活化/失活反应对原子转移自由基共聚产物微观结构的影响

提出了一个可以处理原子转移自由基共聚及其产物微结构的模型,采用计算机模拟产生了包括活化/失活反应的ATRcP稳态增长反应链,得到了有关链段分布的信息.模拟发现,含有休眠过程的ATRcP产物与常规的自由基的相比组成结构和序列结构完全一致,即活化/失活反应不影响ATRcP产物的微组成与微序列结构.     

TCDD的密度泛函理论研究

用B3LYP/6-311G~(**)方法全优经计算22个四氯二苯并对二（左口右恶）英（ 简称TCDD）分子，得到几何构型、总能量、标准熵、标准焓和标准自由能。将2， 3，7，8－TCDD的计算构型与X射线衍射实验测定值进行了比较。计算结果表明，总 能量、标准焓和标准自由能与氯原子量换位置的相关性很高（r > 0.997）.1,3,6, 8-TCDD的总能量处自由能最低，即最稳定，以此参照，得到异构体的总能量的相对 稳定性顺序和自由能的相对稳定性顺序。1,3,7,9－TCDD的稳定性次之，1,3,7,8- TCDD居第三，将这二个顺序与焚烧炉产生的TCDD异构体和合成的异构体对的生成面 分比进行了比较，说明焚烧炉中产生的TCDD和合成的TCDD对的分布主要受热力学控 制。     

Synthesis, X-ray crystal structures, and gas sorption properties of pillared square grid nets based on paddle-wheel motifs: implications for hydrogen storage in porous materials

A systematic modulation of organic ligands connecting dinuclear paddle-wheel motifs leads to a series of isomorphous metal-organic porous materials that have a three-dimensional connectivity and interconnected pores. Aromatic dicarboxylates such as 1,4-benzenedicarboxylate (1,4-bdc), tetramethylterephthalate (tmbdc), 1,4-naphthalenedicarboxylate (1,4-ndc), tetrafluoroterephthalate (tfbdc), or 2,6-naphthalenedicarboxylate (2,6-ndc) are linear linkers that form two-dimensional layers, and diamine ligands, 4-diazabicyclo[2.2.2]octane (dabco) or 4,4'-dipyridyl (bpy), coordinate at both sides of Zn(2) paddle-wheel units to bridge the layers vertically. The resulting open frameworks [Zn(2)(1,4-bdc)(2)(dabco)] (1), [Zn(2)(1,4-bdc)(tmbdc)(dabco)] (2), [Zn(2)(tmbdc)(2)(dabco)] (3), [Zn(2)(1,4-ndc)(2)(dabco)] (4), [Zn(2)(tfbdc)(2)(dabco)] (5), and [Zn(2)(tmbdc)(2)(bpy)] (8) possess varying size of pores and free apertures originating from the side groups of the 1,4-bdc derivatives. [Zn(2)(1,4-bdc)(2)(bpy)] (6) and [Zn(2)(2,6-ndc)(2)(bpy)] (7) have two- and threefold interpenetrating structures, respectively. The non-interpenetrating frameworks (1-5 and 8) possess surface areas in the range of 1450-2090 m(2)g(-1) and hydrogen sorption capacities of 1.7-2.1 wt % at 78 K and 1 atm. A detailed analysis of the sorption data in conjunction with structural similarities and differences concludes that porous materials with straight channels and large openings do not perform better than those with wavy channels and small openings in terms of hydrogen storage through physisorption.     

Synthesis and Crystal Structure of 3,3′-(Hexane-1,6-diyl)bis(1-acetyl-5,5-dimethylhydantoin),a New Inducer of Differentiation

1 INTRODUCTION Hexamethylenebis[acetamide] (HMBA) is an effective agent in phaseⅡclinical trial[1] that induces differentiation of certain types of tumors to nonmalignant phenotypes. In an attempt to discover more efficient inducers, a number of derivatives of HMBA have been synthesized and evaluated in vitro[2, 3]. The results proved that increasing the number of functional groups could enhance the anticancer activity. In addition, it was evident that compounds with six methylene i…     

A Facile Synthesis of Ethyl 2,4-Dimethoxy-6-perfluoroalkyl-benzoates via Acyclic Precursors

Introduction Polysubstituted arenes are important intermediates in synthetic medicines and dyestuffs, and the fluorinated analogues are more attractive as a result of their lipo-philicity and the increment of activity.1,2 Therefore, to study the convenient and efficient synthesis of polysub-stituted arenes is valuable in organic synthetic method-ology. We have designed a simple synthesis of fluori-nated polysubstituted arenes through the intramolecular Wittig reaction of a new phosphorous ylid…     

溴化环氧/Novolacs体系在CEM-3板中的应用

分别以PN、BPFN和BPAN为溴化环氧A80的固化剂,以DMP-30、HMTA和2-MZ为促进剂制备CEM-3覆铜板,研究了这三种线型酚醛树脂作为固化剂对CEM-3覆铜板力学性能、电性能、吸水性和耐热性等的影响.结果表明,以三种线型酚醛树脂为固化剂制备的CEM-3覆铜板的力学性能相近,而吸水性由高至低的顺序为PN＞BPFN＞BPAN,介电性能由高至低的顺序为BPFN≈BPAN＞PN,Tg由高至低的顺序为PN＞BPFN＞BPAN.由BPAN和BPFN为固化剂制备的CEM-3覆铜板经150℃/2h后处理,耐变色性明显优于PN为固化剂制备的CEM-3覆铜板.     

碳化钨负载S2O8^2-/ZrO2固体超强酸催化剂上的正戊烷反应研究

首次研究了碳化钨负载S2 O2 -8 ZrO2 (PSZ)固体超强酸催化剂 (WC PSZ)上正戊烷的反应情况及影响催化剂活性的各种因素 ,并用GC MS ,XRD ,BET等手段分析了正戊烷反应产物和催化剂的物理化学性质等 .结果表明 :WC PSZ对正戊烷具有异构化和裂解的双重催化作用 .PSZ在负载适量碳化钨后对正戊烷反应的活性和选择性显著提高 ,显示出优于Pt PSZ催化剂的效果 ,碳化钨的负载量为 2 0 %的效果最佳 .适当的焙烧、活化和反应温度等条件是取得良好反应效果的关键     

甲基丙烯酸甲酯悬浮聚合实验教学的改进

选用氢氧化镁为分散剂,甲基丙烯酸甲酯(MMA)为单体,进行悬浮聚合反应,研究了分散剂用量、引发剂用量、水和单体比、搅拌速度、反应温度及反应时间对聚合物珠粒大小、均匀程度和产率的影响。结果表明:与目前高分子实验教材普遍选用的以聚乙烯醇(PVA)为分散剂的悬浮聚合反应相比,以氢氧化镁为分散剂,具有操作简单、聚合时间短、体系稳定性高等优点,可代替原有的悬浮聚合反应实验,作为高分子化学实验的教学课程内容。