Isolation and Crystal Structure of 6α,7α-Epoxy-5α,17α,27-trihydroxy-1-oxo-22R-witha-2,24-dienolide monohydrate-A Withasteroid from Withania somnifera Leaves

Abstract  

(5R,6S,7S,8S,9S,10R,13S,14S,17S,20R,22R)-6α,7α-epoxy-5α,17α,27-trihydroxy-1-oxo-22R-witha-2,24-dienolide has been isolated from Withania somnifera leaves. Three-dimensional X-ray intensity data were collected at 293 K on Bruker CCD area-detector diffractometer equipped with graphite-monochromated MoKα radiation (λ = 0.71073 ?). The compound crystallizes in monoclinic space group P21 with unit cell parameters: a = 6.4540(2), b = 11.3656(4), c = 17.4982(5) ?, β = 90.730 ^o(2), Z = 2. The crystal structure was refined to a final R-value of 0.0419 for 6122 observed reflections. One water solvent molecule was observed. All the rings of the steroid skeleton are trans connected. Rings A and B exists in a half-chair conformation, ring C a chair, and five membered ring D is intermediate between half-chair and envelope. The δ-lactone ring E adopts a distorted sofa conformation. The characteristic pattern observed in the packing diagram is the appearance of twisted chains of molecules. The packing of the molecules in the crystal is stabilized by intra- and intermolecular O–H···O and C–H···O interactions.     

Continuous glucose detection using boronic acid-substituted viologens in fluorescent hydrogels: linker effects and extension to fiber optics

A fluorescent anionic dye and a viologen appended with boronic acids, which serve as glucose receptors, have been synthesized and immobilized into a poly(2-hydroxyethyl methacrylate) hydrogel for use as a continuous glucose monitor. The fluorescence of the dye is modulated by the quenching efficiency of the viologen-based receptor, which in turn is dependent on the glucose concentration. Two monomeric versions of the quencher/receptor unit were prepared and their performance within the hydrogel evaluated. By tethering the quencher/receptor to the hydrogel matrix using a single-point attachment, slightly improved glucose sensing was observed. The hydrogels were tested for their ability to continuously and reversibly detect glucose over the course of several hours. The tests were carried out using a cuvette-based system, as well as a fiber-optic-based configuration. Under physiological conditions (0.1 M phosphate buffer, pH 7.4, 37 degrees C), the fluorescent hydrogels display an excellent dynamic response to glucose concentrations within the biologically significant range (2.5-20 mM).     

Evaluation of relative importance of ultrasound reactor parameters for the removal of estrogen hormones in water

The growing interest in sonochemistry as a tool for environmental remediation leads to the need for process optimization. Sonochemistry is a complex process, which depends on physical parameters and also on the process conditions. Physical parameters are interrelated and therefore a systematic approach has to be taken to optimize the process. The effect of physical parameters on the destruction of seven estrogen hormones (17α-estradiol, 17β-estradiol, estriol, 17α-ethinylestradiol, 17α-dihydroequilin, estrone and equilin) is reported in this study. Artificial neural networks (ANN) was used as a tool to identify the correlations between these process parameters. ANN enabled the establishment of relationship between sonication parameters such as power density, power intensity, ultrasound amplitude, as well as the reactor design parameters. The major significance was attributed to the area-specific power density and the volume-specific power intensity. The results of this work provide a sound basis to design pilot and full-scale ultrasound treatment systems. Process optimization lead to a 5-fold decrease in energy consumption as compared to the commercially available reactors, thereby making the process attractive for field applications.     

Palladium@gold bimetallic nanostructures as peroxidase mimic for development of sensitive fluoroimmunoassay

In this paper, gold nanoparticles coated with palladium dots (Pd@Au) bimetallic nanostructures have been reported to have a peroxidase like activity which is not found in their monometallic counterparts. Based on this finding, we have developed an immunoassay in which antibody-modified Pd@Au nanostructure catalyzes the dimerization of a fluorogenic substrate for peroxidase, 3-(4-dihydroxy phenyl) propionic acid (HPPA), to generate high fluorescence signal. Specific antibodies against bensulfuron-methyl were generated by using a well characterized bensulfuron–protein conjugate as an immunogen, and the assay was performed in a competitive immunoassay format where Pd@Au nanostructure was bound to secondary antibody to show the peroxidase like activity. The developed immunoassay exhibited an excellent sensitivity showing a dynamic response range from 0.001 to 100 ng mL⁻¹ for herbicide bensulfuron-methyl with a detection limit of 0.01 ng mL⁻¹ (n = 3). The newly synthesized bimetallic nanostructure shows the advantages of low cost, easy synthesis and tunable catalytic activity, making it a promising substitution of enzyme peroxidase in different applications.     

Rectangular Tiling in Multidimensional Arrays

We study the following tiling problem in d dimensions: given a d-dimensional rectangular array of nonnegative numbers and an integer p, partition the array into at most p rectangular subarrays so that the maximum weight of any subarray is minimized; the weight of a subarray is the sum of its elements. The rectangular tiling problem is motivated by applications in data mining, data partitioning, and video compression. Recently, Khanna, Muthukrishnan, and Paterson [SODA '98], showed that the tiling problem is NP-complete and gave a 2.5-approximation algorithm for d = 2.In this paper, we extend their result to multidimensional arrays and give an algorithm with approximation ratio , for d ≥ 2. The algorithm can be implemented to run in worst-case time O(N + p log N) time, where N is the size of the array, and the constant is of the order d!. We also obtain a similar algorithm for the dual tiling problem, where the goal is to compute a tiling of weight at most W using as few tiles as possible. Our algorithm yields an approximation factor (2d + 1).We implemented our algorithm and ran simulation tests on multidimensional arrays with random data. In our limited experiments, the algorithm always produced approximations that were no worse than factor two from the optimal.     

Analysis of a Fork/Join Synchronization Station with Inputs from Coxian Servers in a Closed Queuing Network

Fork/join stations are commonly used to model the synchronization constraints in queuing models of computer networks, fabrication/assembly systems and material control strategies for manufacturing systems. This paper presents an exact analysis of a fork/join station in a closed queuing network with inputs from servers with two-phase Coxian service distributions, which models a wide range of variability in the input processes. The underlying queue length and departure processes are analyzed to determine performance measures such as throughput, distributions of the queue length and inter-departure times from the fork/join station. The results show that, for certain parameter settings, variability in the arrival processes has a significant impact on system performance. The model is also used to study the sensitivity of performance measures such as throughput, mean queue lengths, and variability of inter-departure times for a wide range of input parameters and network populations.     

Influence of oxygen deficiency on the thermoelectric power of Y1Ba2Cu3O7-x

In this paper we report measurements of the thermoelectric power on a series of Y₁Ba₂Cu₃O_7-x specimens with varying amounts of oxygen deficiency obtained by changing the cooling rate of the sintered specimens. The specimens have been characterized by X-ray diffraction measurements, electric resistivity and oxygen contents. The temperature variation of the thermopower reveals a peak just before the onset of superconducting transition. We examine possible theoretical explanations of this anomaly. In particular we argue that this anomaly is associated with the pairing fluctuations in the normal state close toT _c . We present some theoretical results in support of this conclusion.     

Two colour multiphoton ionization spectroscopy of uranium from a metastable state

Using two pulsed tunable dye lasers, a two colour multiphoton ionization process has been utilised to explore the higher energy levels of uranium. One hundred and thirty eight new UI levels have been observed in the 37540–38420 cm^–1 region. J assignments of these levels have been suggested on the basis of their excitation from intermediate levels with known and contiguous J values. In eight cases the J assignments are unique.     

Mixed hp finite element methods for problems in elasticity and Stokes flow

Summary. We consider the mixed formulation for the elasticity problem and the limiting Stokes problem in , . We derive a set of sufficient conditions under which families of mixed finite element spaces are simultaneously stable with respect to the mesh size and, subject to a maximum loss of , with respect to the polynomial degree . We obtain asymptotic rates of convergence that are optimal up to in the displacement/velocity and up to in the "pressure", with arbitrary (both rates being optimal with respect to ). Several choices of elements are discussed with reference to properties desirable in the context of the -version. Received March 4, 1994 / Revised version received February 12, 1995