绿色化学及其绿色系统工程技术与环境友好

绿色化学理念的基本内涵既有微观意义又有宏观意义与工程技术的意义。绿色化学及其绿色技术在社会生产与生活、传统化学工业改造与创新、资源合理充分利用与循环再生、绿色净化与监测、环境保护与开发等方面发挥重要作用。实施绿色化学及其绿色系统工程技术,使社会生产、生活绿色化,实现人类与环境友好对话,建设“环境友好”家园,营造“环境和谐”生活,是坚持可持续发展、科学发展核心战略的重要举措,是当今世界人类面临的重大挑战与机遇。     

Advancing the Drug Discovery and Development Process

The current state of affairs in the drug discovery and development process is briefly summarized and then ways to take advantage of the ever‐increasing fundamental knowledge and technical knowhow in chemistry and biology and related disciplines are discussed. The primary motivation of this Essay is to celebrate the great achievements of chemistry, biology, and medicine and to inform and inspire students and academics to enter the field of drug discovery and development while, at the same time, continue to advance the fundamentals of their disciplines. It is also meant to encourage and catalyze multidisciplinary partnerships between academia and industry as scientists attempt to merge their often complementary interests and expertise to achieve new improvements and breakthroughs in their respective fields, and the common goal of applying them to the discovery and invention of new and better medicines, especially in areas of unmet needs.     

Semiconductor quantum dots and metal nanoparticles: syntheses,optical properties,and biological applications

We review the syntheses, optical properties, and biological applications of cadmium selenide (CdSe) and cadmium selenide–zinc sulfide (CdSe–ZnS) quantum dots (QDs) and gold (Au) and silver (Ag) nanoparticles (NPs). Specifically, we selected the syntheses of QDs and Au and Ag NPs in aqueous and organic phases, size- and shape-dependent photoluminescence (PL) of QDs and plasmon of metal NPs, and their bioimaging applications. The PL properties of QDs are discussed with reference to their band gap structure and various electronic transitions, relations of PL and photoactivated PL with surface defects, and blinking of single QDs. Optical properties of Ag and Au NPs are discussed with reference to their size- and shape-dependent surface plasmon bands, electron dynamics and relaxation, and surface-enhanced Raman scattering (SERS). The bioimaging applications are discussed with reference to in vitro and in vivo imaging of live cells, and in vivo imaging of cancers, tumor vasculature, and lymph nodes. Other aspects of the review are in vivo deep tissue imaging, multiphoton excitation, NIR fluorescence and SERS imaging, and toxic effects of NPs and their clearance from the body. Figure Semiconductor quantum dots and metal nanoparticles have extensive applications, e.g., in vitro and in vivo bioimaging Tamitake Itoh and Abdulaziz Anas contributed equally to this article.     

印度洋热液区贻贝及栖息沉积物中金属元素的特征分析

本研究采集了印度洋热液区贻贝生物及其栖息沉积物样品,分析了生物体及沉积物中常见微量元素及稀土元素的含量与分布特征,研究了生物体与沉积物金属元素的相关性,以及稀土元素的生态化学特征等.结果表明:印度洋热液区沉积物中常见微量金属主要为Fe(96.62 mg/kg)、Mn(1.143 mg/kg)和Zn(322.6 μg/kg),微量元素归一化计算得Fe含量比值高达98.15%,可获悉该热液区沉积物主要为铁矿类物质.深海贻贝中微量元素及稀土元素的分布趋势与深海沉积物中元素分布存在较好的相关性,相关性系数分别为0.991与0.996,近海贻贝中金属元素的含量及分布与深海贻贝存在差异性.深海沉积物与贻贝中轻重稀土元素均呈现分馏现象,且贻贝中富集轻稀土比较显著;从稀土配分模式可知,沉积物与贻贝中的Eu与Gd均呈现异常现象,深海沉积物和深海贻贝中Eu异常现象较为显著.深海沉积物、贻贝及近海贻贝中δEu分别为9.50、10.68和0.23,而δCe分别为2.21、2.71和4.38,表明近海贻贝中稀土元素富集来源与深海贻贝存在差异性,深海沉积物与深海贻贝稀土元素具有同源性.     

A comparative study of chiral separation of proton pump inhibitors by supercritical fluid chromatography and high-performance liquid chromatography

A comparative study of chiral separation of pantoprazole and rabeprazole is carried out using supercritical fluid chromatography and high-performance liquid chromatography. The columns used were Chiralpak IA and Chiralpak IE. The best mobile phase in supercritical fluid chromatography was carbon dioxide-0.2% triethylamine in methanol (60:40) and 0.1% triethylamine in n-hexane-ethanol (50:50) in high-performance liquid chromatography. For supercritical fluid chromatography, values of the retention factor of pantoprazole enantiomers were 3.97 and 4.88. These values for rabeprazole enantiomers were 6.10 and 7.52. The values of separation and resolution factor for pantoprazole and rabeprazole were 1.23 and 1.23 and 2.20 and 3.36, respectively. Similarly, for high-performance liquid chromatography, the values of retention factor for enantiomers of pantoprazole were 4.02 and 7.32. These values for rabeprazole enantiomers were 5.32 and 7.88, respectively. The values of separation and resolution factor for pantoprazole and rabeprazole were 1.82 and 1.48 and 9.22 and 6.58, respectively. A comparison was carried out, which confirmed supercritical fluid chromatography as the best method due to its fastness, eco-friendly, and inexpensiveness. The reported methods are effective, efficient, and reproducible and may be used to separate and identify pantoprazole and rabeprazole in any unknown samples.     

剌梨利康饮对汞中毒大鼠汞铜锌含量的影响

用高汞水喂养大鼠８周,复制出慢性汞中毒模型,再分别自由饮用利康饮饮料和腹腔注射二巯基丙磺酸钠３周,探讨剌梨利康饮和二巯基丙磺酸钠对慢性汞中毒大鼠体内汞、铜、锌含量的影响。结果显示：慢性汞中毒引起血清、肝、脑和肾中汞含量升高的同时,引起血清、脑和肾中铜、锌含量及肝中锌含量降低;利康饮可降低血清和肾中汞含量,并可提高血清、脑和肾中铜、锌含量及肝含量;二巯基丙磺酸钠虽可降低血清、肝和肾中汞含量,升高血清     

Mutual physiological genetic mechanism of plant high water use efficiency and nutrition use efficiency

Water deficiency and lower fertilizer utilization efficiency are major constraints of productivity and yield stability. Improvements of crop water use efficiency (WUE) and nutrient use efficiency (NUE) is becoming an important objective in crop breeding. With the introduction of new physiological and biological approaches, we can better understand the mutual genetics mechanism of high use efficiency of water and nutrient. Much work has been done in past decades mainly including the interactions between different fertilizers and water influences on root characteristics and crop growth. Fertilizer quantity and form were regulated in order to improve crop WUE. The crop WUE and NUE shared the same increment tendency during evolution process; some genes associated with WUE and NUE have been precisely located and marked on the same chromosomes, some genes related to WUE and NUE have been cloned and transferred into wheat and rice and other plants, they can enhance water and nutrient use efficiency. The proteins transporting nutrient and water were identified such as some water channel proteins. The advance on the mechanism of higher water and nutrient use efficiency in crop was reviewed in this article, and it could provide some useful information for further research on WUE and NUE in crop.     

多糖类生物医用材料—甲壳素和壳聚糖的研究及应用

对甲壳素和壳聚糖的制备工艺,结构与性质以人在固定化酶、药物控释载体、絮凝剂、吸附剂、医用敷料等方面的应用进行了综述。     

近红外光谱快速分析青贮饲料pH值和发酵产物

采用近红外光谱技术,结合偏最小二乘回归法,研究了142个不同种类的秸秆青贮饲料样品的pH值和发酵产物(乳酸、乙酸、丙酸、丁酸和氨态氮),建立了干燥粉碎和新鲜样品的近红外漫反射光谱定量分析模型以及浸提液样品的近红外透射光谱定量分析模型。研究发现,pH值的近红外漫反射光谱和透射光谱的分析效果均较好,校正模型决定系数R2和验证集样品预测值与化学值的相关关系决定系数r2都大于0.80,并且干燥粉碎、新鲜和浸提液样品的RPD值分别为3.44、2.50和2.27;3种状态样品的乳酸、乙酸、丁酸和氨态氮的定量分析模型精度需进一步提高;R2在0.64~0.85之间;RPD值在1.38~1.93之间;丙酸含量的测定结果较差。方差分析显示,3种状态样品的测定结果之间均无显著性差异(P>0.05)。     

Metabolism of 2,4-dinitrotoluene and 2,6-dinitrotoluene, and their dinitrobenzyl alcohols and dinitrobenzaldehydes by Wistar and Sprague-Dawley rat liver microsomal and cytosol fractions

The metabolism of 2,4-dinitrotoluene (2,4-DNT), 2,4-dinitrobenzyl alcohol (2,4-DNB), 2,4-dinitrobenzaldehyde (2,4-DNBAl), 2,6-DNT, 2,6-DNB and 2,6-DNBAl in the microsomal and cytosol fractions prepared from unfortified male Wistar and male Sprague-Dawley (S.D.) rat livers was investigated. Data obtained by high-performance liquid chromatography (HPLC) indicated that the products of dinitrotoluenes (2,4-DNT and 2,6-DNT), dinitrobenzyl alcohols (2,4-DNB and 2,6-DNB), and dinitrobenzaldehydes (2,4-DNBAl and 2,6-DNBAl) in the microsomal and cytosol preparations containing nicotinamide adenine dinucleotide phosphate (NAD(P] and reduced NAD(P)(NAD(P)H) were dinitrobenzyl alcohols (2,4-DNB and 2,6-DNB), dinitrobenzaldehydes (2,4-DNBAl and 2,6-DNBAl), and dinitrobenzoic acids (2,4-DNBA and 2,6-DNBA), and dinitrobenzyl alcohols (2,4-DNB and 2,6-DNB), respectively. From these results, it was concluded that the dinitrobenzaldehydes (2,4-DNBAl and 2,6-DNBAl) were intermediates in the oxidations of dinitrobenzyl alchols (2,4-DNB and 2,6-DNB) to dinitrobenzoic acids (2,4-DNBA and 2,6-DNBA), and that the oxidations of dinitrobenzyl alcohols (2,4-DNB and 2,6-DNB) to dinitrobenzaldehydes (2,4-DNBAl and 2,6-DNBAl) and the reductions of dinitrobenzaldehydes to dinitrobenzyl alcohols (2,4-DNB and 2,6-DNB) were reversible.(ABSTRACT TRUNCATED AT 250 WORDS)     

智能响应材料在磷酸化肽和糖肽富集中的应用

蛋白质的磷酸化和糖基化作为研究最广泛的两种翻译后修饰(PTMs),在疾病的早期无创诊断、预后和治疗评估中表现出越来越大的潜力。蛋白质的异常磷酸化和糖基化经常被用于临床蛋白质组学研究和疾病相关生物标志物的发现。目前已有多种材料被开发用于磷酸化肽和糖肽的富集研究,其中,智能响应材料由于具有独特的响应特性,已被陆续报道用于磷酸化肽和糖肽的富集。智能响应材料可对外界刺激做出响应,发生结构和性质上的变化,将光、电、热、机械等信号转化为生物化学信号。响应分子是决定智能响应材料响应特性的先决条件,它们在不同刺激条件下(如温度、pH、光、机械应力、电磁场等)的可逆异构化将导致材料的宏观物理和化学性质的动态变化。与传统材料相比,智能响应材料可以可逆地“打开”和“关闭”,具有更好的可调控性。由于引起智能材料响应的刺激信号对其性能具有重要的影响,综述根据施加的刺激种类对智能响应材料进行分类,具体分为外源性响应材料和内源性响应材料,且分别总结了外源性响应材料、内源性响应材料以及内外源共同响应材料在磷酸化肽和糖肽富集方面的工作。此外,综述对智能响应材料在磷酸化肽和糖肽富集方面的发展前景进行了展望,并且提出了智能响应材料在其他蛋白质翻译后修饰方面的应用中存在的挑战。     

甲基丙烯酸甲酯聚合动力学和分子量模型及仿真

考虑甲基丙烯酸甲酯聚合过程中体积收缩，反应物和生成物的浓度变化，以及由于凝胶、玻璃化和笼闭等效应对各速率常数和物性参数的影响，从基元反应和物料平衡出发，推导了半间歇，有链转移剂参与情况下的聚合动力学和分子量模型。用模型仿真计算了聚合温度、引发剂、溶剂和链转移剂的种类和浓度等对甲基丙烯酸甲酯聚合动力学和聚合过程中分子量变化的影响规律，并与实验和文献数据进行比较。     

Contributions to the Chemistry of the Binary Compounds of the Transition Elements

Phase and structural relationships of the sulfur, selenium, and tellurium compounds of the 4d and 5d transition elements of groups IV to VII of the periodic system are discussed. Homologous elements behave very similarly with respect to the chalcogens, and this is particularly the case for niobium and tantalum, and for molybdenum and tungsten. However, zirconium, niobium, and molybdenum have a greater tendency towards formation of chalcogen-poor phases than their homologues hafnium, tantalum, and tungsten. Subchalcogenides are known only for zirconium and niobium. The number of phases and the tendency towards formation of solid solutions are considerably smaller among the tellurides than among the sulfides and selenides. The crystal structures of the telluride phases also differ from those of the sulfide and selenide phases of analogous composition. In addition, a review of the phase and structural relationships of the arsenic and antimony compounds of the 4d and 5d transition elements of groups V to VII is given.     

Suppression of adipogenesis by Au nanostructures-conjugated Sargassum seaweed extracts in 3 T3-L1 adipocytes

Recently, with the development of metal nanostructure synthesis technology, Au nanostructures (AuNPs) are synthesized using seaweed extract without using an organic solvent and applied to the pharmaceutical field. In this regard, in this study, AuNPs biosynthesis was mediated through extracts of two brown algae (Sargassum siliquastrum [SS] and Sargassum horneri [SH]) without the use of stabilizers or surfactants. In addition, we investigated the effects of SS-AuNPs (SS-functionalized AuNPs) and SH-AuNPs (SH-functionalized AuNPs) on adipogenesis in adipocytes and their underlying molecular mechanisms. A rapid and simplified synthesis of SS-AuNP and SH-AuP was achieved using aqueous extracts of SS and SH. The morphology, structure and composition of SS-AuNPs and SH-AuNPs were characterized by DLS, FTIR, UV–Vis spectroscopy, HR-TEM and EDS analysis. The stable monodisperse SS-AuNPs and SH-AuPs were synthesized with mean sizes of 17.47 ± 0.13 nm and 21.0 ± 2.74 and zeta potentials of ?31.9 ± 0.75 and ?34.57 ± 4.43, the biosynthetic AuNPs with the face-centered structure of SS-AuNPs and SH-AuPs had crystalline characteristics, and many functional groups that play an important role in the biological reduction present in the SS and SH extracts were adsorbed on the surfaces of the SS-AuNPs and SH-AuPs. This study was conducted to investigate the effect of SS-AuNPs and SH-AuPs on adipogenesis in adipocytes. SS-AuNPs and SH-AuPs reduced morphological changes and increased lipid accumulation by approximately 80% compared with that in mature adipocytes (MDI-induced). This result was accompanied by a reduction in the triglyceride content. SS-AuNPs and SH-AuPs suppressed lipid accumulation by downregulating C/EBPα, PPARγ, SREBP 1, FAS, and aP2 mRNA and protein expression. Furthermore, SS-AuNPs and SH-AuPs induced the mRNA and protein expression of UCP1, PRDM16, and PGC1α to increase mitochondrial biogenesis in mature adipocytes and effectively induced brown adipogenesis. SS-AuNPs and SH-AuPs have potent anti-adipogenic effects and can be used as potential therapeutic agents for obesity.     

Nature spermidine and spermine alkaloids: Occurrence and pharmacological effects

Spermidine and spermine are special polyamines in organisms, and produced in vivo by putrescine and S-adenosylmethionine catalyzed by a variety of enzymes. Spermidine and spermine possess multiple amino groups, and are closely related to cell division, growth and survival. Spermidine and spermine alkaloids are widely distributed in plants, bacteria and marine organisms, and can be divided into macrocyclic and open chain according to the skeletons. Spermidine and spermine alkaloids exhibited numerous pharmacological effects such as anti-inflammatory, antibiotics, anti-tumor, anti-Alzheimer and anti-virus. However, up to now, there are few systematic reviews on spermidine and spermine alkaloids. In this review, based on the number of atoms in the ring, we summarized the distributions and pharmacological effects of spermidine and spermine alkaloids. Spermidine and spermine alkaloids have special chemophenetic significances in the plant kingdom, especially the macrocyclic spermidine and spermine alkaloids. Spermidine alkaloids are much more abundant in nature than spermine alkaloids. The pharmacological activities of the open chain spermidine and spermine alkaloids are studied in depth. Polycyclic guanidine spermidine alkaloids, isolated from marine sponge, exhibit great potential in various cancer cells. However, pharmacological studies of macrocyclic spermidine and spermine alkaloids are scarce. Synthesis is an effective way to get more spermidine and spermine alkaloids and their analogues for further study.     

Insecticidal activity of essential oil of Carum Carvi fruits from China and its main components against two grain storage insects

During our screening program for agrochemicals from Chinese medicinal herbs and wild plants, the essential oil of Carum carvi fruits was found to possess strong contact toxicity against Sitophilus zeamais and Tribolium castaneum adults, with LD?? values of 3.07 and 3.29 μg/adult, respectively, and also showed strong fumigant toxicity against the two grain storage insects with LC?? values of 3.37 and 2.53 mg/L, respectively. The essential oil obtained by hydrodistillation was investigated by GC and GC-MS. The main components of the essential oil were identified to be (R)-carvone (37.98%) and D-limonene (26.55%) followed by α-pinene (5.21), cis-carveol (5.01%) and β-myrcene (4.67%). (R)-Carvone and D-limonene were separated and purified by silica gel column chromatography and preparative thin layer chromatography, and further identified by means of physicochemical and spectrometric analysis. (R)-Carvone and D-limonene showed strong contact toxicity against S. zeamais (LD?? = 2.79 and 29.86 μg/adult) and T. castaneum (LD?? = 2.64 and 20.14 μg/adult). (R)-Carvone and D-limonene also possessed strong fumigant toxicity against S. zeamais (LC?? = 2.76 and 48.18 mg/L) and T. castaneum adults (LC?? = 1.96 and 19.10 mg/L).     

视网膜脱离后PVR的形成与氧自由基和锌、铜关系的研究

为探讨氧自由基和锌、铜在视网膜脱离后增殖性玻璃体视网膜病变 (PVR)中的作用 ,收集了 48例视网膜脱离患者视网膜下液 (SRF) ,利用紫外分光光度计测定了SRF中LPO的含量和SOD的活性 ,用原子吸收光谱法测定了Zn、Cu的含量。结果表明 ,随着PVR程度及玻璃体浑浊的加重、病程的延长 ,LPO含量增加 ,SOD活性明显下降 ,P <0 0 5 ,差异有统计学意义。提示SRF中LPO、Zn、Cu含量及SOD活性的改变与视网膜脱离后PVR的发生、发展有密切关系。     

Volatile components of selected liverworts, and cytotoxic, radical scavenging and antimicrobial activities of their crude extracts

Crude extracts of the Tahitian liverworts Mastigophora diclados and Frullania sp., the Indonesian Frullania sp., Dumortiera hirsuta and Marchantia sp., and the Japanese Porella perrottetiana were investigated chemically by using gas chromatography-mass spectrometry (GC-MS). All extracts contained various volatile sesqui- and diterpenoids and a few aromatic compounds. The Tahitian M. diclados and Frullania sp., and the Indonesian Frullania sp. exhibited cytotoxic activity against HL-60 and KB cell lines. The extracts of the Tahitian M. diclados and the Indonesian Marchantia sp. showed radical scavenging activity, whereas the crude extracts of the Tahitian M. diclados and Frullania sp., and the Indonesian Frullania and Marchantia sp. showed antimicrobial activity against Staphylococcus aureus and Bacillus subtilis.     

A biophysical perspective of understanding nanoparticles at large

In this article we present a biophysical perspective that describes the fate of nanoparticles in both the aqueous phase and in living systems. Specifically, we show the correlations between the physicochemistry of fullerenes and their uptake, translocation, transformation, transport, and biodistribution in mammalian and plant systems, at the molecular, cellular, and whole organism level. In addition to fullerenes and their structural derivatives, we describe the biological and environmental implications and applications of the condensed matter of carbon nanotubes and quantum dots, and the soft condensed matter of plastic and dendrimers. The main purpose of this article is to demonstrate the vast opportunities and unique advantages of applying experimental and simulation biophysics to the nascent research field of understanding nanoparticles at large.