紫草素类似物全合成研究

以1,4-二氢基萘醌为原料,经过甲基化、甲酰化、NHK(Nozaki-Hiyama-Kishi)反应、硝酸铈铵(cAN)和AgO/HNO3氧化脱甲氧基等5步反应,完成了一条紫草素类似物新的合成路线.该路线能够简便、快速地合成紫草素类似物.     

1,4,5,8-四甲氧基萘-2-甲醛的合成工艺研究

紫草素（shikonin）为中药紫草中的有效成分,具有多种生物学活性,如抗菌、抗炎、抗病毒、抗肿瘤、抗生育、抗甲状腺亢进、抗免疫低下、降血糖、保肝扩肝等多种作用,引起人们对其合成的重视,有许多紫草素的全合成研究报道。多数以1,4,5,8-四甲氧基萘-2-甲醛（1）为起始原料,但收率均不高。     

紫草素在玻碳电极上的电化学行为及应用

采用电化学测试方法测定了紫草素在玻碳电极上的电化学行为。结果表明,紫草素在玻碳电极产生一对氧化还原波,在pH为3.98及HAc-NaAc(20%乙醇)缓冲溶液中。证实该反应是以吸附控制为主的电极过程。同时,以氧化峰为对象的循环伏安法研究了峰电流与药物浓度的关系。峰值电流与紫草素浓度在2.08×10~(-8)～1.82×10~(-6)mol·L~(-1)范围内具有良好的线性关系。该方法可用于中草药紫草中紫草素及其衍生物总含量的测定,样品无需预处理即可直接测定。通过方波伏安法测出新疆特有紫草素的平均含量为9.063m·mg~(-1),相对标准偏差3.08%,证明采用此方法测定紫草素含量是可行的。     

薄层色谱—化学发光联用技术测定紫草素含量

１引言紫草为紫草科紫草属植物，新疆紫草和紫草属植物紫草的根，为常用中药，紫草素为其有效成份。药理实验证实紫草素具有抗肿瘤、抗炎、抗菌，促伤口愈合等作用。紫草素测定方法一般采用分光光度法、重量法、薄层扫描法。本文根据化学发光原理，以鲁米诺－过氧化氢－钻离子（Ｃｏ２＋）为发光体系，利用过氧化氢定量氧化紫草素苯环上的羟基，从而消耗发光体系中的Ｈ２Ｏ２来降低发光强度，实现发光值动态猝灭。在一定范围内猝灭强度与紫草素含量呈线性关系。本法具有灵敏度高、仪器简单、线性范围宽等优点，是测定萘酯类药物的又一新方法…     

新疆紫草中左旋紫草素的快速制备

利用快速制备色谱技术,首次开展了从新疆紫草中分离制备左旋紫草素的研究。重点考察了洗脱液、流速、进样量对分离制备的影响。最终选用甲醇-水为两相溶剂系统(80%~100%,V/V),流速为5 m L/min,进样量为10 m L进行分离制备。结果显示40 min内制备得到3种有效成分。所得产物纯度经毛细管电泳检测,结构经NMR确证分别为左旋紫草素、乙酰紫草素和β-羟基异戊酰紫草素3种单体。实际可从10 m L萘醌类提取物中制备左旋紫草素15 mg。该方法为快速制备天然产物的活性成分提供了新手段。     

紫草素及去氧紫草素的ESI离子阱质谱裂解分析

应用电喷雾离子阱多级质谱技术对紫草素及其活性衍生物去氧紫草素的结构和质谱裂解规律进行比较研究,并在负离子模式下解析了紫草素的主要特征碎片离子及其裂解规律。紫草素负离子模式下的主要碎片为m/z 287,269,259,218,190及173;其中,碎片m/z 218是其特征峰,碎片m/z 269和m/z 259均可进一步裂解为m/z 241,碎片m/z 190为m/z 259和m/z 218的共同产物离子;此外,碎片m/z 190和m/z 173均可进一步裂解为m/z 162。去氧紫草素负离子模式下主要裂解为碎片m/z 271、253、228和203;其中,碎片m/z253是其特征峰。紫草素和去氧紫草素均能发生过渡态氢重排β-裂解和连续的CO中性丢失。     

紫草素的电化学研究

建立了测定紫草素的单扫描极谱分析方法;在0.03mol/LNa2CO3+0.2mol/LNaOH(pH=12.63)底液中,紫草素于-0.60V(SCE)处有一灵敏的二次导数还原峰,电流峰高与浓度在7.0×10-8～5.6×10-7mol/L和6.0×10-7～4.2×10-5mol/L范围内呈线性关系,检出限为3.5×10-8mol/L;用于中药紫草中紫草素的测定,结果良好;同时还研究了紫草素的电极反应机理.     

左旋紫草素与溶菌酶相互作用的研究

利用荧光猝灭方法结合紫外光谱(UV)、傅立叶红外光谱(FT-IR)和圆二色性光谱(CD),在模拟生理条件下研究了左旋紫草素和溶菌酶的结合常数、主要作用力以及左旋紫草素对溶菌酶二级结构的影响.在温度为296、303和310 K时,根据Scatchard方程测得左旋紫草素和溶菌酶的结合常数分别为3.022×104、1.894×104、0.958 1×104 L·mol-1,结合位点数分别为0.98、0.76、0.68;焓变(ΔH)和熵变(ΔS)分别为-14.78 kJ/mol、24.26 J/(mol·K),结果表明其主要作用力为疏水性和静电作用力.同步荧光和紫外光谱研究进一步证明左旋紫草素与溶菌酶有着较强的结合,左旋紫草素对溶菌酶的荧光猝灭为多种机理同时存在,并根据F(o)rster能量非辐射转移理论测得结合位置与色氨酸残基间的距离r为4.62 nm.CD和FT-IR研究显示,左旋紫草素使溶菌酶的二级结构发生了变化.该文为左旋紫草素在人体内的储存、运输、作用机理及临床试验提供了具有指导作用的信息.     

紫草素的电化学伏安行为研究

紫草素在0.2 mol/L HAc-NaAc缓冲溶液(pH4.3)中,产生灵敏的线性扫描极谱峰,峰电位EP=-0.186 V(vs.Ag/AgCl)。峰电流与紫草素浓度在5×10-7~1×10-5mol/L范围内呈良好的线性关系。可用于紫草中紫草素含量的测定。用线性扫描和循环伏安法测试表明,该体系属具有反应物吸附性的可逆过程体系。     

方波伏安法测定紫草素及其电化学行为的考察

电化学伏安行为研究表明,在pH 3.98的HAc-NaAc(20%乙醇)缓冲溶液中,紫草素在玻碳电极产生了一对氧化还原波,并证实这一反应是受吸附控制为主的电极过程.同时选用方波伏安法以氧化峰为对象考察峰电流与药物浓度的关系,结果表明:峰电流与紫草素浓度在2.08×10-8～1.82×10-6 mol/L范围内呈较好线性关系.方法用于中药药品紫草中紫草素及其衍生物总含量的测定,样品不经预处理分离即可直接测定,结果令人满意.     

Review of Analytical Methods for Atmospheric Oxidants Measurements

Abstract

Instrumental and manual methods currently available for the measurement of atmospheric oxidants are surveyed. Techniques used in the United States are emphasized and their advantages and disadvantages are discussed. Commercial systems are evaluated in terms of general operating principles rather than of specific instruments. The ability of these techniques to meet the measurement requirements defined by U.S. Federal air quality oxidant criteria are discussed. Alternative chemical techniques that may have some advantages over the neutral, buffered KI procedure are discussed. Also some attractive, alternative instrumental procedures that are ozone-specific are presented. These systems are based on chemiluminescence and ultraviolet absorption photometry. Electrochemical and colorimetric methods for total oxidant measurements are compared. Finally, some data are presented on relationships of ozone and total oxidants.     

Densities,speeds of sound,excess volumes and viscosities of binary mixtures of mtbe with tetralin and decalin at 303.15 k

Measurements of densities, speeds of sound, excess volumes and viscosities of binary mixture of methyl tert-butyl ether with tetralin and decalin are reported at 303.15?K over the entire range of composition. Excess volumes are measured using batch dilatometer technique. Sound speeds are obtained using ultrasonic interferometer. Densities are computed from excess volume data. Isentropic compressibilities are derived from density and sound speed data. Speeds of sound are evaluated on the basis of Jacobson's free length theory and Schaff's collision factor theory. The predicted values are in good agreement with the experimental results. The viscosity data are analysed on the basis of corresponding states approach. Excess volumes and deviation in isentropic compressibilities are negative and deviation in viscosities are positive over the entire composition range. The experimental results are discussed in terms of possible molecular interactions between unlike molecules.     

钼、钨系过氧化物在Sharpless烯烃环氧化反应中的应用*

钼、钨系过氧化物是非常重要的Sharpless烯烃环氧化催化剂,有着非常广泛的工业发展前景。本文综述了钼、钨系过氧化物的种类,结构,合成方法及催化活性,分析了各种钼、钨系过氧化物的特点以及在催化环氧化领域的发展现状。同时,本文还讨论了钼、钨系过氧化物催化烯烃环氧化反应的机理。评述了在催化环氧化领域中两种主要理论——Mimoun机理与Sharpless机理的争论焦点及发展现状,以及计算化学对两种理论中间过渡态的研究进展,并且重点分析了Sharpless机理的过渡态结构。此外,本文还综述了影响钼、钨系过氧化物催化剂反应活性的各种因素以及质子所产生的副反应。最后,本文对应用于催化环氧化领域的钼、钨系过氧化物未来的研究方向提出了建议。     

Contactless conductivity detection for microfluidics: designs and applications

Different methods for construction of contactless conductivity detectors (CCD) for microchip electrophoresis device are described in this review. This includes three main schemes of CCD for microchips, such as (i) the detection electrodes are placed along the microchannel from outside of the microchip and they are insulated from the channel by the cover lid of microchip device; (ii) the electrodes are placed across of the microchannel in the same plane and they are insulated by thin separation channel walls and (iii) electrodes are buried in widened part of microchannel and they are insulated from solution by ultrathin layer of silicon carbide. Specific issues related to the CCD on microfluidics are discussed, such as an influence of shape and magnitude of ac voltage and placement of electrodes and their insulation. Various applications for security, pharmacological, bioassays and food analysis purposes are described.     

异丙醇的O-H伸缩振动泛频光谱和分子构像

使用高灵敏的光腔衰荡光谱(CavityRingDownSpectroscopy)技术测出了异丙醇的O-H伸缩v=4、5振动泛频光谱,每个振动能级都有三个吸收峰,被归属为分子构像的O-H伸缩泛频吸收.给出了光腔衰荡光谱的振动泛频吸收的谱带强度公式,并求得分子不同构像在不同振动能级的O-H伸缩泛频吸收的谱带强度;同时利用局域模理论,求得分子各O-H伸缩局域模振子的机械频率(X1)、非谐性(X2)以及解离能(D).用密度泛函(DFT)B3LYP/6-31+G*理论方法优化了分子的各种可能构像,验证了分子存在反式(trans)和偏转(gauche)两种稳定构像,计算的分子的O-H伸缩频率及构像稳定性同实验结果是一致的.     

Bioinspired Strategies for Stretchable Conductors

Stretchable conductors are indispensable components of stretchable electronic devices, such as stretchable sensors, transistors, light-emitting diode arrays, solar cells, and so on. However, most of the conductive materials are stiff with very low stretchability. Nature has evolved various strategies to realize stretchability, which give a lot of inspirations to the design and fabrication of stretchable conductors. We herein summarized the nature’s strategies to realize stretchability and revealed the underlying mechanisms. After that, the applications of these strategies in fabricating stretchable conductors are exemplified and the effects of some important parameters on the performances are discussed. Then, possible applications of these stretchable conductors are summarized. Finally, critical issues in the stretchable conductors are discussed and several prospective exploration directions are provided.     

Inorganic electrides

Inorganic electrides are a novel kind of ionic compounds in which the anions are electrons confined in a complex array of cavities or channels and the cations are nanoscale arrays of alkali metal ions that provide charge balance. In electrides the donated electron behaves like a low-density correlated electron gas, whereby the dimensionality of the electron gas and its electronic and magnetic properties are determined by the topology of the cavities in the host matrix. Unlike traditional electrides, in which alkali cations are encapsulated within an organic cage, inorganic electrides are thermally stable. The current inorganic electrides based on alkali metal loaded zeolites can be designed as useful reduced-dimensionality materials. Inorganic electrides are powerful reducing agents, and they are able to reduce small aromatic molecules to the radical anions within the channels of the zeolite.     

The Application of NMR Spectroscopy and Chemometrics in Authentication of Spices

Spices and herbs are among the most commonly adulterated food types. This is because spices are widely used to process food. Spices not only enhance the flavor and taste of food, but they are also sources of numerous bioactive compounds that are significantly beneficial for health. The healing effects of spices are connected with their antimicrobial, anti-inflammatory and carminative properties. However, regular consumption of adulterated spices may cause fatal damage to our system because adulterants in most cases are unhealthy. For that reason, the appropriate analytical methods are necessary for quality assurance and to ensure the authenticity of spices. Spectroscopic methods are gaining interest as they are fast, require little or no sample preparation, and provide rich structural information. This review provides an overview of the application of NMR spectroscopy combined with chemometric analysis to determine the quality and adulteration of spices.     

抗生素在水环境中的光化学行为

抗生素是在水环境中广泛存在的一类新兴污染物, 近年来, 由于其“假”持久性并能引起环境菌群的抗药性而备受关注. 光化学降解是水环境中抗生素类污染物的重要消减方式. 本文总结了水环境中抗生素光化学行为研究的最新进展, 介绍了抗生素的直接、间接和自敏化光解动力学, 评述了pH和水中溶解性物质对抗生素光解的影响及典型抗生素的光降解路径与机理, 讨论了抗生素的光致毒性, 最后对抗生素在水环境中光化学行为的研究进行了展望.