Synthesis and properties of alkylated imidazoles

Alkylation of 4(5)-nitroimidazole-5(4)-sulfonamide with benzyl bromide occurred on both ring nitrogens. The structures of the products could be assigned by comparison of the chemical shifts of the sulfonamide hydrogens in the nmr spectra with those of the isomeric methyl derivatives, which were prepared by differing routes. Uv and nmr spectral data are reported for a number of bromo-, nitro-, mercapto-, sulfamyl- and amino- substituted imidazoles as well as for both of the isomeric methylated derivatives of the series.     

Preparation d'alcools acetyleniques et propargyliques F-alkyles

A number of α-β acetylenic carbinols R_FCCC(OH)RR′, in which the acetylenic proton was substituted by a F-alkyl group, were first prepared, from a classical reaction of (F-alkynyl)- lithium derivatives R_FCCLi upon various carbonyl compounds.On another hand, the reaction of propargyl bromide metallic complexes (organoaluminic, or ultrasonic irradiation activated organozinc) upon some polyfluorinated ketones R_FCOR led to the formation, in convenient yields, of the propargylic carbinols HCCCH₂C(OH)RR_F.The synthesis and properties of these series of new (F-alkyl) substituted acetylenic and propargylic alcohols are described and discussed.     

Agonist–PPARγ interactions: Molecular modeling study with docking approach

Docking simulation of 18 agonists with the ligand binding pocket (LBP) of PPARγ has been performed. The binding conformations and binding affinities of these agonists were obtained by use of the flexible docking protocol FlexX. Test compound calculations indicated that FlexX can reproduce the binding conformation of the crystal structure (root mean square deviation = 1.43 Å); moreover, the predicted binding affinities correlate well with the activities of these agonists. The interaction model and pharmacophore of PPARγ agonists were derived and the difference in biologic activities of these agonists can be well explained. The PPARγ agonists must have both polar head and the hydrophobic tail, which form hydrogen bonds and hydrophobic contacts with hydrophilic and hydrophobic regions of the LBP of PPARγ, respectively. In addition, a suitable linker is also necessary. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 93: 405–410, 2003     

Molecular recognition properties of salicylic acid-imprinted polymers

Summary Two molecularly imprinted polymers (MIP) have been prepared using the acidic drug salicylic acid, which can form intramolecular hydrogen bond, as the template and acrylamide or 4-vinylpyridine as the functional monomer. HPLC was used to evaluate the binding performance of the MIP for the template and for several analogues. The results showed that the MIP (P₂) prepared using acrylamide as the functional monomer had no molecular imprinting effect whereas that (P₁) prepared using 4-vinylpyridine as the functional monomer had a significant molecular imprinting effect. The reason the molecular imprinting effect was different for the two MIP was elucidated and the molecular recognition properties of P₁ were studied in detail. It was confirmed that electrostatic interaction played an important role in the molecular recognition of P₁. Scatchard analysis showed that two types of binding site with distinctly different affinity were formed in P₁. Their dissociation constants were estimated to be 7.6×10⁻⁵ mol L⁻¹ and 3.2×10⁻³ mol L⁻¹, respectively. Because P₁ has high affinity and selectivity for salicylic acid not only in organic systems but also in water-containing systems, it gives P₁ the potential for use in the enrichment, separation, and detection of salicylic acid in biological fluids.     

LBL分子沉积法制备葡萄糖氧化酶电极

采用以静电力为主的逐层分子交替沉积技术制备葡萄糖氧化酶（GOD）电极.通过带有正电荷的聚二甲基二烯丙基铵盐酸盐（PDDA）和带有负电荷的GOD交替沉积在修饰有3-巯基-1-丙基磺酸钠（MPS）的金电极表面.以甲酸二茂铁为电子媒介体,用循环伏安法检测GOD电极对葡萄糖的响应.结果表明,当GOD电极组装层数小于4时,电流响应随着层数的增加而增大,超过4层时电流响应减小.其中4层GOD修饰电极的线性范围为0.55～6.63 mmol•L－1,当pH为7.0时,响应最大.同时电极的检测重现性能良好,相对标准偏差为2.4％.     

固体超强酸催化下的醛酮自身缩合及其溶剂效应的研究

研究了在三种固体超强酸催化下醛(酮)自身的羟醛缩合反应,系统考察了反应时间,催化剂用量等因素对反应的影响,优化了反应条件.同时,对该反应的溶剂效应进行了研究.结果表明,当催化剂用量为2 g/1 mol醛(酮),反应5 h,转化率可达40%,溶剂对该反应有明显的抑制作用.超强酸对各种醛都具有较好的催化活性,其催化醛类化合物自身缩合的转化率都在48%以上,选择性在95%以上,证明固体超强酸对该缩合反应有较好的催化活性和选择性.     

Direct synthesis, characterization of Cu-SBA-15 and its high catalytic activity in hydroxylation of phenol by H2O2

Transition metal copper substituted mesoporous silica (Cu-SBA-15) was synthesized using triblock copolymers surfactant as template agent under acidic condition. The result Cu-SBA-15 was characterized with XRD, ICP-AES, FT-IR and N₂ adsorption–desorption measurements, which prove that Cu(II) was mainly incorporated into the framework of Cu-SBA-15. Its catalytic activity was studied for phenol hydroxylation using H₂O₂ (30%). The substituting element (Cu²⁺) is incorporated into the framework position forming a new type of active site which raises the phenol conversion to 62.4% and the diphenol (the mixture of catechol (CAT) and hydroquinone (HQ)) selectivity to 97%. The Cu-SBA-15 has very high selectivity for catechol (about 71% selectivity), which is completely different from that of the microporous titanium silicalite zeolites (47.1% phenol conversion and about 50% selectivity to CAT under same reaction conditions). The results obtained indicate that the selective oxidation of phenol with H₂O₂ by a radical substitution mechanism.     

Visual detection of cysteine and homocysteine

The determination of cysteine and homocysteine levels is of great current interest for the monitoring of desease states. A new colorimetric method for the simultaneous detection of l-cysteine and l-homocysteine has been developed. A fluorescein derivative reacts with the above amino acids, producing their respective thiazolidines resulting in color changes. Interference from other amino acids and proteins is minimal.     

A New Kind of Void Soap-free P（MMA-EA-MAA） Latex Particles

Soap-flee P(MMA-EA-MAA) particles with narrow size distribution were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and methacrylic acid (MAA), and large voids inside the particles were generated by alkali posttreatment in the presence of 2-butanone. Results indicated that the size of void and theparticle volume were related with the amount of 2-butanone. The generation mechanism of voids was proposed.     

Sesquiterpenoids from the Rhizome of Ligularia virgaurea

Two novel sesquiterpene dimers, compounds 1 and 2 , were isolated from the rhizome of Ligularia virgaurea, together with the six known sesquiterpenoids 3 – 8 . Their structures were established by physico‐chemical and spectroscopic methods, especially by means of 1D‐ and 2D‐NMR as well as HR‐MS analyses. A mechanism based on a classical Diels–Alder cyclization is proposed for the formation of the dimer 1 from the precursors 8 and the quinone form of 6 (Scheme).