双酚-S-双(3-甲基丙烯酰氧基-2-羟丙基)醚的聚合及其应用

以MMA为起始原料经转变为GMA,再与双酚-S反应合成了一种新的含有砜基的交联剂BisS-GMA。这种双酚-S型交联剂与MMA可以顺利地用紫外光或BPO-胺体系引发聚合。新的双酚-S型交联剂BisS-GMA与双酚-A型交联剂Bis-GMA相比,具有活性高与粘结强度高两个显著优点。它还可以和二氧化硅填料混合组成复合树脂,经光引发或BPO-DHET体系引发聚合,得到的复合树脂其物性已达到国外同类产品的水平。DHET作为促进剂要比DMT性能好,前者配制的交联剂液体组份贮存稳定性好,经半年后而不“失活”,后者配制的液体组份则在较短的时间内“失活”。     

Resolution of the non-steady-state kinetics of the two-step mechanism for the Diels-Alder reaction between anthracene and tetracyanoethylene in acetonitrile

The Diels-Alder reaction between anthracene and tetracyanoethylene in acetonitrile does not reach a steady-state during the first half-life. The reaction follows the reversible consecutive second-order mechanism accompanied by the formation of a kinetically significant intermediate. The experimental observations consistent with this mechanism include extent of reaction-time profiles which deviate markedly from those expected for the irreversible second-order mechanism and initial pseudo first-order rate constants which differ significantly from those measured at longer times. It is concluded that the reaction intermediate giving rise to these deviations cannot be the charge-transfer (CT) complex, which is formed during the time of mixing, but rather a more intimate complex with a geometry favorable to the formation of the Diels-Alder adduct. The kinetics of the reaction were resolved into the microscopic rate constants for the individual steps. The rate constants, as shown in equation 1, at 293 K were observed to be 5.46 M(-)(1) s(-)(1) (k(f)), 14.8 s(-)(1) (k(b)), and 12.4 s(-)(1) (k(p)). Concentration profiles calculated under all conditions show that intermediate concentrations increase to maximum values early in the reaction and then continually decay during the first half-life. It is concluded that the charge-transfer complex may be an intermediate preceding the formation of the reactant complex, but due to its rapid formation and dissociation it is not detected by the kinetic measurements.     

Acceleration of Organic Reactions Using Microwave

The use of microwave technology in accelerating organic reactions has received intense attention leading to immense growth recently. Accordingly, we have been interested in improving the efficacy of organic processes by microwave irradiation. Here we report our results on the microwave assisted direct amide formation from carboxylic acid and amine, the hydrolysis of biopolymers, and nucleophilic aromatic substitution reaction. The reactions carried out under microwave irradiation, in general, …     

Facile cyclization of amidyl radicals generated from N-acyltriazenes

N-Acyltriazenes serve as a tin-free and initiator-free source for amidyl radicals. Thermal decomposition of N,N′-diaryl-N-(4-pentenoyl)triazenes in refluxing toluene led to the formation of monocyclic and tricyclic lactams in satisfactory yields via 5-exo amidyl radical cyclization.     

Solid Phase Synthesis of 4H-Pyrimido[2,1-b] Benzothiazol-4-ones from Resin-Bound Cyclic Malonic Ester

The solid phase synthesis of 4H-pyrimido[2,1-6] benzothizaol-4-ones has been reported.     

The molecular structure of norbornene as determined by electron diffraction and microwave spectroscopy

The molecular structure of norbornene has been investigated in the gas phase by combining electron diffraction data with microwave spectroscopic rotational constants. The interatomic distances (r_g) and bond angles were obtained by applying a least squares program to the refined experimental molecular diffraction intensities. The CC bond length was found to be 1.336 ± 0.002 Å while the

) bond length was 1. 529 ± 0.007 Å. Other bond lengths and angles included (IUPAC numbering system was used for norbornene): C₁-C₆ = 1.550 ± 0.020 Å, C₁-C₇ = 1.566± 0.005 Å, C₅-C₆ = 1.556 ± 0.005 Å, C-H_ave. = 1.103 ± 0.003 Å, ∠C₁C₂C₄ = 95.3°. The dihedral angle between planes C₁C₂C₃C₄ and C₁C₆C₅C₄ is 110.8 ± 1.5° while that between C₁C₂C₃C₄ and C₁C₇C₄ is 122.3°. The moments of inertia calculated from ED structure are in good agreement with microwave spectroscopic values.     

Molecular structure of 1,2,4-triazole

The molecular structure of 1,2,4-triazole has been determined by gas phase electron diffraction. The intemuclear distances and bond angles were obtained by applying a least-squares analysis to the experimental intensity. The bond distances (r_g) and bond angles were N₁-N₂ = 1.380 ± 0.010 Å, N₂C₃ = 1.329 ± 0.009 Å, C₃-N₄ = 1.348 ± 0.009 Å, N₁-C₅ = 1.377 ± 0.004 Å, N₄C₅ = 1.305 Å (calculated value). N-H = 0.990 Å, C-H = 1.054 Å, ∠N₁N₂C₃ = 102.7± 0.5°, ∠N₂C₃N₄ = 113.8 ± 1.3°, ∠N₂N₁C₅ = 108.9 ± 0.8°, ∠H₁N₁N₂ = 110.9°, ∠H₂C₃N₄ = 119.2°, ∠H₃C₅N₁ = 131.0°, ∠C₃N₄C₅ = 105.7° (calculated value) and ∠N₄C₅N₁ = 108.7° (calculated value).     

Total Synthesis of (+/-)-Leporin A

An efficient synthesis of (+/-)-leporin A (1) has been developed using a tandem Knoevenagel condensation-inverse electron demand intramolecular hetero Diels-Alder reaction to construct the key tricyclic intermediate 3 from pyridone 5 and dienal 6 in one pot in 35% yield. Hydroxylation (71%) of 3 and methylation (77%) of the resulting hydroxypyridone 2 completed the first total synthesis of (+/-)-leporin A (1).     

Study on osmotic pressures for aqueous lysozyme and alpha-chymotrypsin-electrolyte solutions with two Yukawa potentials

The equation of state (EOS) of Duh and Mier-y-Terán for one Yukawa potential is expanded to two Yukawa potentials to describe the nonidealities of the charged lysozyme and alpha-chymotrypsin solutions. Instead of the classical DLVO theory, the attractive dispersion and double-layer repulsion interactions are represented by two Yukawa potentials, respectively. For the aqueous lysozyme solutions, the only adjustable dispersion energy parameter epsilon/k is regressed and the average deviation is 1.76%. For the aqueous alpha-chymotrypsin solutions, two adjustable parameters (the molecular weight and dispersion energy parameter) are regressed and the average deviation is 7.62%. Some correlation and prediction results are discussed.     

Alcohol sensing membrane based on immobilized ruthenium(II) complex in carboxylated PVC and surface covalently bonded alcohol oxidase

Alcohol sensing membranes coated on overhead transparency films for the continuous monitoring of ethanol, propanol and butanol are presented. Alcohol oxidation catalyzed by alcohol oxidase in conjunction with the fluorescence quenching reaction of oxygen-sensitive dye ion-pair, tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) didodecylsulphate was chosen for the determination. Alcohol oxidase was immobilized covalently on a plasticized carboxylated poly(vinyl chloride) membrane and the oxygen-sensitive dye ion-pair was entrapped in the same membrane. The sensing membrane relates oxygen consumption, as a result of enzymatic oxidation, to alcohol concentration. Measurements have been performed in air-saturated alcohol standard solutions of pH 7.0. Storage stability, reproducibility and the effect of pH on sensing membrane performance have been studied in detail. The alcohol sensing membrane proposed here is simple to prepare and has a fairly rapid response time of <1 min. It has been successfully applied to the determination of the ethanol contents in various spirits.