氢氟醚的合成和应用研究进展

第三代氯氟烃替代品之一——氢氟醚类化合物（HFEs）的合成方法分为两类,第一类是醚类化合物的氟化,包括直接氟化法和电化学氟化法;第二类是通过含氟化合物与其他化合物的反应制备氢氟醚,反应类型主要包括不饱和烃与醇的加成反应、含氟羰基化合物的烷基化反应和卤代烷与醇的分子间消除反应。其中,碱催化不饱和烃与醇加成制备氢氟醚操作简便,反应条件相对温和,产物易分离提纯,是一具有工业化前景的氢氟醚合成方法。氢氟醚物化性能优良,且环境友好,在制冷、清洗等行业有着广阔的应用前景。     

含氟聚氨酯弹性体的制备及性能研究

以异佛尔酮二异氰酸酯(IPDI)、端羟基聚丁二烯(HTPB)、氟代二醇、1,4-丁二醇(BDO)和丙烯酸羟乙酯(HEA)为原料,经多步反应合成了可紫外光固化的疏水性聚氨酯弹性体。考察了氟代二醇用量对聚氨酯弹性体的相对分子质量大小、耐热性、疏水性、耐水性、机械强度的影响。结果表明,氟代二醇被成功引入到聚氨酯链段中。随着氟代二醇含量增加,聚氨酯相对分子质量逐渐减小,相对分子质量分布逐渐变宽;当引入8%的氟代二醇,所得聚氨酯弹性体的热分解温度从295℃升高到340℃,膜表面的接触角从82.5°上升到108.6°,吸水率从5.1%下降到1.6%,断裂伸长率及回弹率都明显上升,说明氟代二醇的引入改善了聚氨酯的耐热性、耐水性以及机械强度。     

三聚氟氰合成文献综述及工业化前景分析

三聚氟氰是合成氟代均三嗪活性染料的关键中间体。由于国内的三聚氟氰没有形成大规模工业化生产，价格昂贵，影响了下游氟代均三嗪活性染料的发展，而低价格的三聚氟氰将促进氯代均三嗪活性染料的更新换代。本文综述了三聚氟氰的各种合成方法，着重探讨了在工业上可行的氟化氢法和氟化钠法的优缺点。通过对原料成本、设备腐蚀程度、能耗和“三废”量三个方面进行比较，认为氟化氢法更适合于大规模的工业化生产。     

氟代碳酸乙烯酯的合成与精制进展

综述了氟代碳酸乙烯酯的合成方法,包括直接氟代法、电化学氟化法、卤素交换法,比较了不同合成方法的优缺点,重点介绍了卤素交换法中不同氟化剂的使用。对氟代碳酸乙烯酯的前处理工序及精馏技术进行了总结,并对氟代碳酸乙烯酯的研究前景进行了展望。     

间接电氧化法生产对氟苯甲醛

氟代苯甲醛是一类非常重要的有机化工原料，近年来，在合成医药、农药等新型材料中，氟代苯甲醛作为反应中间体发挥着重大的作用，例如：氟代苯甲醛可合成有取代基的苯基萘基吡喃，用来治疗免疫系统的疾病、糖尿病的并发症等；合成抗氧化剂可用于治疗癌症、肝硬化、动脉硬化等疾病；对氟苯甲醛可用于合成多种医药，如降血压药、解热镇痛消炎药、抗癌药、股肉放松药等。氟代苯甲醛还常用来合成一些重要的化学品，例如氟代苯甲醛和葡萄糖、酵母等作用可得（1R，2S）－1－萘基－1，2－丙二醇；对氟苯甲醛和二茂铁在路易斯酸、一氯化铝等的催化下可合成二茂铁基香在化合物；在KF存在下Al2O3作为固体底物，对氟苯甲醛和芴缩合生成二苯并富烯类化合物。另外氟代苯甲醛还可作为化妆品添加剂、植物保护剂及杀菌剂、除臭剂等。用途极为广泛，因此研制氟代苯甲醛具有良好的经济效益和社会效益。     

溶剂法醇解合成3,3,3-三氟丙基甲基二甲氧基硅烷

以3,3,3-三氟丙烯与甲基二氯硅烷催化合成3,3,3-三氟丙基甲基二氯硅烷。采用 溶剂法,以3,3,3-三氟丙基甲基二氯硅烷和甲醇为原料醇解合成3,3,3-三氟丙基甲基二甲氧基 硅烷。考察溶剂种类、原料配比、冷凝温度、填料大小等因素的影响,确立了最优合成条件。     

芳香族含氟中间体合成技术进展

3．3含氟酸类化合物3．3．1邻氟苯甲酸邻氟苯甲酸是新型医药和农药中间体，用于制备杀菌剂吩唑醇、氟苯嘧啶、氟苯嘧啶醇以及药物氟安啶，另外可以合成多种含氟中间体如，2-氟-5-硝基苯甲酸、2-氟-5-氨基苯甲酸、邻氟苯甲酸甲酯、邻氟苯甲酸乙酯等。邻氟苯甲酸合成工艺有三条：1）以邻氨基苯甲酸为原料，     

N-(2-氟-5-苯硼酸频哪醇酯)-2-吗啉代乙酰胺合成研究

介绍了N-(2-氟-5-苯硼酸频哪醇酯)-2-吗啉代乙酰胺的合成方法。以2-氟-5-溴苯胺为起始原料、先与联硼酸频哪醇酯反应,得到中间体3-氨基-4-氟苯硼酸频哪醇酯,在经过两步反应,得到所要的目标化合物。结果表明:该合成路线目标化合物的总收率为71.7%,其化学结构经MS、1H-NMR经行了确证。该合成工艺具有操作简单,原料易得,后处理方便,总收率较高,适合工业化生产。     

全氟丙酮二水合物毒性作用的病理学

全氟丙酮二水合物是用来合成氟代的饱和与不饱和醇类、胺类、氨基酸以及优良的热稳定聚合物的。全氟丙酮二水合物同它的同系物代表ω-氟代烷基酮和ω-氟代甲基酮的毒性对比,说明它与剧毒的-氟代酮类相似。但是,根据我们过去的实验结果,全氟丙酮二水合物不能生成-氟醋酸,而是经过肾脏的新陈代谢,或是生成氟代酮酸,或是生成与尿甘酸(葡萄糖醛酸)一起以共轭物形式析出的氟代叔醇。因此,全氯丙酮二水合物的     

几种卤代吡啶类农药中间体的合成与应用

概述了3，5，6-三氯吡啶-2-醇、2，3-二氯吡啶、2-氯-5-氯甲基吡啶、2，3-二氟-5-氯吡啶和2，3-二氯-5-三氟甲基吡啶5种卤代吡啶类化合物的合成方法，并对其在农药工业中的应用做了简要介绍。     

High-Performance Polymers for Separation and Purification Processes: An Overview

Separation and purification techniques are applied in many important fields, such as in the medical, chemical, metallurgical, environmental, and pharmaceutical industries. Recent advances in separation science and the urgent need for highly selective purification have necessitated a rapid progress with respect to the reagents, chemicals, and surfactants used in separation processes to attain a high efficiency and selectivity. Polymeric materials have attracted considerable interest, and they have been widely used as extractants, catalysts, and modifiers, in separation and purification processes. This review outlines the recent advances in the use of novel polymers, natural and synthetic, in different separation and purification techniques. Various separation techniques such as chromatography, crystallization, precipitation, distillation, electrophoresis, filtration, and mineral processing methods are discussed, and the polymers used in each method are described in terms of their properties, structure, and function. The application of polymers shows great promise in achieving a highly efficient separation, especially in the areas of membrane separation and water purification. The rational design of new multifunctional polymers with triggered functions presumably presents new opportunities for the development of advanced separation methods.     

污泥生物炭中氮硫行为及环境效应研究进展

污泥生物炭中氮硫元素含量高,其氮硫行为和环境效应对全球气候变化的影响不容忽视。以往的研究中,研究者往往以富碳生物炭作为主要研究对象,关注碳对全球气候变化的行为和功效,而对氮硫元素的作用关注不够。本文从原始污泥基本性质到其热解过程,再到生物炭的老化,逐步对污泥生物炭整个生命周期内氮硫的行为及其环境效应研究进行综述,并对未来应注重开展的研究方向进行展望,为生物炭中氮硫元素固定、释放及与之关联的环境效应和温室气体排放控制研究提供理论基础。分析表明,污泥中氮元素含量普遍高于硫元素,且热解过程中氮比硫更容易转移至气相产物。氮硫元素随热解温度的增加,在三相产物中的分配都是炭中持续减少,油中先增后减,气中一直增加。高温（＞800℃）条件下,气相中的氮含量高于固相,而硫元素则仍然主要存在于固相中。污泥生物炭老化及其环境效应研究表明,污泥生物炭氮硫元素与土壤的相互作用及其温室效应问题在今后的研究中应引起重视。     

The Emerging Roles of Chromogranins and Derived Polypeptides in Atherosclerosis,Diabetes, and Coronary Heart Disease

Chromogranin A (CgA), B (CgB), and C (CgC), the family members of the granin glycoproteins, are associated with diabetes. These proteins are abundantly expressed in neurons, endocrine, and neuroendocrine cells. They are also present in other areas of the body. Patients with diabetic retinopathy have higher levels of CgA, CgB, and CgC in the vitreous humor. In addition, type 1 diabetic patients have high CgA and low CgB levels in the circulating blood. Plasma CgA levels are increased in patients with hypertension, coronary heart disease, and heart failure. CgA is the precursor to several functional peptides, including catestatin, vasostatin-1, vasostatin-2, pancreastatin, chromofungin, and many others. Catestatin, vasostain-1, and vasostatin-2 suppress the expression of vascular cell adhesion molecule-1 and intercellular adhesion molecule-1 in human vascular endothelial cells. Catestatin and vasostatin-1 suppress oxidized low-density lipoprotein-induced foam cell formation in human macrophages. Catestatin and vasostatin-2, but not vasostatin-1, suppress the proliferation and these three peptides suppress the migration in human vascular smooth muscles. Chronic infusion of catestatin, vasostatin-1, or vasostatin-2 suppresses the development of atherosclerosis of the aorta in apolipoprotein E-deficient mice. Catestatin, vasostatin-1, vasostatin-2, and chromofungin protect ischemia/reperfusion-induced myocardial dysfunction in rats. Since pancreastatin inhibits insulin secretion from pancreatic β-cells, and regulates glucose metabolism in liver and adipose tissues, pancreastatin inhibitor peptide-8 (PSTi8) improves insulin resistance and glucose homeostasis. Catestatin stimulates therapeutic angiogenesis in the mouse hind limb ischemia model. Gene therapy with secretoneurin, a CgC-derived peptide, stimulates postischemic neovascularization in apolipoprotein E-deficient mice and streptozotocin-induced diabetic mice, and improves diabetic neuropathy in db/db mice. Therefore, CgA is a biomarker for atherosclerosis, diabetes, hypertension, and coronary heart disease. CgA- and CgC--derived polypeptides provide the therapeutic target for atherosclerosis and ischemia-induced tissue damages. PSTi8 is useful in the treatment of diabetes.     

木质素在超临界甲醇和乙醇溶剂中液化过程分析

通过研究木质素分别在超临界甲醇和乙醇溶剂中的液化过程，分析反应温度（260～340℃）及反应时间（0～120min）对木质素在两种溶剂中的转化率、生物油收率及其组分差异的影响。实验表明，木质素在超临界乙醇中的转化率及产物收率均高于甲醇。当反应温度340℃，反应时间60min，木质素在超临界乙醇中的转化率和生物油收率比在甲醇中分别提高了16.23%和11.54%，残渣收率降低了16.23%。通过GC-MS和FTIR对生物油和残渣分析，发现生物油组分中芳香族化合物相对含量较高，在甲醇和乙醇溶剂中分别达到66.13%和58.84%；随着反应时间的延长，甲醇溶剂中残渣的醚键官能团逐渐增强，而在乙醇溶剂中则先增强后减弱。分析认为在木质素降解过程中，超临界乙醇和甲醇均可产生氢自由基作为供氢体，攻击木质素及其大分子片段中的官能团，同时使液化产物中的活性片段减活，减弱重聚合反应，从而更利于芳烃产物的生成。而甲醇在液化过程中容易与木质素断键产生的苯酚中间体发生脱氢缩合反应，通过醚键聚合产生长链芳香族化合物，形成残渣，降低生物油收率。     

Theanine,Antistress Amino Acid in Tea Leaves,Causes Hippocampal Metabolic Changes and Antidepressant Effects in Stress-Loaded Mice

By comprehensively measuring changes in metabolites in the hippocampus of stress-loaded mice, we investigated the reasons for stress vulnerability and the effect of theanine, i.e., an abundant amino acid in tea leaves, on the metabolism. Stress sensitivity was higher in senescence-accelerated mouse prone 10 (SAMP10) mice than in normal ddY mice when these mice were loaded with stress on the basis of territorial consciousness in males. Group housing was used as the low-stress condition reference. Among the statistically altered metabolites, depression-related kynurenine and excitability-related histamine were significantly higher in SAMP10 mice than in ddY mice. In contrast, carnosine, which has antidepressant-like activity, and ornithine, which has antistress effects, were significantly lower in SAMP10 mice than in ddY mice. The ingestion of theanine, an excellent antistress amino acid, modulated the levels of kynurenine, histamine, and carnosine only in the stress-loaded SAMP10 mice and not in the group-housing mice. Depression-like behavior was suppressed in mice that had ingested theanine only under stress loading. Taken together, changes in these metabolites, such as kynurenine, histamine, carnosine, and ornithine, were suggested to be associated with the stress vulnerability and depression-like behavior of stressed SAMP10 mice. It was also shown that theanine action appears in the metabolism of mice only under stress loading.     

TRPA1 Expression and Pathophysiology in Immune Cells

The non-selective cation channel TRPA1 is best known as a broadly-tuned sensor expressed in nociceptive neurons, where it plays key functions in chemo-, thermo-, and mechano-sensing. However, in this review we illustrate how this channel is expressed also in cells of the immune system. TRPA1 has been detected, mainly with biochemical techniques, in eosinophils, mast cells, macrophages, dendritic cells, T cells, and B cells, but not in neutrophils. Functional measurements, in contrast, remain very scarce. No studies have been reported in basophils and NK cells. TRPA1 in immune cells has been linked to arthritis (neutrophils), anaphylaxis and atopic dermatitis (mast cells), atherosclerosis, renal injury, cardiac hypertrophy and inflammatory bowel disease (macrophages), and colitis (T cells). The contribution of TRPA1 to immunity is dual: as detector of cell stress, tissue injury, and exogenous noxious stimuli it leads to defensive responses, but in conditions of aberrant regulation it contributes to the exacerbation of inflammatory conditions. Future studies should aim at characterizing the functional properties of TRPA1 in immune cells, an essential step in understanding its roles in inflammation and its potential as therapeutic target.     

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.     

Effect of Empagliflozin on Sphingolipid Catabolism in Diabetic and Hypertensive Rats

The profile of sphingomyelin and its metabolites shows changes in the plasma, organs, and tissues of patients with cardiovascular, renal, and metabolic diseases. The objective of this study was to investigate the effect of empagliflozin on the levels of sphingomyelin and its metabolites, as well as on the activity of acid and neutral sphingomyelinase (aSMase and nSMase) and neutral ceramidase (nCDase) in the plasma, kidney, heart, and liver of streptozotocin-induced diabetic and Angiotensin II (Ang II)-induced hypertension rats. Empagliflozin treatment decreased hyperglycemia in diabetic rats whereas blood pressure remained elevated in hypertensive rats. In diabetic rats, empagliflozin treatment decreased sphingomyelin in the plasma and liver, ceramide in the heart, sphingosine-1-phosphate (S1P) in the kidney, and nCDase activity in the plasma, heart, and liver. In hypertensive rats, empagliflozin treatment decreased sphingomyelin in the plasma, kidney, and liver; S1P in the plasma and kidney; aSMase in the heart, and nCDase activity in the plasma, kidney, and heart. Our results suggest that empagliflozin downregulates the interaction of the de novo pathway and the catabolic pathway of sphingolipid metabolism in the diabetes, whereas in Ang II-dependent hypertension, it only downregulates the sphingolipid catabolic pathway.     

Lipid components of flax,perilla, and chia seeds

Composition of fatty acids, tocopherols, sterols, and TAGs in the lipids of flax, perilla, and chia seeds were investigated where lipid content was at 45, 40, and 35%, respectively. α‐Linolenic acid (ALA) dominated among fatty acids in all oils and accounted for 58.2, 60.9, and 59.8% in flax, perilla, and chia, correspondingly in these three oils trilinolenin was the main TAG found at 19.7, 22.6, and 21.3%. Triunsaturated TAGs accounted for 77.9, 77.5, and 74.5% of the total amounts in flax, perilla, and chia oils. Contents of tocopherol were at 747 in flax, 734 in perilla, and 446 mg/kg in chia seed lipids. γ‐Tocopherol was the dominating isomer contributing 72.7% in flax, 94.3% in perilla, and 94.4% in chia to the total amount of tocopherols. Flaxseed lipids contained 25.6% of plastochromanol‐8, derivative of γ‐tocotrienol with longer side chain; perilla and chia oils contained only 1.4% of it. Phytosterols were present at 4072, 4606, and 4132 mg/kg in those seeds, respectively. Among sterols, β‐sitosterol dominated and was found at 35.6, 73.3, and 49.8% of the total amounts of sterols in flax, perilla, and chia seed lipids. All of the investigated oilseeds have an excellent nutritional quality and can be a potential source of nutraceutical fats which can enrich diet in linolenic acid and other functional components.