2-甲基-6-乙基-N-丁氧甲基-N-氯乙酰基苯胺的合成

以2 甲基 6 乙基苯胺、甲醛、氯乙酰氯和正丁醇等为主要原料,以一种经济环保的工艺路线合成了杀菌剂2 甲基 6 乙基 N 丁氧甲基 N 氯乙酰基苯胺。考察了反应条件对反应结果的影响,获得了较佳的反应条件:烯胺化反应中n(甲醛)/n(2 甲基 6 乙基苯胺)=1 5,反应温度70～75℃,反应时间2h;酰化反应中n(氯乙酰氯)/n(2 甲基 6 乙基苯胺)=1 15,反应温度30～35℃,反应时间1 0h;醚化反应中n(丁醇)/n(2 甲基 6 乙基苯胺)=5 5,反应温度50℃,反应时间5h。在较佳反应条件下,产品质量分数和收率分别达到93%和90%。     

二聚脱氢芳樟醇碱分解反应制备6-甲基-5-庚烯-2-酮

以脱氢芳樟醇水蒸气蒸馏残液为原料,反应压力为常压,反应温度为103~142℃,残液中的二聚脱氢芳樟醇和脱氢芳樟醇在浓KOH或NaOH水溶液催化作用下进行分解反应,生成6-甲基-5-庚烯-2-酮和乙炔。考察了碱浓度、温度、油碱质量比对残液分解反应的影响,提出了反应历程。以w(KOH)=50%的水溶液为催化剂,反应温度124~127℃,残液与碱液质量比15∶1,残液中的二聚脱氢芳樟醇、脱氢芳樟醇质量分数分别为60.1%、33.6%,搅拌速度100~200 r/min,反应5 h,脱氢芳樟醇水蒸气蒸馏残液分解生成6-甲基-5-庚烯-2-酮的反应收率为94.3%,反应液中的6-甲基-5-庚烯-2-酮质量分数为92.1%。     

1-苄基-6-溴吲哚-3-甲醛的合成

以6-溴吲哚(2)为原料,通过Vilsmeier-Haack反应、 N-苄基保护,两步反应合成得到1-苄基-6-溴吲哚-3-甲醛(1)。对反应工艺进行了优化,确定合成6-溴-1H-吲哚-3-甲醛(3)的反应温度为25℃,反应时间为5 h;合成1的优化反应条件为:n(3)∶n(BnBr)=1.0∶1.3, n(3)∶n(KOH)=1.0∶1.5,反应温度25℃,反应时间3 h。在优化条件下,两步反应总收率86.5%。产物结构经1H NMR和ESI-MS确证。     

辣椒碱合成方法的改进

以6-溴己酸为起始原料,经Wittig反应、胺化还原反应、N-酰化反应,制备了N-[（4-羟基-3-甲氧基苯基）-甲基]-8-甲基-6-壬烯酰胺,经EI-MS、1H NMR等测试技术分析确定了目标化合物的分子结构。     

2-乙基-4-乙氧基-6-羟基嘧啶的合成工艺研究

以丙腈为初始原料 ,依次合成丙脒盐酸盐 ,2 -乙基 - 4,6 -二羟基嘧啶 ,最后合成目标产物 2 -乙基 - 4-乙氧基 - 6 -羟基嘧啶 ,考察了催化剂用量、物料配比、碱浓度、反应时间、反应温度对 2 -乙基 -4-乙氧基 - 6 -羟基嘧啶收率的影响 ,在优化工艺条件下 :以四乙基碘化铵为催化剂 ,用量为 6‰ (相对于 2 -乙基 - 4,6 -二羟基嘧啶的摩尔分数 ) ,物料配比 1∶ 1 .1 5 ,氢氧化钠质量百分比浓度为 1 0 % ,反应时间 6 h,反应温度 6 0°C,反应总收率高达 80 .2 %。同时对反应产物及其各个中间体进行了定性定量分析     

3-溴-2-氟苯甲酸的合成

以2-氨基-6-氟苯腈为原料,经溴化、水解和重氮化脱氨基反应合成3-溴-2-氟苯甲酸,产物的含量为99.20%(HPLC),总摩尔产率约38%。产物结构通过MS和1 H NMR验证。其中溴化反应的最佳条件为n(2-氨基-6-氟苯腈)∶n(NBS)=1∶1.05,n(2-氨基-6-氟苯腈)∶n(DMF)=1∶6,反应温度为5℃;水解反应的最佳反应条件为n(2-氨基-5-溴-6氟苯腈)∶n(NaOH)=1∶1.5,水解时间为8h,温度控制在回流状态下。该法具有生产成本低、反应条件温和、易于工业化生产的优点。     

9α-氟-6α-甲基氢化泼尼松的合成研究

以6α-甲基氢化泼尼松为起始原料,经酯化、脱水、溴化、环合、二次酯化、加成6步反应合成了目标化合物9α-氟-6α-甲基氢化泼尼松,总收率13%。该合成路线反应步骤较少,反应条件温和,操作简单,对工业生产具有较好的参考价值。     

4-甲基-2-乙基-6-羟基嘧啶的合成研究

以丙腈为原料，与氯化氢、氨气反应合成丙眯盐酸盐，在水溶液中同乙酰乙酸乙酯反应合成4-甲基-2-乙基-6-羟基嘧啶。考察了反应时间、反应温度、物料配比、pH值对4-甲基-2-乙基-6-羟基嘧啶收率的影响。优化条件为：反应温度40℃、反应的pH=12．4、反应时间为6～7h、乙酰乙酸乙酯与丙腈的物质的量比为1．09：1．0，在此条件下反应的总收率为88．7％。     

3-(2-甲基-6-硝基苯基)-4,5-二氢异噁唑的合成研究

研究了常压下一锅法制备3-(2-甲基-6-硝基苯基)-4,5-二氢异噁唑的方法。原料2-甲基-6-硝基苯甲醛肟溶解后通入氯气进行氯化反应,氮气吹脱过量的氯气和生成的氯化氢后,通入乙烯、滴加缚酸剂进行环合反应得到产品。探索了溶剂、溶剂的量、反应温度和反应时间等因素对反应的影响,优化条件为以1,2-二氯乙烷为溶剂、溶剂量为原料的5倍、室温反应、通入乙烯反应8 h,反应转化率99.5%。优化条件下,收率为90.5%。     

6-苯基-5-氯-3(2H)-哒嗪酮合成工艺的改进

6-苯基-3-哒嗪酮经三氯化磷和氯气氯代,所得中间体6-苯基-3,5-二氯哒嗪经氢氧化钠皂化、盐酸酸化制得标题化合物,通过回收皂化反应的副产物6-苯基-3-氯-5-羟基哒嗪作为氯代反应的原料,总收率56.6%,考察了回收物料及氯气流量对氯代反应的影响,讨论了皂化产物的分离工艺,最终产物经1HNMR结构确证.     

The Uniqueness of Tryptophan in Biology: Properties,Metabolism, Interactions and Localization in Proteins

Tryptophan (Trp) holds a unique place in biology for a multitude of reasons. It is the largest of all twenty amino acids in the translational toolbox. Its side chain is indole, which is aromatic with a binuclear ring structure, whereas those of Phe, Tyr, and His are single-ring aromatics. In part due to these elaborate structural features, the biosynthetic pathway of Trp is the most complex and the most energy-consuming among all amino acids. Essential in the animal diet, Trp is also the least abundant amino acid in the cell, and one of the rarest in the proteome. In most eukaryotes, Trp is the only amino acid besides Met, which is coded for by a single codon, namely UGG. Due to the large and hydrophobic π-electron surface area, its aromatic side chain interacts with multiple other side chains in the protein, befitting its strategic locations in the protein structure. Finally, several Trp derivatives, namely tryptophylquinone, oxitriptan, serotonin, melatonin, and tryptophol, have specialized functions. Overall, Trp is a scarce and precious amino acid in the cell, such that nature uses it parsimoniously, for multiple but selective functions. Here, the various aspects of the uniqueness of Trp are presented in molecular terms.     

环境对改性塑料表面亲/疏水转变的作用机制

塑料制品因其质量轻、性质稳定等优点而得到广泛使用,但大部分废旧塑料未被合理回收而成为污染物,对环境造成了危害。因此,废旧塑料回收、再加工成为保护环境和资源利用的有效途径。而分离是废旧塑料能进行再加工的重要环节,目前已经发展了丰富的分离方法,其中塑料浮选法因具有工艺简单、污染少的特点而受到人们的青睐。但在塑料浮选中,其表面亲疏水性受环境的影响,该过程进一步恶化分离效果。为了避免分离过程的波动性,急需探究环境因素对亲疏水性的作用。基于此,本文选取了ABS、PC、PS三种废旧塑料,探究环境对浮选分离及表面亲疏水性基团重构的影响。结果表明：氧化改性后的ABS、PC、PS处于极性环境时,塑料可浮性基本未发生改变,接触角发生轻微浮动,表面仍保持亲水性。处于乙醇环境中,塑料可浮性上升,其接触角上升至75°左右,表面疏水性恢复速度大于极性环境。而在非极性环境中,塑料可浮性上升速度较快,表面完全恢复为未改性前的疏水性。在极性环境中,亲水基团更容易停留在表面,随着极性的减小,亲水基团逐渐迁移至本体,塑料表面恢复为疏水。因此,极性环境更有利于塑料表面保持亲水性。     

重组胶原蛋白的绿色生物制造及其应用

胶原蛋白存在于各个组织器官,与动物胶原蛋白相比,重组胶原蛋白组分单一、安全性高、生产过程可控。本篇综述简述了重组胶原蛋白不同表达体系的构建,包括动植物以及微生物表达体系,比较了不同体系的优缺点。着重介绍了微生物体系中影响产物表达的不同发酵参数的调控,产物的分离纯化工艺以及重组胶原蛋白在医学领域的应用。提出微生物发酵体系较动植物体系成本低,操作简单,易于扩大生产;温度、pH、溶解氧、葡萄糖、乙酸浓度等影响大肠杆菌发酵中的蛋白表达量;酵母发酵中,甲醇添加量、温度、pH和溶解氧是主要影响参数;微生物发酵体系均需通过不同的粗纯及精纯技术获得纯度较高的产物。同时,重组胶原蛋白在生物医学领域发挥着重要作用。     

Pheromonal activity of single castoreum constituents in beaver,Castor canadensis

Behavioral activity of single components of beaver castoreum was demonstrated for the first time. In four experiments samples were presented to free-ranging beaver in their family territories. First, responses to whole castoreum and anal gland secretion (AGS) from males and females were tested. Second, 24 compounds, known to be constituents of beaver castoreum, were individually screened for activity. Four of these consistently released immediate responses during the observation periods. These are the phenols 4-ethylphenol and 1,2-dihydroxybenzene and the ketones acetophenone and 3-hydroxyacetophenone. In the most complete responses, the beaver sniffed from the water, were attracted to the odor, swam toward its source, went on land, and then approached, sniffed, pawed, and scent-marked the artificial scent mound. 4-Ethoxyphenol, a compound not yet found in castoreum, also released these responses. Five additional compounds resulted in a few delayed visits to the samples during the night following the observations, as evidenced by destroyed scent mounds. These are 4-methyl-1,2-dihydroxybenzene, 4-methoxyacetophenone, 5-methoxysalicylic acid, salicylaldehyde, and 3-hydroxybenzoic acid. Third, mixtures of 24 and six compounds were tested. Responses to these mixtures could be as strong as those to whole castoreum. Fourth, the four regularly active compounds were tested in two additional beaver populations and proved to be active there, too. The response was strongest in the densest beaver population.     

Neuroinflammation in Post-Ischemic Neurodegeneration of the Brain: Friend,Foe, or Both?

One of the leading causes of neurological mortality, disability, and dementia worldwide is cerebral ischemia. Among the many pathological phenomena, the immune system plays an important role in the development of post-ischemic degeneration of the brain, leading to the development of neuroinflammatory changes in the brain. After cerebral ischemia, the developing neuroinflammation causes additional damage to the brain cells, but on the other hand it also plays a beneficial role in repair activities. Inflammatory mediators are sources of signals that stimulate cells in the brain and promote penetration, e.g., T lymphocytes, monocytes, platelets, macrophages, leukocytes, and neutrophils from systemic circulation to the brain ischemic area, and this phenomenon contributes to further irreversible ischemic brain damage. In this review, we focus on the issues related to the neuroinflammation that occurs in the brain tissue after ischemia, with particular emphasis on ischemic stroke and its potential treatment strategies.     

生物质热解制备高品质生物油研究进展

生物质热解制备生物油是能源富集的有效途径,是实现碳闭路循环的重要方式,作为一种环境友好型技术受到广泛关注和研究。然而,生物质热解反应过程复杂,生成的生物油热值低、含氧量高及强酸性等特点,制约了生物油的分离提纯、制备合成气以及燃烧等方面的应用,生物油品质的提升迫在眉睫。本文从生物质三组分、原料预处理、反应参数、催化剂、反应器等方面综述了影响生物油品质的主要因素,分析了生物油的特点,不同预处理下生物质特性的变化与生物油的关系,催化剂参与的热解行为对提升生物油品质的导向作用以及常用生物质热解反应器的特点,并对影响生物油品质的主要因素进行了总结。最后,针对影响制备高品质生物油的诸多因素提出建议,以期为制备高品质生物油提供参考和借鉴。     

油气集输过程中含油污泥减量化

集输过程中的含油污泥具有成分复杂、含液率高、乳化胶结稳定等特性，占油田危险废物新增量的约60%，是污染防治的重点。近年来，学者们开展了大量“调质-固液分离”减量化技术降低其环境风险和处置成本，但仍存在需要针对含油污泥不同来源优选相匹配的减量化调质方法和装置的难题。为此，本文回顾了氧化、破乳、絮凝、干化/半干、超声波、微波等化学与物理调质方法，离心机、叠螺机、压滤机3种固液分离装置研究进展，通过分别对各种调质方法及装置的对比分析，重点阐述了其作用机理、优缺点、适用对象。其中化学调质方法中破乳氧化、加酸更适用于高含聚油泥；表面活性剂破乳需加热，可与超声波相结合；有机和无机絮凝剂配合可提高罐底泥中油回收效果；干化/半干化法受经济效益制约。在文献基础上，认为未来应加强生物表面活性剂、生物电化学系统、椭圆叠螺机、基于固液分离装置数值模型基础上的设计与优化软件、多学科相结合的减量化耦合技术研究。     

钒钛磁铁矿流态化直接还原技术现状与发展趋势

钒、钛是重要的生产生活资料,90%以上赋存于钒钛磁铁矿中. 我国钒钛磁铁矿资源储量丰富,但在当前高炉?转炉工业流程中,受高炉冶炼条件限制,钒钛磁铁精矿中的钛元素未能得到回收利用. 面对钒钛磁铁精矿铁钒钛资源全面提取利用难题和资源环保集约综合利用的迫切需求,直接还原?电炉熔分两步法流程受到广泛关注,其中流化床法因直接采用粉矿入炉、工序流程短、低温综合反应效率高,在直接还原工序中优势突出. 本工作阐述并对比了钒钛磁铁精矿流化床直接还原工艺,分析了钒钛磁铁精矿难还原的原因,重点介绍了流态化预氧化强化还原方法,同时归纳流化床直接还原过程中影响粘结失流的主要因素,总结了5种抑制铁矿粉粘结失流的直接方法,并提出了添加MgO惰性添加剂、碳包覆及改进床型结构的研究发展方向.     

Comparative Analysis of Brain Lipids in Mice,Cats, and Humans with Sandhoff Disease

Sandhoff disease (SD) is a glycosphingolipid (GSL) storage disease that arises from an autosomal recessive mutation in the gene for the β-subunit of β-Hexosaminidase A (Hexb gene), which catabolizes ganglioside GM2 within lysosomes. Accumulation of GM2 and asialo-GM2 (GA2) occurs primarily in the CNS, leading to neurodegeneration and brain dysfunction. We analyzed the total lipids in the brains of SD mice, cats, and humans. GM2 and GA2 were mostly undetectable in the normal mouse, cat, and human brain. The lipid abnormalities in the SD cat brain were generally intermediate to those observed in the SD mouse and the SD human brains. GM2 comprised 38, 67, and 87% of the total brain ganglioside distribution in the SD mice, cats, and humans, respectively. The ratio of GA2–GM2 was 0.93, 0.13, and 0.27 in the SD mice, cats, and humans, respectively, suggesting that the relative storage of GA2 is greater in the SD mouse than in the SD cat or human. Finally, the myelin-enriched lipids, cerebrosides and sulfatides, were significantly lower in the SD brains than in the control brains. This study is the first comparative analysis of brain lipids in mice, cats, and humans with SD and will be important for designing therapies for Sandhoff disease patients.     

A review of ZrO2 nanoparticles applications and recent advancements

The many branches of nanoscience have made significant strides and advancements during the past ten years, as has the entire scientific community. Zirconia nanoparticles have several uses as adsorbents, nanosensors, nanocatalysts, and other types of nanomaterials. Their outstanding biomedical uses in dental care and drug delivery, as well as their intriguing biological characteristics, such as their anti-cancer, anti-microbial, and antioxidant activity, have further encouraged researchers to investigate their physicochemical properties using various synthetic pathways. Due to the popularity of zirconia-based nanomaterials, the current research comprehensively examines several synthesis techniques and their effects on the composition, dimensions, forms, and morphologies of these nanomaterials. In general, there are two methods for creating zirconia nanoparticles: chemical synthesis, which uses hydrothermal, solvothermal, sol-gel, microwave, solution combustion, and co-precipitation processes; and a greener method, which uses bacteria, fungi, and plant components. The aforementioned techniques have been evaluated in the present review for achieving particular phases and shapes. A thorough analysis of zirconia-based nanomaterial's uses is also included in the review. Furthermore, comparisons with their equivalent composites for various applications as well as the influence of particular phases and morphologies have been added. The final portion includes the summary, future outlook, and potential application.