均匀沉淀法直接合成有机阴离子柱撑水滑石

以尿素为沉淀剂用均匀沉淀法直接合成有机阴离子柱撑水滑石(Layered Double Hydroxides，LDH)及CoAl水滑石等，并用XRD，FT—IR，TGA，TEM等分析手段对所合成的水滑石进行了表征．结果表明，尿素均匀沉淀法可以直接合成有机阴离子柱撑水滑石及CoAl水滑石等，并且可以方便地消除原料中阴离子的干扰，是合成有机阴离子柱撑水滑石及CoAl水滑石等的一个简便快速的新方法。     

Optimization strategies in micellar electrokinetic capillary chromatography

Summary Computer-assisted procedures for the one-parameter optimization of the surfactant concentration and the concentration of urea or D-glucose as modifiers in micellar electrokinetic capillary chromatography have been developed. These procedures permit a rapid optimization of one parameter on the basis of only two experiments. Predicted values are compared to empirically obtained optimum values. The influence of the modifier concentration on the critical micelle concentration of sodium dodecyl sulfate was experimentally determined in buffers commonly employed in micellar electrokinetic chromatography. The alteration of retention factors of solutes caused by the influence of urea addition on the critical micelle concentration of sodium dodecyl sulfate was calculated under the assumption of constant distribution coefficients and compared to experimentally obtained values. It was demonstrated that the addition of urea or of D-glucose does not alter the phase ratio substantially.     

Interaction of urea with pluronic block copolymers by 1H NMR spectroscopy

Solution 1H NMR techniques were used to characterize the interaction of urea with poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers. The urea was established to interact selectively with the PEO blocks of the block copolymer, and the interaction sites were found not to change with increasing temperature. Such interactions influence the self-assembly properties of the block copolymer in solution by increasing the hydration of the block copolymers and stabilizing the gauche conformation of the PPO chain. Therefore, urea increases the critical micellization temperature (CMT) values of PEO-PPO-PEO copolymers, and the effect of urea on the CMT is more pronounced for copolymers with higher PEO contents and lower for those with increased contents of PPO segments.     

ITSTUDIES ON THE EFFECT OF UREA ON THE COMPATIBILITY OF PMMA/PVC MIXTURES IN DMF BY A DILUTE- SOLUTION VISCOMETRY METHOD

The interaction between poly(methymethacrylate) (PMMA) and poly(vinyl chloride) (PVC) has been studied indilute urea solutions of dimethylformamide (DMF) at 28℃ using a dilute solution viscometry method. The results show thatthe polymer mixtures are compatible in DMF solution in the absence of urea. The influence of urea addition on the degree ofcompatibility of the polymer mixtures has been studied in terms of the compatibility parameters (△b_m and △[η]_m). It wasfound that the compatibility of the polymer mixtures is decreased with increasing urea addition, passing through a minimumat 0.5 M urea.     

Hydrophobic interactions in urea-trimethylamine-N-oxide solutions

The influence of osmolytes urea and trimethylamine- N-oxide (TMAO) on hydrophobic interactions is investigated employing molecular dynamics simulations. These osmolytes are of interest because of their opposing influence on proteins in solution; the denaturing effect of urea can be countered with TMAO. A neopentane pair is used to model typical nonpolar entities. Binary water-urea and water-TMAO as well as ternary water-urea-TMAO systems are considered. Neopentane-neopentane potentials of mean force, neopentane-water, and neopentane-osmolyte distribution functions are reported. Urea is found to have only modest influence on the neopentane-neopentane potential of mean force, but the hydrophobic attraction is completely destroyed by the presence of TMAO. It is shown that TMAO tends to act as a simple "surfactant" displacing water and urea (if it is present) from the first solvation shell of neopentane. It is likely the surfactant-like influence of TMAO that accounts for the elimination of the hydrophobic attraction. The implications of our results for explanations of the action of TMAO in protein solutions are discussed.     

溶剂法合成对甲苯甲腈

对甲苯甲腈是很重要的有机合成中间体,被广泛地应用在药物、染料及其它精细化工产品的合成上。它的主要合成方法有重氮盐的Sandmeyer 反应法^[1],醛肟脱水法^[2]和羧酸脱水法^[3,4]等。从工艺的可行性和经济角度来考虑,由对甲苯甲酸脱水（熔融法）直接制备对甲苯甲腈较为合理,但该法反应物升华严重,升华物易造成管道堵塞,给实际操作带来极大的不便。近年来廖道华等^[5]提出了溶剂法由羧酸直接合成腈的方法,该法与熔融法相比,产品收率高,工艺条件也得到了改善。本文研究对甲苯甲酸在溶剂中同尿素反应制备对甲苯甲腈的工艺条件,与熔融法相比,该方法所得产品收率高,工艺条件也得到了改善,易于工业化生产,值得推广。     

氘代DMSO试剂中残留~1H的检测

本文提出一种利用尿素作为内标物质,通过加入不同量的尿素测量它与氘代DMSO中溶剂残留信号峰面积比变化的方法。结果表明,尿素和DMSO溶剂峰的1H共振峰面积比与它们之间摩尔比之间有很强的线性关系,进而可以计算DMSO溶剂的氘代率。该方法简单、快速,所需试剂较少,低毒,可在实验室准确测试DMSO试剂的氘代率,也可以将此方法推广到其他氘代试剂的检测。     

Quantitative analysis of urea in human urine and serum by 1H nuclear magnetic resonance

A convenient and fast method for quantifying urea in biofluids is demonstrated using NMR analysis and the solvent water signal as a concentration reference. The urea concentration can be accurately determined with errors less than 3% between 1 mM and 50 mM, and less than 2% above 50 mM in urine and serum. The method is promising for various applications with advantages of simplicity, high accuracy, and fast non-destructive detection. With an ability to measure other metabolites simultaneously, this NMR method is also likely to find applications in metabolic profiling and system biology.     

Synthesis and characterization of photolabile o-nitrobenzyl derivatives of urea

We present here the synthesis and characterization of four photolabile derivatives of urea in which alpha-substituted 2-nitrobenzyl groups are covalently attached to the urea nitrogen. These derivatives photolyze readily in aqueous solution to release free urea. The alpha-substituents of the 2-nitrobenzyl group strongly influence the rate of the photolysis reaction measured with transient absorption spectroscopy. Rates of photolysis at pH 7.5 and room temperature (approximately 22 degrees C) for N-(2-nitrobenzyl)urea, N-(alpha-methyl-2-nitrobenzyl)urea, N-(alpha-carboxymethyl-2-nitrobenzyl)urea, and N-(alpha-carboxy-2-nitrobenzyl)urea are, respectively, 1.7 x 10(4), 8.5 x 10(4), 4.0 x 10(4), and 1.1 x 10(5) s(-)(1). The quantum yields determined by measurement of free urea following irradiation by a single laser pulse at 308 nm were 0.81 for N-(2-nitrobenzyl)urea, 0.64 for N-(alpha-methyl-2-nitrobenzyl)urea, and 0.56 for N-(alpha-carboxy-2-nitrobenzyl)urea. The caged N-(alpha-carboxy-2-nitrobenzyl)urea is not a substrate of the enzyme urease, while the photolytically released urea is. Also, neither this caged urea nor its photolytic side products inhibit hydrolysis of free urea by urease. Thus, the alpha-carboxy-2-nitrobenzyl derivative of urea is suitable for mechanistic investigations of the enzyme urease.     

尿素/H2O2溶液同时脱硫脱硝机理研究

在填料塔上对尿素/H₂O₂溶液同时脱硫脱硝进行了实验研究。结果表明,尿素溶液对SO₂具有很高的去除效率,但对NO_x的去除受到多种因素的影响。实验主要研究了H₂O₂浓度、吸收反应温度、溶液pH值等因素对脱硝效率的影响,并确定了最佳实验条件,在此条件下脱硫脱硝效率分别达到100%和52.6%。同时,采用化学分析法和气相色谱法对尿素溶液同时脱硫脱硝的反应产物进行分析,推导出尿素/H₂O₂溶液同时脱硫脱硝的反应机理和总化学反应方程式。该技术可用于对现有湿法脱硫技术的改造,使其同时具有脱硫脱硝功能。     

C-Bound or O-Bound Surface: Which One Boosts Electrocatalytic Urea Synthesis?

The electrocatalytic C−N coupling from carbon dioxide and nitrate under ambient conditions is kind of sustainable and promising alternative method for urea synthesis. To date, the influence of catalyst surface properties on molecular adsorption configuration and electrocatalytic urea synthesis activity is unclear. In this work, we proposed that the urea synthesis activity is closely linked with the localized surface charge on bimetallic electrocatalysts, it is found that a negatively charged surface induces C-bound path and boosts urea synthesis. The urea yield rate can reach 13.1 mmol g⁻¹ h⁻¹ on negatively charged Cu₉₇In₃-C, which is about 13 times that of positively charged Cu₃₀In₇₀-C counterpart with O-bound surface. This conclusion also applies to Cu−Bi and Cu−Sn systems. The molecular modification shifts the surface of Cu₉₇In₃-C to positively charged state, which leads to a sharp decline in urea synthesis performance. We demonstrated that the C-bound surface is more favorable than O-bound one to boost electrocatalytic urea synthesis.     

Separation of pesticides by capillary gas chromatography. Part 1: s-Triazines and substituted urea herbicides

The authors have shown that capillary columns are perfectly adequate for the separation of s-triazine herbicides and urea herbicides. The method presented remains adequate when the initial molecules are accompanied by some of their metabolites.     

KF/Al2O3催化剂上苯脲醇解合成苯氨基甲酸甲酯的研究

采用浸渍法制备负载KF固体碱催化剂,应用于苯脲和甲醇制备苯氨基甲酸甲酯的反应,考察了氧化物载体、卤化钾种类对催化剂性能的影响,KF/Al₂O₃催化剂显示出良好的催化活性和苯氨基甲酸甲酯的选择性。通过对KF/Al₂O₃催化剂中KF的负载量和催化剂焙烧温度的研究发现,在500 ℃焙烧4 h、负载质量分数50%KF的催化剂能够更好地促进MPC生成,苯脲转化率和苯氨基甲酸甲酯选择性分别达到96.5%和86.3%。XRD分析表明,KF与Al₂O₃之间存在较强的相互作用,部分转化为K₃AlF₆。KF与K₃AlF₆分别对甲醇的活化和苯脲的选择性起促进作用,两者的协同效应共同促进了目标产物苯氨基甲酸甲酯的生成。     

三种氨基酸在尿素水溶液中的体积性质

精密密度法详细测定甘氨酸、L-丙氨酸、L-丝氨酸在尿素水溶液中的表观摩尔体积,计算了三种氨基酸从水到尿素水溶液的迁移偏摩尔体积,结合前期的氨基酸从水到尿素水溶液的迁移焓,探讨尿素水溶液的结构特点及其对氨基酸与尿素在水溶液中相互作用的影响。结果表明,尿素分子在水溶液中自缔合,引起溶剂结构的变化并削弱其与氨基酸分子的结构相互作用,造成氨基酸从水到尿素水溶液的迁移偏摩尔体积和迁移焓随尿素浓度的增加而出现多个变化点,这一效应随着氨基酸疏水性的增强而增大,表明氨基酸的疏水性越强,其与尿素相互作用引起的去水化作用越明显。     

Influence of urea on initiation and termination of reaction between nitric acid and formic acid

The influence of urea on initiation and termination of the reaction between nitric and formic acids was experimentally examined. The urea injection can terminate the denitration reaction in 2 to 10M salt-free nitric acid solutions and the simulated high level liquid wastes (HLLWs) with a nitric acid concentration of 2 to 6M. An excess of urea can interrupt the initiation of denitration in both simulated HLLW and salt-free nitric acid solutions. The initiation and termination of denitration are in relation with nitrous acid formation and decomposition. Urea reacts with nitrous acid easily in the denitrating solution and decomposes nitrous acid. As the urea concentration increases in the solution, the continuance of denitration become impossible because the decomposition rate of nitrous acid exceeds the generation rate. In addition, the nitrous acid concentration can not be high enough to initiate the denitration in the solution with an excess of urea because nitrous acid is decomposed by urea.     

Effects of organic solvents on the partitioning of enzymes in aqueous two-phase systems

Organic solvents (ethylene glycol, glycerol, dimethyl sulphoxide, dimethylformamide, dioxane, methanol and propanol-2, as well as sucrose and urea) have been included in aqueous two-phase (liquid-liquid) systems comprised of water, dextran and poly(ethylene glycol). The concentration of the organic solvent was in most cases 20% (w/w). The influence of these solvents on the phase-forming properties, the volume ratio, the freezing point and the partitioning of a polymer-bound ligand, Procion Red HE-3B poly(ethylene glycol), has been studied. The partition coefficients for alkaline phosphatase decrease with ethylene glycol, glycerol, sucrose and urea (factors of 0.25-0.5), but increase with the other substances (factors of 1.2-1.6). The temperature effects on the partitioning of alkaline phosphatase from calf intestine as well as of phosphofructokinase from yeast in systems containing ethylene glycol have been studied and compared with partitioning in standard systems, not containing solvents. The possible uses of the above systems for partitioning studies of enzymes are discussed.     

Mechanism of linear and nonlinear optical properties of the urea crystal family

First-principles calculations of the second-order optical response functions and the dielectric functions of urea [CO(NH(2))(2)] and some of its derivatives such as monomethylurea (H(2)NCONHCH(3), MMU), and N,N'-dimethylurea (H(3)CHNCONHCH(3), DMU) crystals are performed. On the basis of the density functional theory (DFT) in the local-density approximation (LDA), the highly accurate full-potential projected augmented wave (FP-PAW) method was used to obtain the electronic structure. Over a wide frequency range (0.0-10.0 eV), the dielectric constants and second-harmonic generation (SHG) susceptibilities of the urea crystal family have been obtained, and the results are in good agreement with the experimental values. The origin of the linear and nonlinear optical (NLO) properties of the urea crystal family has been analyzed by coupling the calculated electronic structure and optical spectrum. The prominent spectra of χ((2)) are successfully correlated with the dielectric function ε(ω) in terms of single-photon and double-photon resonances. The virtual electron (VE) and virtual hole (VH) processes have also been performed for the urea crystal family. From the research into the electron deformation density, crystal configuration, substitutional group, and so forth, it is found that the origin of the SHG of the urea crystal family is the charge transfer due to the strong "(?)push-pull" effect along the hydrogen bond, which favors a head-to-tail arrangement of the molecules and enhances the SHG response. The electron-donating substitutional group supplies more electrons to the electron-accepting group, and helps to form large dipoles in molecules. The influence on the NLO properties of the local symmetry of the substitutional group is also discussed in detail.     

均匀沉淀法制备一维结构的氧化锌

以硝酸锌和尿素为反应原料,利用均匀沉淀法在水溶液中直接制备了多种形貌的氧化锌．考察了反应物浓度,加热方式等对产物形貌和结构的影响,利用透射电子显微镜,X射线衍射仪等分析手段对所得产物的形貌和结构进行了表征．     

Urea and urotropine conversion in the preparation of microspherical metal oxide particles by internal gelation

The results of studies on urea and urotropine product distribution in solutions formed in microspherical nuclear fuel preparation by internal gelation are presented. It is shown that urea, urotropine and formaldehyde, the urotropine hydrolysis product, undergo various conversions in solutions, resulting in methylolurea and urea-formaldehyde resins formation. Results on the influence of acidity on the process as a function of time are presented. The organic content in the resulting solutions and microspheres has been determined.