Targeting Chemical and Biological Warfare Agents at the Molecular Level

After the September 11 tragedies of 2001, scientists and law‐enforcement agencies have shown increasing concern that terrorist organizations and their “rogue” foreign government‐backers may resort to the use of chemical and/or biological agents against U.S. military or civilian targets. In addition to the right mix of policies, including security measures, intelligence gathering and training for medical personnel on how to recognize symptoms of biochemical warfare agents, the major success in combating terrorism lies in how best to respond to an attack using reliable analytical sensors. The public and regulatory agencies expect sensing methodologies and devices for homeland security to be very reliable. Quality data can only be generated by using analytical sensors that are validated and proven to be under strict design criteria, development and manufacturing controls. Electrochemical devices are ideally suited for obtaining the desired analytical information in a faster, simpler, and cheaper manner compared to traditional (lab‐based) assays and hence for meeting the requirements of decentralized biodefense applications. This articler presents a review of the major trends in monitoring technologies for chemical and biological warfare (CBW) agents. It focuses on research and development of sensors (particularly electrochemical ones), discusses how advances in molecular recognition might be used to design new multimission networked sensors (MULNETS) for homeland security. Decision flow‐charts for choosing particular analytical techniques for CBW agents are presented. Finally, the paths to designing sensors to meet the needs of today's measurement criteria are analyzed.     

毒剂的生化分析技术

本文论述了酶法分析、核酸探针、免疫分析法特别是生物传感器在毒剂检测中的应用，提出了毒剂生化分析的发展方向。     

Profiling the Heme-Binding Proteomes of Bacteria Using Chemical Proteomics

Heme is a cofactor with myriad roles and essential to almost all living organisms. Beyond classical gas transport and catalytic functions, heme is increasingly appreciated as a tightly controlled signalling molecule regulating protein expression. However, heme acquisition, biosynthesis and regulation is poorly understood beyond a few model organisms, and the heme-binding proteome has not been fully characterised in bacteria. Yet as heme homeostasis is critical for bacterial survival, heme-binding proteins are promising drug targets. Herein we report a chemical proteomics method for global profiling of heme-binding proteins in live cells for the first time. Employing a panel of heme-based clickable and photoaffinity probes enabled the profiling of 32–54 % of the known heme-binding proteomes in Gram-positive and Gram-negative bacteria. This simple-to-implement profiling strategy could be interchangeably applied to different cell types and systems and fuel future research into heme biology.     

基于碳量子点荧光探针测定法莫替丁的研究

以木炭为碳源,采用回流的方法制备了碳量子点。用荧光光谱、紫外光谱法研究了该碳量子点与法莫替丁的相互作用。实验发现,在pH为7.1的Tris-HCl缓冲溶液中,法莫替丁的加入可使碳量子点荧光信号显著增强,其浓度在8.0×10~(-9)~1.0×10~(-7) mol/L范围内与碳量子点荧光信号强度的增加值△F呈良好的线性关系,相关系数r为0.9993。据此,提出了以碳量子点为荧光探针测定法莫替丁的新方法,方法检出限(3s/k)为2.0×10~(-9) mol/L。该方法简便、快捷、灵敏,应用于样品中法莫替丁含量的测定,回收率范围为98.50%~103.2%。     

A Fluorescent Probe for Investigating the Role of Biothiols in Signaling Pathways Associated with Cerebral Ischemia-Reperfusion Injury

Cerebral ischemia-reperfusion injury (CIRI) is intimately associated with the redox regulation of biothiol, a crucial antioxidant marker that precludes the onset of ROS. We designed a novel fluorescent probe, DCI-Ac-Py , showing various physicochemical properties, such as high selectivity, exceptional signal-to-noise ratio, near-infrared (NIR) optical window, and blood–brain barrier (BBB) penetrability, for detecting biothiols in the brain. The picolinate serves as a specific recognition group that is rapidly activated by biothiol and undergoes nucleophilic substitution with the adjacent acrylic ester to yield the desired NIR probe. Additionally, the probe's lipid solubility is improved through the inclusion of halogen atoms, which aids in penetrating the BBB. Using DCI-Ac-Py , we investigated changes of biothiols in vivo in the brains of mice during CIRI. We found that biothiol-mediated NF-kB classical (P65-related) and nonclassical (RelB-related) pathways contribute to abundant ROS production induced by CIRI and that biothiols are involved in redox regulation. These findings provide new insights into the study of CIRI and shed light on the physiological and pathological mechanisms of biothiols in the brain.     

A New Trace Analytic Method for the Determination of Sequence-Specific DNA with Fluorescent Probes

A new method of fluorescence spectrometry detection of single-strand DNA (ssDNA) was established by hybridizing the ssDNA with its complementary ssDNA to form double-stranded DNA (dsDNA). Our results show that the fluorescence intensity increased significantly when the nucleic acid molecular “light switch"(Ru(phen)₂dppx²⁺) or Hoechst 33258 dye interacted with dsDNA, and the fluorescence intensity also increased as the DNA concentration increased. The changing law was also studied about how the fluorescence intensity changed when the two kinds of fluorescent probes interacted with oligonucleotide of different lengths and different sequences, as well as DNA-DNA′ hybridization products. Then, the effect of the bases mismatch, varying length of DNA chain, and different DNA sequences on the fluorescence intensity were explored at the same time, by detecting the specific DNA sequence of avian influenza H1N1 virus, cauliflower mosaic virus, and hepatitis C virus. Additionally, the selectivity, linear range, and sensitivity of the two probes were compared.     

一类用化学指纹特征鉴别中药材真伪的方法

提出用Fisher因子表征中药材质量模式,根据类间距离最大、类内距离最小原则,计算色谱图中各峰的权值,并以各峰权值为变换向量从各峰面积值中计算出Fisher因子,用于中药材质量模式分类.以红参主根的真伪鉴别为实例,从定量评价、目视比较和聚类分析等方面将Fisher因子、主成分及指纹峰进行分类效果对比研究.结果表明,Fisher因子能更好地表征红参化学模式特征,分类准确性最高.因此,用本文方法提取的Fisher因子是一类能表征中药材质量模式的化学指纹特征参量,适宜用作鉴别中药材真伪.     

Monitoring Chemical Warfare Agents: A New Method for the Detection of Methylphosphonic Acid

Methylphosphonic acid (MPA) is the degradation product of many chemical warfare agents. The convenient detection of this substance would aid in field testing to confirm illicit manufacture and use of banned chemical weapons. Efficient functionalization of MPA with an aromatic diazo compound allowed binding by monoclonal antibodies elicited by using an analogous hapten (see scheme). An ELISA assay was rapid, sensitive, and specific.     

Exploring the Binding Proteins of Glycolipids with Bifunctional Chemical Probes

Glycolipids are important structural components of biological membranes and perform crucial functions in living systems, including signaling transduction and interaction with extracellular environment. However, the mechanistic exploration of glycolipids in vivo is challenging because they are not genetically encoded. Herein, we designed and synthesized a series of bifunctional monogalactosyldiacylglycerol (MGDG) probes as a model by introducing diazirine and terminal alkyne moieties on an aliphatic chain. In combination with proteome profiling and molecular modeling, we have demonstrated that MGDG alleviates inflammation by antagonizing TLR4.     

The Biological and Chemical Ameliorative Effects of Bread Substituted with Dried Moringa Leaves

This study conducted to evaluate the effect of additional dried moringa leaves on bread and their effects on the chemical and biological of rats fed it. Wheat flour with dried moringa leaves powder (DMLB) is used at different levels (6 and 9%) to produce moringa bread. We performed a sensory evaluation of wheat bread substituted with dried moringa leaves, chemical properties (approximate composition and antioxidants), microbiology (total bacteria, spore-forming bacteria, fungi, and yeast) and biological analysis (Triglycerides, total cholesterol, HDL and LDL, ALT, AST, urea, creatinine). Therefore, histopathology examination for kidney and livers of male albino rats fed fortified bread with dried moringa leaves compared with the control sample. The results of the approximate analysis showed significant differences by adding moringa leaves and the percentage of ash, protein, fat, and fiber increased with the moisture content. Moreover, carbohydrates decreased from fortified bread with dried moringa leaves compared to the control sample. The best treatment was fortified bread with 6% dried moringa leaves for all sensory evaluations compared to the other samples and moringa bread (DMLB 9%) helped reduce the microbial load during storage. The effect of moringa bread on liver cirrhosis was evaluated in rats induced by carbon tetrachloride CCl₄. We found out that the effect of moringa leaves on liver and kidney functions in a state of improvement, as for high-density lipoprotein (HDL) and low-density lipoprotein (LDL), the proportion of LDL was less than HDL compared to the control sample. At the same time, moringa leaves have a significant effect on reducing cholesterol, triglycerides, urea, and creatinine in the serum of rats, which may be attributed to the presence of biologically active plant components. It can be concluded that moringa leaves can improve biological and histological of rats feed it.     

4-(1H-1,2,4-三唑-1-亚甲基)苯甲酸过渡金属配合物的合成、结构、抑菌活性及DNA裂解活性

以4-（1H-1,2,4-三唑-1-亚甲基）苯甲酸（HL）为配体,水热合成了三个过渡金属配合物[Cu_0.5L]_n（1）,{[Ni（L）₂·（H₂O）₂]·（H₂O）₂}_n（2）,{[Co（L）₂·（H₂O）₂]·（H₂O）₂}_n（3）;运用红外光谱、元素分析、单晶X射线衍射、热分析、紫外光谱和荧光光谱等手段对化合物进行了表征. 结构分析表明,配合物1 呈现一维（1D）的链状结构,而同构的配合物2 和3 则通过链间的氢键连接为三维（3D）网状结构. 抑菌活性研究表明,配合物对镰刀菌、苹果腐烂病菌、苹果轮纹病菌、梨炭疽病菌和烟草赤星病菌均有良好的抑菌效果,特别是配合物1 的抑菌效果最为显著. 质粒DNA（pUC 18）裂解活性实验结果表明,相比较于化合物2 和3,化合物1 能更有效地促进质粒DNA裂解. 进一步采用光谱法检测三种配合物对DNA的结合作用. 结果显示三种配合物均可插入DNA分子中,其中配合物1的插入作用最为强烈.     

Study on the Chemical Composition and the Biological Activities of Vitis vinifera Stem Extracts

Vitis vinifera (V. vinifera) is a herbaceous plant, cultivated worldwide and known for its biological benefits. The aim of this study is the investigation of the chemical composition as well as the determination of the biological potential of different grape stem extracts obtained by maceration and accelerated solvent extraction (ASE). The HPLC analysis of the tested extracts led to the identification of 28 compounds of which 17 were identified for the first time in grape plants, in addition to seven revealed in the stem part for the first time. Twenty-nine volatile molecules have been detected by GC-MS in the grape stem part; among them seven were identified for the first time in the grape plant. For the biological analysis, the ethyl acetate extract (EtOAc) obtained by maceration showed a significant potential regarding antioxidant activity (IC₅₀ = 42.5 µg/mL), anti-Alzheimer (IC₅₀ = 14.1 µg/mL), antidiabetic (IC₅₀ = 13.4 µg/mL), cytotoxic with HCT-116 (IC₅₀ = 12.5 µg/mL), and anti-inflammatory (IC₅₀ = 26.6 µg/mL) activities, as well as showing the highest polyphenol content (207.9 mg GAE/g DW).     

4-(1H-1,2,4-三唑-1-亚甲基)苯甲酸过渡金属配合物的合成、结构、抑菌活性及DNA裂解活性

Three novel transitionmetal compounds [Cu_0.5L]_n (1), {[Ni(L)₂·(H₂O)₂]·(H₂O)₂}_n(2), and {[Co(L)₂·(H₂O)₂]· (H₂O)₂}_n (3), were hydrothermally synthesized with 4-(1H-1,2,4-triazol-1-ylmethyl) benzoic acid (HL) and characterized by infrared spectroscopy, elemental analyses, single-crystal X-ray diffraction, thermal analyses, UV-Vis spectroscopy, and fluorescence spectroscopy. Structural analyses reveal that compound 1 features a one-dimensional (1D) chain, while isomorphic 2 and 3 exhibit a three-dimensional (3D) network structure with interchain hydrogen-bonding. Antifungal activities tests reveal that 1 has the highest antifungal effect on the five fungi (Fusarium graminearum, Vasa mali, Macrophoma kawatsukai, Colletotrichum gloeosporioides, and Alternaria alternate) among the three compounds. Furthermore, DNA cleavage experiments indicate that compound 1 has more efficient DNA (pUC 18) cleavage activity than compounds 2 and 3. The binding properties of the three compounds with DNA were also investigated by absorption. The results show that the three compounds can intercalate into DNA, and the interaction of compound 1 is the strongest.     

Syntheses,Reactions, Characterization,and Antifungal Activities of Chloro-bis-(2,2-dithio-1,3,2-dioxaphospholane/dioxaphosphorinane)bismuth(III)

Abstract

Chloro-bis(2,2-dithio-1,3,2-dioxaphospholane/dioxaphosphorinane)bismuth(III) compounds have been synthesized by the reaction of bismuth trichloride with sodium 2,2-dithio-1,3,2-dioxaphospholane/dioxaphosphorinane in 1:2 molar ratio in benzene solution. Reactions of these chloro-bis(2,2-dithio-1,3,2-dioxaphospholane/dioxaphosphorinane)-bismuth(III) compounds with sodium tetraisopropoxyborate in equimolar ratio in benzene solution yield the corresponding heterobinuclear bismuth derivatives with boron. All compounds were characterized by elemental analyses and molecular weight measurements. Plausible structures are proposed on the basis of IR and ¹H, ¹¹B, ¹³C, and ³¹P spectroscopic studies. 2-Mercapto-2-thioxo-1,3,2-dioxaphospholanes-/dioxaphosphorinanes and the corresponding chloro-bis(2,2-dithio-1,3,2-dioxaphospholane/dioxaphosphorinane)bismuth (III) compounds show antifungal activities against Fusarium and Trichoderma.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

铼-锇测年法中锇的化学行为的研究

本文研究了不同介质中Os的价态变化和蒸馏过程以及等离于体质谱(ICP/MS)测定中的同位素分馏现象。用水吸收蒸馏出的OsO_4可使Os的ICP/MS测量灵敏度提高到50倍.在此基础上建立了辉钼矿的Re-Os测年法。测得的辉钼矿Re-Os年龄符合地质背景,并与其它传统测年法的结果一致。     

CO2化学利用的一条新途径

C02开发利用一直是世界各国大型化工企业异常关注的研究课题，但是，由于C02结构稳定，化学活性差，因而决定了该领域的研究课题难度较大，进展比较缓慢．本文报道了一种利用天然气还原C02制备会成气的最新研究结果，该过程不仅可以为破一化学工业提供廉价原料，从而开辟一条极重要的非石油原料的化学工业路线，而且对减缓全球性温室效应也具有一定的社会意义．1实验日分1·1催化剂制备按表1所列组成，以7－AI。0。、硝酸镍、硝酸镁和稀土硝酸盐为原料，采用常规浸渍法参照文献［‘］制备催化剂．1·Zfffe反应评价催化反应评价采用双套管…     

Chemical Composition and Biological Activities of Essential Oils from the Leaves,Stems, and Roots of Kadsura coccinea

The chemical composition and biological activities of the essential oils from the leaves, stems, and roots of Kadsura coccinea (K. coccinea) were investigated. The essential oils were extracted by hydro distillation and analyzed by gas chromatography mass spectrometry (GC-MS) and gas chromatography with flame ionization detector (GC-FID). Antioxidant activities of the essential oils were examined with DPPH radical scavenging assay, ABTS cation radical scavenging assay, and ferric reducing antioxidant power assay. Antimicrobial activities were evaluated by determining minimum inhibitory concentrations (MIC) and minimum microbiocidal concentrations (MMC). Acetylcholinesterase and butyrylcholinesterase inhibitory activity of the essential oils were also tested. A total of 46, 44, and 47 components were identified in the leaf, stem, and root oils, representing 95.66%, 97.35%, and 92.72% of total composition, respectively. The major compounds of three essential oils were α-pinene (16.60–42.02%), β-pinene (10.03–18.82%), camphene (1.56–10.95%), borneol (0.50–7.71%), δ-cadinene (1.52–7.06%), and β-elemene (1.86–4.45%). The essential oils were found to have weak antioxidant activities and cholinesterase inhibition activities. The essential oils showed more inhibitory effects against Staphylococcus aureus (S. aureus) than those of other strains. The highest antimicrobial activity was observed in the root oil against S. aureus, with MIC of 0.78 mg/mL. Therefore, K. coccinea essential oils might be considered as a natural antibacterial agent against S. aureus with potential application in food and pharmaceutical industries.     

化学污染的稀土降解研究

本文对化学污染的稀土降解进行了研究，研究结果表明，只需控制施用的稀土的浓度和总量，即可达到既增产又解毒的目的，它是一种具有良好发展前景的肥料。     

氯参与的化学气相淀积金刚石的热力学分析

用非平衡热力学耦合模型研究了金刚石在CHCl体系中的生长,计算所得CHCl体系的金刚石生长的相图与大量实验结果符合良好.通过热力学分析讨论了氯的添加对提高金刚石薄膜生长速率及其质量的影响以及降低淀积温度的作用.