Electric Cell-Substrate Impedance Sensing (ECIS) as a Convenient Tool to Assess the Potential of Low Molecular Fraction Derived from Medicinal Fungus Cerrena unicolor in Action on L929 and CT-26 Cell Lines

The increase in the incidence of cancer has contributed to the search for new therapeutic methods. In recent years, the use of preparations of natural origin from medical fungi has increased. One such active substance is the extracellular, low molecular active fraction obtained from the medicinal fungus Cerrena unicolor. This study aimed to monitor the pharmacokinetics of different concentrations of substances isolated from the medicinal fungus Cerrena unicolor (ex-LMS) using the ECIS technique. In the study, mouse L929 fibroblasts and colon cancer CT26 cell lines were treated with different concentrations of the active fractions obtained from Cerrena unicolor: C1 = 2.285 (μg/mL); C2 = 22.85 (μg/mL); and C3 = 228.5 (μg/mL). This study demonstrated that the tested preparation from Cerrena unicolor had no considerable effect on the resistance, capacitance, and impedance of L929 fibroblast cells, which was an indicator of no significant effect on its physiological processes. At the same time, those parameters exhibited a decrease in colon cancer cell viability. Following our previous and current studies on Cerrena unicolor, ex-LMS extracts can be safely used in anticancer therapy or chemoprevention with no significant harmful effects on normal cells.     

Amperometric detection of mono- and diphenols at Cerrena unicolor laccase-modified graphite electrode: correlation between sensitivity and substrate structure

Graphite electrode modified with laccase from Cerrena unicolor served as a biosensor for detection of 30 phenolic compounds with different structures. Some correlations of the sensor response to the structures of substrates are discussed. This biosensor responded to: (i) nanomolar concentrations of some of the selected phenolic compounds, e.g., 2,6-dimethoxyphenol, coniferyl alcohol, caffeic acid, DOPAC and hydroquinone, (ii) micromolar concentrations, e.g., ferulic acid, syringic acid, dopamine, 3,4-dihydroxybenzoic acid and dl-noradrenaline, and (iii) millimolar concentrations in the case of phenol and 4-hydroxybenzaldehyde. Among the ortho- or para-substituted phenols, the sensitivity of the C. unicolor laccase-modified electrode increased in the following order H, CH(3), OH, OCH(3) and NH(3)(+) but in the case of para-substituted phenols, the K(m)(app) values were lower. The sensitivity of the laccase electrode increased with an additional OH group in para-substituted phenols. In the case of the selected compounds, kinetic data from electrochemical flow injection system were compared with those obtained from experiments in solution.     

Direct electron transfer reactions between human ceruloplasmin and electrodes

In an effort to find conditions favouring bioelectrocatalytic reduction of oxygen by surface-immobilised human ceruloplasmin (Cp), direct electron transfer (DET) reactions between Cp and an extended range of surfaces were considered. Exploiting advances in surface nanotechnology, bare and carbon-nanotube-modified spectrographic graphite electrodes as well as bare, thiol- and gold-nanoparticle-modified gold electrodes were considered, and ellipsometry provided clues as to the amount and form of adsorbed Cp. DET was studied under different conditions by cyclic voltammetry and chronoamperometry. Two Faradaic processes with midpoint potentials of about 400 mV and 700 mV vs. NHE, corresponding to the redox transformation of copper sites of Cp, were clearly observed. In spite of the significant amount of Cp adsorbed on the electrode surfaces, as well as the quite fast DET reactions between the redox enzyme and electrodes, bioelectrocatalytic reduction of oxygen by immobilised Cp was never registered. The bioelectrocatalytic inertness of this complex multi-functional redox enzyme interacting with a variety of surfaces might be associated with a very complex mechanism of intramolecular electron transfer involving a kinetic trapping behaviour.     

Spectroscopic and Spectroelectrochemical Studies of Interaction of Nile Blue with DNA

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Studies on synthesis and magnetic resonance of lanthanide complexes with novel Schiff base derived from noncyclic polyether and β-diketone

Nine h( III) complexes with a novel Schiff base derived from diglycolamine and benzoylacetone (BZDA) have been synthesized and characterized. They can be formulated as [Ln₂(BZDA)₃(NO₃)₃](NO₃)₃-nH₂O (Ln? La, Pr, Nd, Sm, n = 4; Ln = Gd, Tb, Er, Yb, Y, n = 7). Enamic form mechanism in this β-diketone Schiff base and its Complexes were suggested and proved by IR, UV and NMR methods. The ¹³C spin-lattice relaxation time T₁ and the ratios of r(C_i-In)/ ^r (c_j-in) were measured by a 500 MHz NMR instrument for elucidating the formation of the stable six-membered chelate ring structure in these complexes. The EPR spectrum of the Gd( III) complex exhibits the “U” spectral feature and “zero field effect”. On the basis of them, the crystal field strength and the local symmetry around Gd ³⁺ in the complex have been discussed.     

Substituent effects on the redox potentials of dihydroxybenzenes: theoretical and experimental study

The redox reactions of p-hydroquinone and pyrocatechol undergo a two-proton-two-electron process in aqueous solution. We calculated their redox potentials at the B3LYP/6-311+G(d,p) level, and verified the values by employing cyclic voltammetry experiments. Then we selected seven substituent groups (–F, –Cl, –OH, –COOH, –CN, –NH₂, and –NO₂ groups) to systematically investigate the substituent effect, including the sort, position, and number of the substituent, on the redox potentials of p-hydroquinone and pyrocatechol. The calculated results show that –NH₂ and –OH groups can decrease the redox potentials, while –F, –Cl, –COOH, –CN, and –NO₂ groups increase the potential values of p-hydroquinone and pyrocatechol. The calculations can accurately predict the substituent effects on the redox potentials of pyrocatechol and p-hydroquinone. We would expect that the accurate calculation results for the model systems could be applied in the prediction of electrode potentials of other molecules.     

Schiff碱吲哚醌缩吉拉尔特试剂T的晶体结构

用X-射线晶体结构衍射测定了吲哚醌缩吉拉尔特试剂T（C13H18N4O2Cl）的晶体结构。该晶体属单斜晶系，空间群P21/n， a =12.250(2)，b = 13.631(2)， c = 9.777(1) ?，β= 113.506(7) °，V =1497.1(4) ?3，Mr =297.76，Dc =1.321g/cm3，m =2.6cm-1，F(000)=628，Z =4，R =0.0715，wR =0.1843, (I>2σ(I))。晶体结构呈蝎形，由于空间位阻的影响，该配体很难与金属离子形成配合物。     

Degradation of Polycyclic Aromatic Hydrocarbons by <Emphasis Type="Italic">Rigidoporus lignosus</Emphasis> and its Laccase in the Presence of Redox Mediators

The metabolism of polycyclic aromatic hydrocarbons (PAHs) was studied in vivo and in vitro in systems consisting of Rigidoporus lignosus and its laccase, in the presence of so-called “mediator” compounds. The static culture of the native fungal strain was able to metabolize anthracene and 2-methylanthracene, but not 9-nitroanthracene. The addition of redox mediators 2,2’-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), 1-hydroxybenzotriazole (HBT) or violuric acid (VA) led to a significant increase in the degradation of substrates. The oxidation of PAHs was not significant when purified laccase was used without the addition of mediators. The addition of these compounds increased the oxidation of all substrates by approximately 70–80% after 72 h of incubation. The degradation rate was highest for 2-methylanthracene in the presence of VA.     

染料敏化纳米薄膜太阳电池中DMPII浓度的优化

利用超微铂电极和循环伏安法及电化学阻抗谱研究了在1,2-二甲基-3-丙基咪唑碘(DMPII)的3-甲氧基丙腈(MePN)溶液中I₃^－和I^－的氧化还原行为，并对比了由不同浓度的I2和DMPII组成的电解质溶液，其染料敏化纳米薄膜太阳电池(DSCs)的光伏性能. 发现以MePN为溶剂，含1.0 mol•dm^-3 DMPII、0.12 mol•dm^-3 I2、0.10 mol•dm^-3 LiI和0.50 mol•dm^-3 4-叔丁基吡啶的电解质溶液，其DSCs的短路光电流密度为16.67 mA•cm^-3、开路电压为0.69 V、填充因子为0.70、光电转换效率达8.08%.     

Synthesis and Insulin—sensitizing Activity of a Series of 2—Benzyl—1,3—dicarbonyl Derivatives

A series of 2-benzyl-1,3-dicabonyl derivatives was synthesized.Their insulin-sensitizing activity was evaluated in 3T3-L1 preadipocyte cells.Compounds3,26 and 27 were found to possess strong insulin-sensitizing activity in vitro and were selected for further hypoglycemic evaluation in vivo.     

1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物的合成及其抗肿瘤活性研究

通过1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷与酸反应或1-(3-氯丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷与胺反应,合成了14种1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物.体外细胞培养试验结果表明,某些1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物对艾氏腹水癌细胞具有较好的杀伤活性.     

甘油催化氢解的研究与应用

近年来由于生物柴油产业的快速发展,甘油作为其生产过程中的副产品大量生成,合理利用这些过剩的甘油将有助于增加整个生物柴油产业的经济效益。本文对近年来利用甘油为原料催化氢解合成二元醇（1,2-丙二醇、1,3-丙二醇和乙二醇）的研究进展进行了综述,介绍了甘油催化氢解的研究背景,着重讨论了甘油催化氢解生成二元醇的反应机理（包括脱水-加氢机理、脱氢-加氢机理和螯合机理）和甘油催化氢解在生产二元醇上的应用,并对甘油催化氢解的发展前景做了展望。     

Spectroelectrochemical Studies on the Interactions of Complexes of Cu(phen)_2~(2 ) and Cu(bpy)_2~(2 ) with DNA

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Two New Dammarane Glycosides from the Acid Hydrolysis Product of Panax Notoginseng

In our continuing research works on Panax notoginseng (Burk.) F. H. Chen, a famous traditional Chinese herb medicine1, two new dammarane glycosides named notoginsenosides T1 (1) and T2 (2) were isolated from the mild acid hydrolysis products of the root saponins. We report herein the structure elucidation of these two novel glycosides.Notoginsenosides T1(1) was obtained as white solid, [(] = +14.49 (0.50, MeOH). Its negative mode HR-FAB-MS spectrum showing the quasimolecular ion peak a…     

Increasing Reduction Potentials of Type 1 Copper Center and Catalytic Efficiency of Small Laccase from Streptomyces coelicolor through Secondary Coordination Sphere Mutations

The key to type 1 copper (T1Cu) function lies in the fine tuning of the Cu^II/I reduction potential (E°′_T1Cu) to match those of its redox partners, enabling efficient electron transfer in a wide range of biological systems. While the secondary coordination sphere (SCS) effects have been used to tune E°′_T1Cu in azurin over a wide range, these principles are yet to be generalized to other T1Cu-containing proteins to tune catalytic properties. To this end, we have examined the effects of Y229F, V290N and S292F mutations around the T1Cu of small laccase (SLAC) from Streptomyces coelicolor to match the high E°′_T1Cu of fungal laccases. Using ultraviolet-visible absorption and electron paramagnetic resonance spectroscopies, together with X-ray crystallography and redox titrations, we have probed the influence of SCS mutations on the T1Cu and corresponding E°′_T1Cu. While minimal and small E°′_T1Cu increases are observed in Y229F- and S292F-SLAC, the V290N mutant exhibits a major E°′_T1Cu increase. Moreover, the influence of these mutations on E°′_T1Cu is additive, culminating in a triple mutant Y229F/V290N/S292F-SLAC with the highest E°′_T1Cu of 556 mV vs. SHE reported to date. Further activity assays indicate that all mutants retain oxygen reduction reaction activity, and display improved catalytic efficiencies (k_cat/K_M) relative to WT-SLAC.     

功能化聚(2,5-二甲氧基苯胺)膜的电化学和电催化性质研究

聚(2，5-二甲氧基苯胺)含有对称的环取代基，其电化学活性可与PAni相比拟．该聚合物具有三种氧化态，即完全还原态(L)、半氧化态(E)和完全氧化态(P)，在伏安曲线上分别于0．19和0．51V处出现L／E和E／P转变峰．掺杂态聚合物和本征态聚合物的氧化还原分别经历L=EH=P和LH=EH=P路径，其中E／P转变峰电位随pH升高而发生负移．铂化的聚合物电极对异丙醇的氧化具有明显的催化作用，且随着扫描时间延长，氧化电流逐渐提高；聚合物与铂微粒相互作用，改变铂微粒的几何结构和电子性质，使催化体系具有良好的催化活性和抗中毒能力．在pH=4．7的缓冲溶液中，该修饰电极对异丙醇氧化仍具有催化活性．聚合物在空气中存放太久(3年)会发生降解，从而影响其电化学性质．     

1-三氯锡烷基-2,3-丁二烯和2-三氯锡烷基-1,3-丁二烯与甲醛反应的B3LYP研究

用密度泛函方法在B3LYP/6-31G^**水平上研究了1-三氯锡烷基-2,3-丁二烯和2-三氯锡烷基-1,3-丁二烯与甲醛的反应.优化得到各驻点的几何构型,通过振动分析和内禀反应坐标对过渡态进行了确认,解析了反应路径.并用SCRF(PCM)方法在同一水平上对在CH₂Cl₂溶液中的两反应进行了研究.计算了两反应在气相和CH₂Cl₂溶液中的活化能垒、自由能和平衡常数.结果表明,反应具有很强的选择性,主要得到1-三氯锡烷基-2,3-丁二烯与甲醛反应的产物.该结果与实验事实一致.     

CH2FCF3与O(1D)反应机理的理论研究

用量子化学密度泛函理论(DFT)和G3(MP2)B3方法,对O(1↑D)与CH2FCF3的反应进行了研究．在UB3LYP/6-31G(d)计算水平上,优化了反应势能面上各驻点的几何结构,在G3(MP2)B3水平上进行了单点计算,并利用UB3LYP/6-311 G(3df,3pd)计算的波函数进行了电荷密度分析．通过内禀坐标(IRC)计算和振动分析,对反应过渡态进行了确认,并确定了反应机理．     

锂离子电池正极材料LixNi1／3Mn1／3及电化学性能研究CO1／3O2的合成及电化学性能研究

应用以氢氧化物共沉淀为前驱体的高温固相烧结法合成LiNi1/3Mn1/3Co1/3O2正极材料，研究了沉淀温度及烧结过程锂盐投入量对该材料的结构和电化学性能的影响．结果表明，以室温（-20℃）下合成的氢氧化物为前驱体制备的LiNi1/3Mn1/3Co1/3O2具有较好的电化学性能．高温固相烧结会导致部分LiOH损失，因而在合成过程中需加入过量的氢氧化锂，实验表明Li1.08Ni1/3Mn1/3Co1/3O2材料的电化学性能最优．     

A new diarylheptanoid from Alpinia officinarum promotes the differentiation of 3T3-L1 preadipocytes

A new diarylheptanoid, namely trans-(4R,5S)-epoxy-1,7-diphenyl-3-heptanone (1), and a new natural product, 7-(4″-hydroxy-3″-methoxyphenyl)-1-phenyl-hepta-4E,6E-dien-3-one (2), were obtained from the aqueous extract of Alpinia officinarum Hance, together with three other diarylheptanoids, 5-hydroxy-1,7-diphenyl-3-heptanone (3), 1,7-diphenyl-4E-en-3-heptanone (4) and 5-methoxy-1,7-diphenyl-3-heptanone (5). The structures were characterised mainly by analysing their physical data including IR, NMR and HRMS. This study highlights that the 4,5-epoxy moiety in 1 is rarely seen in diarylheptanoids. In addition, the five isolates were tested for their differentiation activity of 3T3-L1 preadipocytes. The results showed that these compounds could dose-dependently promote adipocyte differentiation without cytotoxicity (IC₅₀ > 100 μM).