Effects of double substitution on the thermodynamic stabilities of nitrogen radicals

Ｓｔｕｄｉｅｓｏｎｋｉｎｅｔｉｃｓｏｆｒａｄｉｃａｌｒｅａｃｔｉｏｎｓ[1]ａｎｄｏｎＣＨｂｏｎｄｄｉｓｓｏｃｉａｔｉｏｎｅｎｅｒｇｉｅｓ(ＢＤＥ)[2]ｈａｖｅｓｈｏｗｎｔｈａｔｃａｒｂｏｎｒａｄｉｃａｌｓａｒｅｓｔａｂｉｌｉｚｅｄｂｙｅｉｔｈｅｒａｎｅｌｅｃｔｒｏｎｄｏｎａｔｉｎｇｇｒｏｕｐ(ＥＤＧ)ｏｒａｎｅｌｅｃｔｒｏｎｗｉｔｈｄｒａｗｉｎｇｇｒｏｕｐ(ＥＷＧ),ａｎｄｔｈａｔｉｆａｃａｒｂｏｎｒａｄｉｃａｌｉｓｓｕｂｓｔｉｔｕｔｅｄｗｉｔｈｂｏｔｈａｎＥＤＧａｎｄａｎＥＷＧａｔｔｈｅｓａｍｅｃｅｎ…     

铝－5＇－硝基水杨基荧光酮－溴化十六烷基吡啶显色反应的研究及应用

本文研究了铝－５＇－硝基水杨基荧光酮（５＇－ＮＳＦ）－溴化十六烷基吡啶（ＣＰＢ）体系的显色条件。试验结果表明，在ｐＨ４．５～６．０范围内，铝与５＇－ＮＳＦ及ＣＰＢ形成紫红色的三元配合物，其最大吸收波长为５５８ｎｍ，摩尔吸光系数为１．３×１０￣５，配合物的组成为Ａｌ：５＇－ＮＳＦ：ＣＰＢ＝１：２：２。铝浓度在０～４μｇ／２５ｍＬ范围内符合比耳定律。方法用于石灰石、石英沙、石膏中铝的测定，结果令人满意。     

壳聚糖对鞣酸絮凝作用的研究

以壳聚糖为絮凝剂，采用絮凝法除去中药药液中的杂质。以鞣酸为研究对象，从鞣酸浓度，体系温度，ＰＨ絮凝剂用量粘均分子量等方面探讨其絮凝规律，用正交试验优化其絮凝条件，为实施中药药液的絮凝法精制工艺提供参考。     

Nucleation mechanisms and speciation of metal oxide clusters

The self-assembly mechanisms of polyoxometalates (POMs) are still a matter of discussion owing to the difficult task of identifying all the chemical species and reactions involved. We present a new computational methodology that identifies the reaction mechanism for the formation of metal-oxide clusters and provides a speciation model from first-principles and in an automated manner. As a first example, we apply our method to the formation of octamolybdate. In our model, we include variables such as pH, temperature and ionic force because they have a determining effect on driving the reaction to a specific product. Making use of graphs, we set up and solved 2.8 × 10⁵ multi-species chemical equilibrium (MSCE) non-linear equations and found which set of reactions fitted best with the experimental data available. The agreement between computed and experimental speciation diagrams is excellent. Furthermore, we discovered a strong linear dependence between DFT and empirical formation constants, which opens the door for a systematic rescaling.

The self-assembly mechanisms of polyoxometalates (POMs) are still a matter of discussion owing to the difficult task of identifying all the chemical species and reactions involved. The POMSimulator deals with that complexity in an automated manner.     

Enantioselective iodolactonization catalyzed by chiral quaternary ammonium salts derived from cinchonidine

Chiral quaternary ammonium salts derived from cinchonidine have been applied to catalyze the stereoselective iodolactonizations of trans-5-aryl-4-pentenoic acids leading to a mixture of two regioselectively iodolactonized products with fair to excellent yield (37-98%) and moderate enantioselectivity (exo = 42.0% ee, endo = 31.0% ee) under mild conditions. This work is the first example of asymmetric iodolactonization reaction in the presence of less than a stoichiometric amount of chiral reagent.     

新型膦配体PDBPDS在氢甲酰化反应中催化剂配体性能的研究

用量子化学 AMI方法优化了 1 -苯基二苯并膦二磺化产物 ( PDBPDS)和三磺化三苯基膦 ( TPPTS)的几何构型 .比较两种化合物的空间结构和电子结构发现 ,在氢甲酰化铑膦催化反应体系中 ,PDBPDS的配体性能优于 TPPTS.首次研究了以 PDBPDS为配体的铑膦催化剂对丙烯氢甲酰化反应的催化性能 ,考察了反应温度、压力、膦铑物质的量比和搅拌速度对催化活性和选择性的影响 .结果表明 ,在 2 .0 MPa,1 0 0℃ ,膦铑物质的量比为 35 ,搅拌速度为 5 0 0 r/min及 V( H2 ) /V( CO) =1 /1的条件下 ,催化活性可达到 2 80 0 g(丁醛 ) /[g(铑 )·h],正异构产物物质的量比为 1 2 .3,在相同条件下与传统的三磺化三苯基膦 ( TPPTS)为配体的铑膦催化剂相比 ,催化活性和选择性提高了 2倍 .反应结束后 ,有机相和水相分离简单 ,有机相铑浓度仅为3.6× 1 0 - 8mol/L,有效地解决了铑流失问题 ,表明 PDBPDS是极具开发前景的新型水溶性配体     

有机/无机杂化材料担载季铵盐催化剂的制备及其在相转移催化反应中的应用

利用溶胶-凝胶(S0l-gel)技术制备了新型的有机／无机杂化材料担载的季铵盐催化剂。优化了制备方法、反应条件等多种因素；考察了其作为相转移催化剂在1-溴代正庚烷与碘化钾的亲核取代反应中的应用，转化率最高可达到95％。     

Ni-B和Ni-Ce-B超细非晶态合金的退火晶化及其催化性能

 采用XAFS,XRD和DTA方法研究了Ni－B和Ni－Ce－B超细非晶态合金在退火过程中的结构变化及其结构与催化性能的关系．活性结果表明,在退火温度为623K时,Ni－B和Ni－Ce－B样品的苯加氢催化反应转化率最高,分别为63％和81％,0．3％Ce的掺入提高了Ni－Ce－B的催化活性．DTA结果表明,Ni－B超细非晶态合金在598和653K有两个晶化峰,而Ni－Ce－B样品有548,603,696和801K四个晶化峰．XAFS和XRD结果进一步说明,在573K退火时,Ni－B样品晶化生成晶态Ni3B和纳米晶Ni,此时Ni－Ce－B仅有少量晶态Ni3B生成．在673K退火时,Ni－B样品中的Ni3B开始分解生成晶态Ni,同时纳米晶Ni聚集并形成大颗粒晶态Ni,而Ni－Ce－B样品晶化生成晶态Ni3B和纳米晶Ni．在773K和更高的温度退火处理后,Ni－B样品中Ni的局域环境结构与金属Ni箔基本一致,但Ni－Ce－B样品晶化生成的Ni晶格有较大畸变,同时Ni3B并未分解．说明0．3％的Ce对提高Ni－Ce－B样品的稳定性有显著作用．本文首次报道了Ni－B和Ni－Ce－B超细非晶态合金中苯加氢催化活性中心为纳米晶Ni和类似于金属Ni的Ni－B非晶态合金．     

Synthesis and properties of tadpole-shaped gold nanoparticles

In this communication, gold nanoparticles with a tadpole shape were synthesized by a simple aqueous-phase chemical method. The unusual three-dimensional and crystallized structures were demonstrated by TEM, AFM, and HRTEM methods. The SEM and UV-visible absorption measurements and electrophoresis experiments revealed that the tadpoles had novel optical and electrical properties. These attractive structures and properties are expected to find uses in many fields such as electrics, optics, electrochemistry, and biological sensing.     

Influence of ultrasonic field on microcystins produced by bloom-forming algae

Under the background of algae removal and growth inhibition by ultrasonic irradiation, the effects of ultrasonic irradiation on removal of Microcystis, the concentration variation of microcystins (MC) produced by Microcystis in Microcystis suspension, and sonochemical degradation of microcystins in water, were studied in the paper. The results showed that ultrasonic irradiation could efficiently inhibit the growth of Microcystis, and ultrasonic irradiation shorter than 5 min would not introduce the increase of microcystins dissolved in Microcystis suspension simultaneity. Also, microcystins dissolved in Microcystis suspension would not increase as ultrasonic power increasing. Further research showed that microcystins were effectively degraded in ultrasonic fields. After 20 min ultrasonic irradiation at 150 kHz and 30 W, the removal rate of microcystins reached 70%.