General and efficient strategy for erythrinan and homoerythrinan alkaloids: syntheses of (+/-)-3-demethoxyerythratidinone and (+/-)-erysotramidine

[reaction: see text] A general and efficient strategy to both aromatic-type and nonaromatic-type erythrinan and homoerythrinan alkaloids has been developed. This approach involves a key two-step sequence, an alkylation of a ketone with various N-substituted iodoacetamides followed by a N-acyliminium ion promoted intramolecular cyclization, and represents one of the shortest routes to erythrinan and homoerythrinan alkaloids. As the application, the formal total synthesis of (+/-)-3-demethoxyerythratidinone and the total synthesis of (+/-)-erysotramidine have been achieved, respectively.     

A novel and efficient 4-oxothiazolidine-1,2-dithiole rearrangement induced by Lawesson's reagent

Functionalized 1,2-dithioles have been synthesized by a ring opening-closing process of 5-substituted- and 5-unsubstituted-2-alkylidene-4-oxothiazolidines with Lawesson's reagent. The ¹³C NMR data confirmed the meso-ionic structure of these aromatic-type 1,2-dithioles.     

Methane dehydroaromatization with periodic CH_4-H_2 switch:A promising process for aromatics and hydrogen

Long-term stability test of Mo/HZSM-5-N catalysts(HZSM-5-N stands for nano-sized HZSM-5) in methane dehydroaromatization(MDA)reaction has been performed with periodic CH4-H2 switch at 1033-1073 K for more than 1000 h.During this test,methane conversion ranges from 13% to 16%,and mean yield to aromatics(i.e.benzene and naphthalene) exceeds 10%.N2-physisorption,XRD,NMR and TPO measurements were performed for the used Mo/HZSM-5 catalysts and coke deposition,and the results revealed that the periodic hydrogenation can effectively suppress coke deposition by removing the inert aromatic-type coke,thus ensuring Mo/HZSM-5 partly maintained its activity even in the presence of large amount of coke deposition.The effect of zeolite particle size on the catalytic activity was also explored,and the results showed that the nano-sized zeolite with low diffusion resistance performed better.It is recognized that the size effect was enhanced by reaction time,and it became more remarkable in a long-term MDA reaction even at a low space velocity.     

Oxidation-Induced Structural Alterations and Its Effect on Chaperone Function of Rat Lens α-Crystallin

An ascorbate-FeCl₃-EDTA-H₂O₂ system was used to oxidize rat lens α-crystallins. Under this oxidative insult, the chaperone activity of α-crystallin toward γ-crystallin was shown to decrease significantly, which is quite different from the result reported by Wang and Spector. (Invest. Ophthalmol. Vis. Sci. 1995 , 36, 311-321.) Fluorescence spectroscopy and circular dichroism were employed to characterize the structural changes of oxidized α-crystallin. It was found that fluorescence intensity of l-anilinonaphthalene-8-sul-phonate (ANS) bound to oxidized α-crystallin increased comparing to that bound to normal α-crystallin, suggesting oxidation causes the exposure of more hydrophobic regions. Further, α-crystallin's fluorescence intensity in response to tryptophan residues showed a pseudo first order decline. Amino acid analysis of normal versus oxidized α-crystallin confirmed actual decline in tryptophan levels, showing about 80% of tryptophan being modified after 10-hour oxidation. Circular dichroism showed both changes in the secondary and tertiary structures of oxidized α-crystallin, characterized by a large loss of aromatic-type amino acid interactions and a large loss of β-sheet structure. In conclusion, modified tryptophan, secondary and tertiary structural changes of α-crystallin correlate best with the reduction of chaperone function, the curves all showing a linear slope for 10 hours, then plateauing. These results indicate that the decrease of α-crystallin chaperone activity is attributed to the structural changes.     

最小二乘—红外光谱法定量测定羟基化合物

根据羟基伸缩振动吸收带的特性，用最小二乘法有效消除了溶液中羟基间的缔合作用对测定结果的影响。此方法已用于聚合物中羟基含量的测定。     

An ion grouping method for calculating the Madelung constant for the sodium chloride lattice

A method has been developed for calculating the Madelung constant for a sodium chloride lattice. In this method, a reference ion is selected and all other ions are placed in groups around the reference ion. To include ions in all locations, seven types of groups are necessary. Recursion formulas are obtained to compute the effect of each group of ions and the Madelung constant is computed from the total effect produced by all the groups. A total of 29 cubical shells of ions around the reference ion were used in the calculation. The computation produces an oscillating function which alternately goes above and below the actual Madelung constant as the computation is expanded to include each successive shell of ions. A numerical method is described to obtain the average value of the oscillating function. A value of the Madelung constant of 1.74759 results from the abbreviated calculation.     

p-carboxylation of linear high molecular-mass polystyrene

A simple method is reported for the post-polymerization partial p-carboxylation of linear polystyrene without degradation or crosslinking of the polymer. The method is based on Friedel–Crafts acetylation of the polystyrene under mild conditions, followed by oxidation of the acetyl groups by means of a phase-transfer-catalyzed haloform reaction. The method is well suited for the synthesis of high molecular mass, monodisperse ionomers with p-carboxylate groups situated randomly along the polystyrene chain. © 1993 John Wiley & Sons, Inc.     

An ion chromatographic method for the estimation of tresyl groups on activated supports

Summary A simple and sensitive ion chromatographic method for the estimation of tresyl groups on several activated supports (tresylated diol silica, tresylated Sepharose 4B and Tresyl-5PW) has been developed. The method involves the hydrolysis of tresyl groups on the supports followed by ion chromatographic determination of the liberated 2,2,2-trifluoroethanesulfonic acid. It is useful for the prediction of the immobilization efficiency of proteins.     

A spectrophotometric assay for solid phase primary amino groups

A rapid, sensitive, and convenient spectrophotometric assay was developed for the measurement of amino groups on solid supports. This method is based on the reaction of amino groups of solids with an excess ofo-phthaldialdehyde (OPA) and subsequent quantitative determination of unreacted OPA by reaction with glycine. Four solids possessing variable quantities of amino groups were examined. Results indicate that about 70% of the total surface amino concentration (determined by the microKjeldahl method) are available for ligand attachment. Unlike the spectrophotometric 2,4,6-trinitrobenzenesulfonic acid method, the OPA spectrophotometric assay is more rapid, sensitive, and convenient, and unlike the spectrofluorimetric OPA, it does not require sophisticated instrumentation.     

Synthesis of series of 1- and 3-differently substituted xanthines from imidazoles

A new and general method is described for the synthesis, in three steps and in good overall yields, of tetrasubstituted xanthines from an easily prepared imidazole precursor. The method is especially useful for the preparation in standardized conditions of series of xanthines combining a broad variety of primary or secondary alkyl, benzyl or aryl groups at N1 and of alkyl or arylmethyl groups at N3, that are not readily available by other methods.     

三溴甲基芳烃合成新方法的研究

报道了一种以三氯甲基芳烃与三溴化硼反应制备系列三溴甲基芳烃的新方法. 该方法反应条件温和, 收率高, 选择性好. 同时, 对影响该反应的因素进行了研究, 发现当芳环上连有强吸电子基团时, 不利于反应的进行, 而连有推电子基团时, 则有利于反应进行; 当取代基处于邻位时, 则明显阻碍反应的进行. 采用这种方法已合成了十多个三溴甲基芳烃, 其中1个是未见文献报道的新化合物.     

A mild C-O bond formation catalyzed by a rhenium-oxo complex

A mild method for the regioselective synthesis of propargyl ethers by the coupling of propargyl alcohols with a range of other alcohols is described. The method employs an air- and moisture-tolerant rhenium-oxo complex ((dppm)ReOCl3) as a catalyst for the formation of sp3-carbon-oxygen bonds without the need for prior activation of the propargyl alcohol or deprotonation of the alcohol nucleophile. A broad range of functional groups is tolerated, including aryl halides, olefins, esters, and acid-labile functional groups such as acetals. Furthermore, displacement of the alcohol occurs preferentially even in the presence of other electrophiles such as primary alkyl halides and conjugated esters.     

Neues Verfahren zur Bestimmung der endständigen Carboxylgruppen von Peptiden

A new and simple method for the determination of the C-terminal groups of peptides is proposed. The carboxyl groups are converted into the corresponding peptide-triazines by treating with dimethylbiguanide. These derivatives are then hydrolysed by Streptomyces griseus protease and the amino-acid derivatives in the hydrolysate are identified by thin-layer or paper chromatography.     

Determination of carbonyl-containing functional groups in oxidized polyethylene

A combined (chemical and infrared (IR) spectrophotometric) method is discussed for the simultaneous determination of concentrations of carboxyl (A), ketone (K), and ester (E) groups formed in the oxidation of polyethylene (PE). The IR absorptivities of these functional groups were determined by using model compounds [stearic acid, stearone, poly-(1,4-butylene sebacate)]. The integral absorption of the C?O band of polymer samples which contained several oxo groups of different types was found to be additive. This method was applied to the determination of the carboxyl, ester, and ketone content of samples oxidized at different oxygen pressures.     

脂肪酸甲酯乙氧基化物的气相色谱分析

用0.5 mol/L KOH乙醇溶液水解脂肪酸甲酯乙氧基化物(FMEO),酯键断裂,其疏水基甲 酯化、亲水基硅醚化后分别用气相色谱法测定其组成,并采用峰面积归一化法进行了组分的 定量。成功测定了各种FMEO样品的疏水基组成和环氧乙烷(EO)加成数分布,方法简单,重复性 好,尤其是对原料为混碳脂肪酸甲酯的FMEO更有意义。     

Quantitative treatment of the dye partition method of analysis of surfactants and of ionic groups in high polymers

A quantitative treatment of the extraction of ionic dyes from aqueous solutions into organic solvents of low dielectric constant by surfactants or polymers with ionic groups having a charge opposite to that of the dye ion, is presented. The assumption is made that the extracted species are ion-paired in the organic phase. Based on this, a graphical extrapolation method is suggested for the quantitative estimation of ionic groups in polymers. Theoretically, the method should yield quantitative results irrespective of polymer chain length and character. This method of analysis does not require any calibration data.     

A practical preparation of highly versatile N-acylpyrroles from 2,4,4-trimethoxybutan-1-amine

A novel method for the preparation of N-acylpyrrole is described. The method involves condensation of carboxylic acids with 2,4,4-trimethoxybutan-1-amine, followed by acid-mediated cyclization to form the pyrrole ring. The preparative procedure is highly tolerant of a variety of functional groups.     

Detection of carbonyl groups in triterpenoids by hydroxylamine hydrochloride derivatization using electrospray ionization mass spectrometry

A rapid, simple electrospray ionization mass spectrometry (ESI-MS) sensitivity enhancement method for detecting carbonyl groups in triterpenoids has been developed by using hydroxylamine hydrochloride (NH(2)OH . HCl) as a derivatization reagent. We use the oxime formed during the derivatization reactions and its Beckmann rearrangement intermediates as a means of detecting the carbonyl groups originally present in these triterpenoids. In comparison with other derivatization methods reported in the literature, this method is simple, specific and can be used to detect carbonyl groups in triterpenoids which have low polarity and are poorly or non-ionizable. Moreover, it can also be used to detect hydroxyl groups by using the Dess-Martin periodinane (DMP) to convert primary and secondary hydroxyls into carbonyl groups.     

Amino-functionalization of large-pore mesoscopically ordered silica by a one-step hyperbranching polymerization of a surface-grown polyethyleneimine

A simple method for surface functionalization of large-pore mesoporous silica by hyperbranching polymerization resulting in a high loading of amine groups is presented.     

Reversed-phase liquid chromatographic method for the analysis of aminoglycoside antibiotics using pre-column derivatization with phenylisocyanate

A pre-column derivatization liquid chromatographic method has been developed for the analysis of aminoglycoside antibiotics using phenylisocyanate as a derivatization reagent. Derivatives including kanamycin, neomycin and gentamicin were formed by reaction of the analytes with phenylisocyanate in the presence of triethylamine. Phenylisocyanato groups were attached to corresponding amino groups of aminoglycoside and their molecular mass was confirmed by liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS). The experimental conditions for derivatization and separation of aminoglycoside derivatives were optimized and validated. A simple liquid chromatographic method for the determination of aminoglycoside antibiotics was demonstrated.