褐煤氧化升温中含氧基团的变化规律

煤分子中的含氧基团是发生煤氧复合反应,引起煤炭自燃灾害的关键因素。通过原位傅里叶红外光谱试验,对褐煤氧化升温过程中的含氧基团变化进行了定性和定量分析,研究煤氧复合反应过程中含氧基团的变化规律。结果表明:低温氧化过程中,褐煤中羟基含氧官能团是参与早期30℃～80℃范围煤氧复合反应的关键含氧官能团,含氧官能团中其化学活性最高,特征吸收峰强度下降幅度最大,220℃时,下降幅度超过了70%;羧基、羰基、脂肪醚基和芳香醚基等4类含氧官能团含量随温度升高而升高,上升幅度依次:羰基羧基脂肪醚芳香醚。煤氧复合反应的低温阶段20℃～220℃为高温阶段积累了大量的羧基、羰基化合物等中间过渡产物。     

羟基(—OH)对煤自燃侧链活性基团氧化反应特性的影响

针对煤结构及其氧化反应机理不明等问题,以羟基(—OH)和煤自燃侧链活性基团—OCH,—CHOHCH 3和—OCH 3为研究对象,采用密度泛函理论(DFT)的B3LYP-311G(d,p)方法,构建出了羟基(—OH)处于侧链活性结构邻位的小分子结构模型。基于前线轨道理论和量子化学理论,采用Gaussian 16软件对小分子模型的静电势、前线轨道的能级和电荷分布及煤氧复合反应过程中的热力学参数进行了模拟计算,探究了侧链活性基团的低温氧化特性和羟基(—OH)对其的影响。计算结果显示,在侧链活性结构中,氢原子周边呈强正电势,为亲核反应活性位点,而氧原子附近呈强负电势,为亲电反应活性位点。当羟基(—OH)处于侧链活性基团邻位时,会削弱侧链活性基团的亲电反应能力,增加—CHO和—CHOHCH 3的亲核反应能力,而使—OCH 3的亲核反应能力消失;通过分析各活性基团最高占据轨道(HOMO:Highest Occupied Molecular Orbital)和最低未占轨道(LUMO:Lowest Unoccupied Molecular Orbital)可知,侧链活性基团的稳定性与其前线轨道的成键能力并不一致,而活性基团与氧气发生复合反应的难易程度主要取决于该基团前线轨道中LUMO的成键能力,成键能力越强,复合反应越容易发生;由于羟基(—OH)改变了侧链活性基团前线轨道上的电子特性,故当其与侧链基团共存时,会使—CHO和—CHOHCH 3与氧气的复合反应更容易发生,而使—OCH 3与氧气的复合由自发的放热反应转变为非自发的吸热反应。该研究成果可为揭示煤自燃微观作用机理和研发煤自燃新型高效阻化材料提供参考。     

纳米二氧化硅粒径尺寸调控及其对表面化学修饰的影响研究

本文通过sol-gel法制备了粒径可控的纳米SiO2,最小粒径为35 nm,最大粒径为350 nm.采用比表面积测试仪、透射电镜(TEM)、扫描电镜(SEM)以及红外光谱(FTIR)表征了纳米SiO2的物理化学特性,研究了不同粒径纳米SiO2对其表面化学修饰的影响机制.结果表明,sol-gel法制备纳米SiO2用水量显著影响粒径尺寸,粒径小于80 nm时,SiO2表面呈粗糙和不规则球形.粒径小于80 nm的SiO2表面的羟基主要以孤立的羟基存在,而粒径大于180 nm时,其表面的羟基以氢键结合的状态为主.纳米SiO2表面的羟基结合状态决定了其表面与硅氧烷化学反应活性,氢键结合的羟基基团不利于硅氧烷的化学修饰,孤立存在的羟基基团有利于纳米SiO2与硅氧烷反应.这一研究结果对指导纳米二氧化硅的表面处理和化学修饰具有重要意义.     

长焰煤低温氧化主要官能团迁移规律研究

煤自燃是引起煤矿火灾的主要原因,宏观上表现为煤自燃释放热量不断积聚,最终导致煤体升温引发火灾;微观上表现为煤中的活性官能团不断与氧进行各种氧化反应产生热量,不同煤种微观结构的种类和数量不同导致煤自燃倾向性不同。为研究典型杨伙盘长焰煤的原始波谱图、特征温度点的红外结构参数变化规律和主要官能团的迁移规律,采用原位漫反射傅里叶变换红外光谱测试系统,测量煤氧化过程中官能团的变化,得到了长焰煤原始煤样的波谱图;采用Origin软件对原始波谱进行分峰拟合,得出了各官能团的含量;计算分析了不同特征温度点下的红外结构参数,并与阳泉无烟煤进行了对比分析。结果表明:原始煤样中长焰煤的内表面积比较大,内部结构疏松,脂肪氢含量较多,脂肪链长度较短,芳香缩合度较低,更易发生自燃;随温度升高,各个温度点结构参数I_1长焰煤小于无烟煤,结构参数I_2长焰煤大于无烟煤,结构参数I_3长焰煤为先递减后递增的趋势;长焰煤中羟基、脂肪烃和含氧官能团是较活跃的基团,主要受自身羟基含量、烷基侧链和脂肪烃长链的影响,在煤氧化过程中变化较大,对煤的氧化反应影响较大;芳香烃在长焰煤中的变化较小,相对比较稳定。     

Research progress on chemical modification of silk fibroin and its applications北大核心CSCD

Mulberry silk is composed of the two major parts of two triangle-like silk fibroin fibers and sericin covering the fibers and a few lipids. After removing the sericin on the raw silk what is left is the silk fibroin fiber. Silk fibroin is the main part of silk accounting for about 75% of the total weight. Silk fibroin contains 18 natural amino acids such as glycine Gly alanine Ala serine Ser serine aspartic acid Asp and tyrosine Tyr . The secondary structure of silk fibroin has three main conformations α-helix β-fold and random coil. Under certain conditions the three conformations can transform into each other and change the mechanical properties of the silk fibroin material. Silk fibroin extracted from silk fiber is a natural polymer with biocompatibility and biodegradability. It can be further processed into different forms of materials nanoparticles films hydrogels sponges etc. It has been applied in many fields such as biomedicine and cosmetics. In order to meet the needs of different fields researchers have conducted further chemical modification treatment based on the original excellent properties of silk fibroin. Meanwhile the active groups on various amino acid residues in silk fibroin also provide chemical reaction sites for the chemical modification of silk fibroin. The chemical modification methods of silk fibroin mainly include amino acid residue modification macromolecular grafting modification and crosslinking reaction modification. Among them amino acid residue modification can modify protein amino acid residues by chemical reagents and some groups can be introduced into the side chains of silk fibroin macromolecules. Grafting modification of silk fibroin macromolecules is one of the main means to bind functional compounds to silk fibroin macromolecular chains. The properties of grafted silk fibroin are affected by the type and grafting rate of the grafts. The chemical crosslinking reaction modification of silk fibroin macromolecules is to make the macromolecular chains connected by covalent bonds and form a network structure by means of crosslinking agents enzymes or ultraviolet irradiation. The cross-linking reaction can not only form covalent bonds within and between the molecular chains of silk fibroin thus changing its structural properties and improving its stability but be used to form covalent bonds with other polymers. At present the chemical modification of silk fibroin is mainly applied in the fields of silk textiles biomedicine and environmental science. In the field of silk textiles graft copolymerization modification of vinyl and other monomers crosslinking agent modification and other methods are used to overcome the shortcomings of silk like being easy to wrinkle. The graft modified monomers mainly include ethylene methacrylate and methylacrylamide. The active groups on crosslinking agents such as polycarboxylic acid / anhydride and epoxide are covalently combined with carboxyl hydroxyl and amino groups on macromolecules of silk fibroin to improve the wrinkle resistance of silk fabrics. In the field of biomedicine silk fibroin materials with appropriate chemical modification have better biological activity drug delivery ability antimicrobial properties and mechanical properties. The optimization of these properties enables silk fibroin materials to show great potential in drug control delivery tissue regeneration and wound repair. The applied research in the field of environmental science mainly focuses on the adsorption separation and catalysis of impurities in water. Therefore the modification of amino acid residues grafting and cross-linking of protein macromolecules can change some important properties of silk fibroin and meet the requirements of various applications and functionalization of silk fibroin. In many fields of chemical modification and application of silk fibroin protein fruitful results have been achieved which has laid a good foundation for the further development of related fields and also shows that the chemical modification of silk fibroin material has great potential and application prospects. However there are still some problems that need to be overcome and further improved in the current chemical modification methods such as mild modification conditions and accurate adjustment of the degree of modification which will be the research direction of related fields in the future. © 2022 Authors. All rights reserved.     

蛋白酶水解底物特异性机制研究进展

蛋白酶酶解底物位点的专一性,对酶解产物的组成与比例都有较大影响,直接影响最终产物的价值。酶法水解蛋白质存在水解效率低、特异性成分产率低以及后期纯化成本高等问题,使得特异性的酶解方式难以实现大规模工业化应用。解决这一问题则亟需探究蛋白酶特异性水解机理,得到酶解产物的分子机制。基于此,文章围绕蛋白酶的水解特异性,综述了目前与特异性相关的底物基团性质、结合部位氨基酸性质与空间位置,以及酶分子表面电荷等方面的相关机制,以期为今后蛋白酶的特异性酶解体系研究与应用提供参考。     

双酚芴环氧树脂体系热性能和粘接性能研究

环氧树脂是一种性能优异的热固性树脂，在结构胶粘剂和纤维增强复合材料领域应用广泛。但是常见的环氧树脂体系耐热性普遍较差，近年来，航空航天领域对材料的热性能提出了更高的要求，常规的环氧树脂体系已经无法满足耐高温需求。针对该问题，我们设计了一种耐热性较高的双酚芴型环氧树脂体系，并对其热性能和粘接性能进行了研究。在本文中，首先采用流变学方法和DSC研究了其工艺性能，使用DMA和TGA法分析了环氧树脂体系的耐热性能，并通过单搭接剪切试验测试了该环氧体系的粘接性能。结果表明，双酚芴型环氧树脂体系可在180℃固化，固化后的玻璃化转变温度达到190℃，失重5%时的温度为392℃，150℃时的剪切强度为5.8 MPa，展现了优异的耐热性能和粘接性能。     

含有多种活性基团的腐植酸有机肥及其制备方法

<正>申请(专利权)人:上海禾绿生物有机肥有限公司申请日期:2013.02.05申请(专利)号:CN201310045904主分类号:C09K101/00;C09K17/40本发明提供了一种含有多种活性基团的腐植酸有机肥,其特征在于,由秸秆10~15重量份、废菌苞20~25重量份、鸡粪10~15重量份、猪粪10~15重量份、牛粪30~40重量份和活性腐植酸5~10重     

中科院开发新型聚氨酯材料

<正>近日,中国科学院青岛生物能源与过程研究所生物基材料院重点实验室万晓波研究员带领的生物基及仿生高分子团队成功开发出新型聚氨酯材料,有望打破国外企业对此类材料的垄断。研究人员通过对亲水性聚氨酯树脂分子结构的精心设计,调整了聚合物中链段排布方式及功能基团的密度,促使凝胶时形成均匀而致密的交联网络,突破了相关关键技术,合成了具有高抱水量(最高可达为自身体积40倍)、高机械强度、优异乳化性能的聚     

清洁制浆工艺实现棉浆绿色生产

北京多欧联合科技发展有限公司袁志平、李朝旺两位专家利用十年时间研发的氧化清洁制浆法,可使短棉绒的得浆率提高10%,并且整个生产过程中无黑液和有害物质产生,废液可循环再利用,建立起了一套封闭型的绿色制浆生产体系。目前,自偶氧化清洁制棉浆工艺已经完成中试测试,其结果显示该工艺可使棉短绒得浆率从75%提高到85%,棉短绒甲纤含量、聚合度、灰分等11项指标均达到或超过黏胶