主客体化学新法合成脂肪族α-氨基酸

以脂肪醛、氯仿、氢氧化钾和氨水为原料,利用尿素对直链脂肪醛的主客体包合作用,将尿素作为反向相转移催化剂,与正向相转移催化剂十六烷基三甲基溴化铵协同催化一锅合成脂肪族α-氨基酸,取得了一定的效果,并具有操作简单方便、反应条件温和、不用剧毒物等优点。     

氟硅酸钾容量法测定岩石中的二氧化硅

应用容量法测定岩石中的二氧化硅是比较普遍的,但是,在分析质量上还不够稳定。因为用氢氧化钾与过氧化钠在银(镍)坩埚中熔融矿样易发生喷溅,熔融物常“爬”出坩埚外部,易造成损失。某些矿样,如角闪斜长辉石岩,用氢氧化钾与过氧化钠熔融制成盐酸溶液后,常析出硅酸,使容量法测硅产生严重误差。用过氧化钠-碳酸钠,在银坩埚中熔融,不仅矿样不会损失,而且熔融物制成盐酸溶液后,也不易析出硅酸,保证了容量法测定硅的质量。利用上述熔矿方法,对岩石系统分析也是方便的,它能迅速分解所有矿样,而带进溶液中的杂质却不多。因此利用测硅的溶液,以原子吸收法、比色法及容量法进行铁、锰、钙、镁、铬、镍、铝及钛等元素测定,而不     

硼砂与尿素合成六方氮化硼的机理

研究了N_2气氛下硼砂与尿素反应生成六方氮化硼以及主要副产物产生和变化的过程,采用热重-差示扫描量热法(TG-DSC)、X射线衍射(XRD)、扫描电子显微镜(SEM)等检测手段对反应产物和氮化硼样品进行了分析.研究结果表明,氮化硼在700℃左右完全生成,随焙烧温度的提高其结晶度不断提高.反应副产物偏硼酸钠的生成是导致氮化硼产率较低的主要原因,在高温焙烧过程中偏硼酸钠的存在有利于六方氮化硼的结晶过程.研究结果可为硼砂-尿素法六方氮化硼制备工艺的优化和改进提供理论基础.     

尿素作为添加剂低温制备高活性的TiO2光催化剂

以钛酸丁酯为原料,尿素作为添加剂,在酸性水溶液中室温制备了稳定透明的TiO2水溶胶。经过300℃低温焙烧2 h,得到了由锐钛矿和金红石组成的TiO2混晶。用XRD、FT-IR对催化剂进行了表征。以甲基橙为降解对象研究了TiO2的光催化活性,实验结果显示所制备的TiO2具有比Degussa P25更高的催化活性,15m in后的降解率达到了78%(P25,58%)。考察了尿素添加量以及焙烧温度对TiO2催化性能的影响,当尿素与钛酸丁酯物质的量之比为3∶1,300℃下焙烧2 h为较适宜的催化剂制备条件。初步探讨了尿素作为添加剂在低温制备高活性TiO2过程中的作用。     

1-溴丁烷与氢氧化钠或氢氧化钾醇溶液反应探讨

为了明确直链伯卤代烷与氢氧化钠或氢氧化钾醇溶液共热是以取代为主 ,还是以消去为主 ,以及取代产物以何物为主 ,用 1 溴丁烷为代表物进行了实验。结果发现 ,1 溴丁烷与饱和氢氧化钠或氢氧化钾乙醇溶液在回流状态下反应 ,1 丁烯产率最高仅为 13%左右 ,即主要进行取代反应 ;用气相色谱法对取代产物进行分析 ,发现主要为乙丁醚 ,只有少量 1 丁醇。由此可知 ,直链伯卤代烷与氢氧化钠或氢氧化钾醇溶液共热 ,主要进行取代反应生成醚 ,消去反应居于次要地位。一些较早文献的介绍 ,是完全正确的     

气相色谱法研究H型丝光沸石对甲苯的吸附性质及其催化活性

本文用脉冲色谱技术,在接近反应条件的高温下,研究了H型丝光沸石(HM)对甲苯的吸附性质,测得了不同焙烧温度的HM对甲苯的比保留体积和吸附热。说明焙烧温度未改变HM对甲苯的吸附能量和吸附表面积,而只改变了沸石单位面积上的吸附中心数目。并从实验结果看出,焙烧温度对HM的甲苯歧化活性的影响与比保留体积随焙烧温度的变化趋势颇为相似。     

滴定法测定食品用硅藻土中硅含量

食品用硅藻土助滤剂中硅的测定方法主要有动物胶重量法和氢氟酸重量法.本文提出试样经氢氧化钾熔融后在强酸介质中与氟化铵和氯化钾生成六氟合硅酸钾(K_2SiF_6)沉淀,沉淀离心分离后水解析出氢氟酸,用氢氧化钠标准溶液进行滴定.1 试剂氯化钾乙醇溶液:5%,称取氯化钾5.0g溶于水50ml,加乙醇(95%)50ml.氢氧化钠标准溶液:0.5mol·L~(-1)2 操作方法准确称取硅藻土样品0.1～0.2g于镍坩埚中,加入氢氧化钾固体1～2g,放入550℃马弗炉中熔融15min,取出冷却,加少量水用塑料棒搅动溶解,转入塑料烧杯中,用少量水洗涤坩埚2～3次后合并洗涤液于塑料烧杯中,使总体积不超过15ml为宜.     

均分散球形氧化铕超细微粒的制备和表征

采用尿素分解法制备了均分散球形Eu(OH)CO~3·H~2O超细沉淀粒子,进一步在空气中750℃下焙烧4h,得到了均分散球形氧化铕超细微粒。考察了各种反应条件的影响,获得了最佳的制备条件。用XRD,IR,TEM,TG以及比表面测定等手段对样品进行了表征。     

共沉淀法制备铝酸镧超微粉末的研究

用尿素-氨水在热水溶液中调pH共沉淀制备铝酸镧超微粉末。研究了氨水浓度、尿素浓度和尿素-氨水滴加速度对超微粉末颗粒的影响和焙烧温度对超微粉末颗粒微观变化的作用。在选定的条件下,制备成粒径为0.1～0.7μm、比表面93～112m~2/g的铝酸镧超微粉末。     

5-羟基-3,4-二氢异喹啉-1-酮的合成

以异喹啉为起始原料,经成盐、磺化得异喹啉-5-磺酸(3),3与熔融的氢氧化钠和氢氧化钾反应得1,5-二羟基异喹啉(4),以5%Pd-C为催化剂还原4得5-羟基-3,4-二氢异喹啉-1-酮(1),总收率47.6%。1的结构经1H NMR和MS确证。     

Preparation and properties of N-fluoro- and N-nitrobis(2,2,2-trinitroethyl)ureas

Fluorination and nitration of bis(2,2,2-trinitroethyl)urea has given the novel N-fluoro-bis(2,2,2-trinitroethyl)urea and N-nitro-bis(2,2,2-trinitroethyl)urea. The thermal decomposition rates and parameters for bis(2,2,2-trinitroethyl)urea and its derivatives have been found, and the standard enthalpies of combustion, and the standard enthalpies of formation of these compounds calculated therefrom, have been determined.Institute of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1857–1863, August, 1992.     

Thermoanalytical Investigations on Intercalated Kaolinites

The thermal behaviour of ordered kaolinites from Hungary and Australia intercalated with potassium acetate, cesium acetate and urea has been investigated by simultaneous TG-DTG-DTA, TG-MS, Raman microscopy and XRD. Remarkable changes in the thermal decomposition pattern of the intercalates were obtained as a function of the nature of the intercalating re-agents. Replacing the potassium cation to cesium leads to a change in the OH environments resulting in a more complicated dehydroxylation pattern. The urea intercalates can be decomposed completely without dehydroxylating the mineral, although further treatments are necessary to restore the original d-spacing. This revised version was published online in July 2006 with corrections to the Cover Date.     

TG–MS–FTIR (evolved gas analysis) of kaolinite–urea intercalation complex

The products evolved during the thermal decomposition of kaolinite–urea intercalation complex were studied by using TG–FTIR–MS technique. The main gases and volatile products released during the thermal decomposition of kaolinite–urea intercalation complex are ammonia (NH₃), water (H₂O), cyanic acid (HNCO), carbon dioxide (CO₂), nitric acid (HNO₃), and biuret ((H₂NCO)₂NH). The results showed that the evolved products obtained were mainly divided into two processes: (1) the main evolved products CO₂, H₂O, NH₃, HNCO are mainly released at the temperature between 200 and 450 °C with a maximum at 355 °C; (2) up to 600 °C, the main evolved products are H₂O and CO₂ with a maximum at 575 °C. It is concluded that the thermal decomposition of the kaolinite–urea intercalation complex includes two stages: (a) thermal decomposition of urea in the intercalation complex takes place in four steps up to 450 °C; (b) the dehydroxylation of kaolinite and thermal decomposition of residual urea occurs between 500 and 600 °C with a maximum at 575 °C. The mass spectrometric analysis results are in good agreement with the infrared spectroscopic analysis of the evolved gases. These results give the evidence on the thermal decomposition products and make all explanation have the sufficient evidence. Therefore, TG–MS–IR is a powerful tool for the investigation of gas evolution from the thermal decomposition of materials and its intercalation complexes.     

Studies on the structure and thermal behaviour of the Mn—urea complex

The urea complex of manganese was synthesized and its structure established to be [Mn(Urea)(H₂O)₃Cl₂] from elemental analyses, IR and UV and visible spectroscopy and magnetic susceptibility measurements. The thermal behaviour has been studied by thermogravimetry (TG) in nitrogen and air atmospheres and differential thermal analysis (DTA) in air. TG analysis shows three main steps of decomposition leading to oxide formation in the final stage when the complex is heated in air, and MnCl₂ formation when it is heated in nitrogen. The kinetics of decomposition of the complex have been studied. Plots of the Coats—Redfern equation show two breaks from which three values of the activation energy are reported. From the results, it is concluded that decomposition of the complex is a heterogeneous process.     

The thermal decomposition of sym-dichlorobis (2,4,6-trichlorophenyl) urea in KBr

Infrared spectra of sym-dichlorobis (2,4,6-trichlorophenyl) urea over the range 4000–250 cm⁻¹ have been obtained on samples prepared in KBr discs and stored for several hours at elevated temperatures. The subject compound undergoes thermal decomposition by cleavage of the N---Cl bond and the formation of sym-2,4,6-trichlorophenyl urea with some aromatic halogenation of 2,4-dichlorophenyl groups present in the sample.     

Fluorescent aromatic polyamides with urea binding sites and fluorene or dansyl signaling units

This work describes six novel fluorescent aromatic polyamides with bulky dansyl or fluorene pendant groups or with the fluorene moiety in the main chain. The fluorescent signaling dansyl or fluorene moieties are chemically connected to, or within, the main polymer chains through a urea group, a well-known binding site in supramolecular chemistry. These polyamides are amorphous and soluble in polar aprotic solvents and demonstrate a film-forming capability. They also show yellowish-green or blue fluorescence in solution and in the solid state depending on the signaling unit, with the former corresponding to the dansyl and the latter to the fluorene residue. The water uptake and the thermal behavior have also been evaluated and related to the chemical structure. The polar amide, urea, and sulfonamide groups give rise to a high water sorption of up to 3.8 water molecules per repeating unit. The thermal behavior has been investigated by means of DSC and TGA. The glass transition temperatures of the polymers are high (up to 331 °C) and the decomposition temperatures (around 300 °C) are due to the moderate thermal stability of the urea group.     

铽芳香族羧酸配合物的热分解机理及动力学研究

本文采用TG-DTA-DTG等技术研究了铽羧酸配合物的热分解过程,通过对中间产物进行红外光谱、元素分析、确定了热分解机理。采用三种方法尝试求得了希土羧酸配合物热分解过程的活化能和焓变,发现并总结了其相变过程。     

STUDY ON THERMAL DECOMPOSITION KINETICS OF URUSHIOL METAL CHELATE POLYMERS

The thermal decomposition kinetics of urushiol-Cu, urushiol-Nd and urushiol-Ti chelatepolymers has been studied by non-isothermal thermogravimetry. The results suggest that thethermal decomposition kinetics of three chelate polymers are all of first order. Their averageactivation energy values of the thermal decomposition calculated by Ozawa-(I) method are 110,79, 136. 98 and 163. 64 kJ mol~(-1) respectively, which increase linearly with the metal valence of themetal chelate polymers     

Dehydrated halloysite intercalated mechanochemically with urea: Thermal behavior and structural aspects

Urea has been intercalated mechanochemically into dehydrated halloysite and analyzed by X-ray powder diffraction (XRPD), Fourier transform infrared spectroscopy (FTIR), diffuse reflectance ultraviolet/visible spectroscopy (DRUV–VIS), thermal analysis (TGA/DTA), transmission electron microscopy (TEM), and electron paramagnetic resonance (EPR). The basal distance expands from 7.4 to 10.7 Å and the interaction of urea to adjacent layers of halloysite through hydrogen bonds increases the structural order of the matrix. After heat treatment in air at different temperatures, decomposition products begin to appear starting from 100 °C. Although the basal distance remains constant up to 160 °C and collapses to the original value at 200 °C, urea and the decomposition products are still present in the sample. Starting from 125 °C, urea decomposition products reduce halloysite structural Fe³⁺ centers to Fe²⁺, as indicated by DRUV–VIS and EPR spectroscopy.     

一些抑制剂对脲酶反应速率的影响

利用氨气敏电极研究硝酸镍，磷酸盐及ＥＤＴＡ等酶抑制剂对脲酶分解尿素反应速率的影响以及抑制作用机理。