Nickel‐Catalyzed α‐Carbonylalkylarylation of Vinylarenes: Expedient Access to γ,γ‐Diarylcarbonyl and Aryltetralone Derivatives

We report a Ni‐catalyzed regioselective α‐carbonylalkylarylation of vinylarenes with α‐halocarbonyl compounds and arylzinc reagents. The reaction works with primary, secondary, and tertiary α‐halocarbonyl molecules, and electronically varied arylzinc reagents. The reaction generates γ,γ‐diarylcarbonyl derivatives with α‐secondary, tertiary, and quaternary carbon centers. The products can be readily converted to aryltetralones, including a precursor to Zoloft, an antidepressant drug.     

Investigation into the determination of trimethylarsine in natural gas and its partitioning into gas and condensate phases using (cryotrapping)/gas chromatography coupled to inductively coupled plasma mass spectrometry and liquid/solid sorption techniques

Speciation of trialkylated arsenic compunds in natural gas, pressurized and stable condensate samples from the same gas well was performed using (Cryotrapping) Gas Chromatography-Inductively Coupled Plasma Mass Spectrometry. The major species in all phases investigated was found to be trimethylarsine with a highest concentration of 17.8 ng/L (As) in the gas phase and 33.2 μg/L (As) in the stable condensate phase. The highest amount of trimethylarsine (121 μg/L (As)) was found in the pressurized condensate, along with trace amounts of non-identified higher alkylated arsines. Volatile arsenic species in natural gas and its related products cause concern with regards to environment, safety, occupational health and gas processing. Therefore, interest lies in a fast and simple field method for the determination of volatile arsenicals. Here, we use simple liquid and solid sorption techniques, namely absorption in silver nitrate solution and adsorption on silver nitrate impregnated silica gel tubes followed by total arsenic determination as a promising tool for field monitoring of volatile arsenicals in natural gas and gas condensates. Preliminary results obtained for the sorption-based methods show that around 70% of the arsenic is determined with these methods in comparison to volatile arsenic determination using GC-ICP-MS. Furthermore, an inter-laboratory- and inter-method comparison was performed using silver nitrate impregnated silica tubes on 14 different gas samples with concentrations varying from below 1 to 1000 μg As/m³ natural gas. The results obtained from the two laboratories differ in a range of 10 to 60%, but agree within the order of magnitude, which is satisfactory for our purposes.     

Rapid Screening of Lipase Inhibitors from Ophiopogonis Radix Using High-Performance Thin Layer Chromatography by Two Step Gradient Elution Combined with Bioautographic Method

In this study, a high-performance thin layer chromatography (HPTLC) method by two step gradient elution with two mobile phases was developed for the simultaneous analysis of seven constituents in Ophiopogonis Radix. The chromatography was performed on silica gel 60 F₂₅₄ plate with dichloromethane-methanol-ethyl acetate-water (70:25:12:3, v/v/v/v) and dichloromethane-methanol (300:1, v/v) as the mobile phase for two step gradient elution. Then, the HPTLC profiles were observed after derivatization with 10% sulfuric acid in ethanol solution. The obtained HPTLC images were further analyzed by chemometric approaches and the samples could be clustered based on regions and/or growth years, which were two important factors affecting the constituents in Ophiopogonis Radix. Furthermore, five compounds including ophiopogonin D, ophiopojaponin C, ophiopogonin D’, ophiopogonin C’ and methylophiopogonanone B were screened as potential lipase inhibitors from Ophiopogonis Radix by the HPTLC-bioautographic method. The binding modes and interactions between the five compounds and lipase were further explored by molecular docking analysis. The developed HPTLC method could be used for quality control of Ophiopogonis Radix and screening of the potential lipase inhibitors.     

Ultrasonically controlled polymeric drug delivery

The area of polymeric controlled drug delivery systems has been a field of increasing interest. However, relatively little attention has been given to developing systems in which the rate of delivery can be manipulated externally. We now report that release rates of biologically active substances from a polymeric matrix can be repeatedly modulated from a position external to the environment of use by ultrasonic energy. The ultrasound affects the degradation rate of bioerodible polymers as well as permeation through non-erodible polymers. The system has been shown to be responsive in vivo. Skin histopathology of the ultrasound treated area didn't reveal any differences between the treated skin and the untreated controls.     

Response of bare 1-3 piezocomposite array to localized electrical excitation

The theoretical response of a 1-3 piezocomposite plate submitted to localized electrical excitation was studied with the theory of guided waves. The theoretical modeling was based on the global matrix method, and the piezocomposite material was considered as a homogeneous medium. To validate the theoretical results, experimental displacement measurements were performed with an interferometric probe on two piezocomposite plates, one with a single element and one with an array of electrodes. The measured response on the single-element plate was mainly supported by the S0 and S3 modes of the plate. Homogenization limits of the composite in terms of frequency and wave number are defined on the basis of data from this sample. Within these limits, the piezocomposite material operates as a homogeneous medium, and comparison between theoretical and experimental results allows the equivalent electroacoustic parameters to be evaluated. A second sample was measured to study the effects of the electrode array on the electroacoustic response of the plate. Two kinds of electrical excitation were studied.     

An improved method for the analysis of major antioxidants of Hibiscus esculentus Linn

Major antioxidants of aqueous ethanol extract from Lady's Finger (Hibiscus esculentus Linn) were systematically investigated in this study. Firstly, high-performance liquid chromatography (HPLC) was applied to identify antioxidant peaks in a sample by spiking the sample extract with 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) free radical, which was prepared from manganese dioxide and ABTS. Secondly, in order to identify the elution period of major antioxidant peaks, the antioxidant capacities of different fractions from solid-phase extraction (SPE) were measured, and the chromatograms of fractions were also recorded. Lastly, multiple mass spectrometry (MS(n)) was used to elucidate the possible chemical structures of antioxidants, and nuclear magnetic resonance (NMR) was further applied for structure confirmation. The major antioxidant compounds in lady's finger were identified to be quercetin derivatives and (-)-epigallocatechin using HPLC-MS and HPLC-MS(n) (n = 2-4) techniques. It was found that about 70% of total antioxidant activity was contributed by four quercetin derivatives. The structures of major antioxidants, which were isolated by semi-preparative RP-HPLC with two tandem C18 columns, were further confirmed using UV-vis absorption spectroscopy and 13C NMR spectra. Quercetin 3-O-xylosyl (1' --> 2') glucoside, quercetin 3-O-glucosyl (1' --> 6') glucoside, quercetin 3-O-glucoside and quercetin 3-O-(6'-O-malonyl)-glucoside were first identified and characterized as major antioxidants in lady's finger.     

Observation of geometric phases for mixed states using NMR interferometry

Examples of geometric phases abound in many areas of physics. They offer both fundamental insights into many physical phenomena and lead to interesting practical implementations. One of them, as indicated recently, might be an inherently fault-tolerant quantum computation. This, however, requires one to deal with geometric phases in the presence of noise and interactions between different physical subsystems. Despite the wealth of literature on the subject of geometric phases very little is known about this very important case. Here we report the first experimental study of geometric phases for mixed quantum states. We show how different they are from the well-understood, noiseless, pure-state case.     

Adsorptive refolding of a highly disulfide-bonded inclusion body protein using anion-exchange chromatography

α-Fetoprotein (AFP) is a prospective biopharmaceutical candidate currently undergoing advanced-stage clinical trials for autoimmune indications. The high AFP expression yields in the form of inclusion bodies in Escherichia coli renders the inclusion body route potentially advantageous for process scale commercial manufacture, if high-throughput refolding can be achieved. This study reports the successful development of an ‘anion-exchange chromatography’-based refolding process for recombinant human AFP (rhAFP), which carries the challenges of contaminant spectrum and molecule complexity. rhAFP was readily refolded on-column at rhAFP concentrations unachievable with dilution refolding due to viscosity and solubility constraints. DEAE-FF functioned as a refolding enhancer to achieve rhAFP refolding yield of 28% and product purity of 95% in 3 h, at 1 mg/ml protein refolding concentration. Optimization of both refolding and chromatography column operation parameters (i.e. resin chemistry, column geometry, redox potential and feed conditioning) significantly improved rhAFP refolding efficiency. Compared to dilution refolding, on-column rhAFP refolding productivity was 9-fold higher, while that of off-column refolding was more than an order of magnitude higher. Successful demonstration that a simple anion-exchange column can, in a single step, readily refold and purify semi-crude rhAFP comprising 16 disulfide bonds, will certainly extend the application of column refolding to a myriad of complex industrial inclusion body proteins.     

Optimization of asymmetric hydrogenation of 3-phenyl-3-butenoic acid catalyzed by rhodium(I)-4,5-bis[(diphenylphosphino)methyl]-2,2-dimethyldioxolane (DIOP)

Enantioselective, homogeneous hydrogenation of 3-phenyl-3-butenoic acid (1) has extensively been examined in the presence of the rhodium(I)/4,5-bis[(diphenylphosphino)methyl]-2,2-dimethyldioxolane (DIOP) catalyst systems. Optimization of the reaction conditions was undertaken mainly by controlling effects of added tertiary amines as well as solvent polarities on the enantio-selectivity of the product. The best asymmetric yield (85.1% e.e.) was attained when the hydrogenation was carried out in the presence of triethylamine (5 mol%) in 75% aqueous methanol using a neutral rhodium-DIOP catalyst.     

Charged patch attraction in dispersion: effect of polystyrene sulphonate molecular weight or patch size

The molecular weight (Mw) effect of polystyrene sulphonate (PSS) on the yield stress of ZrO₂ dispersion was evaluated. Three “monodispersed” samples with Mw of 1430, 9960 and 130,000, and two broad distribution samples of Mw 70,000 and 1.0 million were investigated. Adsorbed PSS gave rise to charged patch attraction that enhanced the maximum yield stress, τ _{y max}, of dispersions at charge neutral condition [3]. As a PSS patch consists of only one molecule, the patch size should increase with increasing Mw. For PSS of Mw 1430 with just only seven repeating units the patch formed would be rectangular (linear) and small with a high charge density. For Mw of 9960 and higher, the patch would be irregular in shape with a smaller charge density. At a moderate surface coverage of ˜20%, the τ _{y max} increases quite sharply from Mw 9960 to 130,000 and very gradually from 130,000 to 1.0 million. From Mw 9960 to 130,000, the strength of the patch attraction increases quite strongly with increasing patch size. From Mw 130,000 to 1million, the small increase in τ _{y max} reflected a limiting patch size effect. At the limiting size, the attraction is at maximum strength. At the same coverage, PSS of Mw 1430 also displayed a strong charge patch attraction. This was attributed to a higher number of charged patch interactions at the closest point of separation and also to the high charge density of the PSS patch. The low surface coverage of 6% revealed no significant molecular weight effect on τ _{y max}. The network structure consisted of a mixture of charge patch and bare surface interactions. Received: 4 July 2000/Accepted: 18 July 2000