-triplet state (S=1).