The aim of this paper is to present two different approachs in order to obtain an existence result to the so-called quadrature
surface free boundary problem. The first one requires the shape derivative calculus while the second one depends strongly
on the compatibility condition of the Neumann problem. A necessary and sufficient condition of existences is given in the
radial case. 相似文献
Protein-polymer conjugates are widely used in biotechnology and medicine, and new methods to prepare the bioconjugates would be advantageous for these applications. In this report, we demonstrate that bioactive "smart" polymer conjugates can be synthesized by polymerizing from defined initiation sites on proteins, thus preparing the polymer conjugates in situ. In particular, free cysteines, Cys-34 of bovine serum albumin (BSA) and Cys-131 of T4 lysozyme V131C, were modified with initiators for atom transfer radical polymerization (ATRP) either through a reversible disulfide linkage or irreversible bond by reaction with pyridyl disulfide- and maleimide-functionalized initiators, respectively. Initiator conjugation was verified by electrospray-ionization mass spectroscopy (ESI-MS), and the location of the modification was confirmed by muLC-MSMS (tandem mass spectrometry) analysis of the trypsin-digested protein macroinitiators. Polymerization of N-isopropylacrylamide (NIPAAm) from the protein macroinitiators resulted in thermosensitive BSA-polyNIPAAm and lysozyme-polyNIPAAm in greater than 65% yield. The resultant conjugates were characterized by gel electrophoresis and size exclusion chromatography (SEC) and easily purified by preparative SEC. The identity of polymer isolated from the BSA conjugate was confirmed by (1)H NMR, and the polydispersity index was determined by gel permeation chromatography (GPC) to be as low as 1.34. Lytic activities of the lysozyme conjugates were determined by two standard assays and compared to that of the unmodified enzyme prior to polymerization; no statistical differences in bioactivity were observed. 相似文献
Guanine bases are the most easily oxidized sites in DNA. Electron-deficient guanine species are major intermediates produced in DNA by the direct effect of ionizing radiation (ionization of the DNA itself) because of preferential hole migration within DNA to guanine bases. By using thiocyanate ions to modify the indirect effect (ionization of the solvent), we are able to produce these single-electron-oxidized guanine radical species in dilute aqueous solutions of plasmid DNA where the direct effect is negligible. The guanyl radical species produce stable modified guanine products. They can be detected in the plasmid by converting them to strand breaks after incubation with a DNA repair enzyme. If a phenol is present during irradiation, the yield of modified guanines is decreased. The mechanism is reduction of the guanine radical species by the phenol. It is possible to derive a rate constant for the reaction of the phenol with the guanyl radical. The pH dependence shows that phenolate anions are more reactive than their conjugate acids, although the difference for guanyl radicals is smaller than with other single-electron-oxidizing agents. At physiological pH values, the reduction of a guanyl radical entails the transfer of a proton in addition to the electron. The relatively small dependence of the rate constant on the driving force implies that the electron cannot be transferred before the proton. These results emphasize the potential importance of acidic tyrosine residues and the intimate involvement of protons in DNA repair. 相似文献
Guanidine-based peptide nucleic acid (GPNA) with a d-backbone configuration and alternate spacing binds sequence-specifically to RNA and is readily taken up by both human somatic and embryonic stem (ES) cells. 相似文献
Solutions are presented herein of some contact problems connected with the torsion of a composite half-space. In the general case the problem of the torsion of a composite elastic half-space is examined by means of the rotation of a stiff finite cylinder welded into a vertical recess of this half-space. Moreover, the following particular problems on the torsion of such a half-space are considered.
1. 1) A composite half-space with a vertical elastic infinite core, twisted by means of the rotation of a stiff stamp affixed to the upper endplate of the elastic core.
2. 2) A half-space with a vertical cylindrical infinite hole, twisted by means of the rotation of a stiff finite cylinder welded into the upper part of this hole.
In the general case the solution of the problem reduces to the solution of an integral equation of the second kind on a half-line. The question of the solvability of this fundamental integral equation is investigated, and it is shown that its solution may be constructed by successive approximations.
Let us note that the problem of the torsion of a homogeneous half space and of an elastic layer by means of rotation of a stiff stamp has been considered by Rostovtsev [1], Reissner and Sagoci [2], Ufliand [3], Florence [4], Grilitskii [5] and others.
The problem of the torsion of a circular cylindrical rod and the half-space welded to it which are subject to a torque applied to the free endface of the rod has been considered by Grilitskii and Kizyma[6].
The torsion of an elastic half-space with a vertical cylindrical inclusion of some other material by the rotation of a stiff stamp on the surface of this half-space has been considered in [7], wherein it has been assumed that the stamp is symmetrically disposed relative to the axis of the inclusion and lies simultaneously on both materials. 相似文献
The direct conversion of a variety of heteroaromatic bromides into heteroaromatic amides is described. This reaction utilizes Mo(CO)6 as the carbon monoxide source and is performed using microwave heating allowing for very short reaction times. This convenient methodology allows for the preparation of a variety of heteroaromatic amides useful in medicinal chemistry applications. 相似文献
The crystal structures of hydrate (1) and anhydrate (2) forms of 2,3-pentamethylene-3,4-dihydroquinazolin-4-one hydrochloride have been determined by X-ray structure analysis. Crystal data of 1 are 2(C13H14N2O)*3(HCl)*4.5 (H2O), triclinic P?1, Z=2, a=8.004(5), b=13.129(7), c=15.725(7) Å, α=106.45(4), β=92.61(4), γ=97.98(5), R=0.0652 and 2 are C13H14N2O*HCl, monoclinic C2/c, Z=8, a=21.360(4), b=5.954(1), c=21.263(4), β=117.89(3), R=0.0556. The crystal of the hydrate form 1is unstable. This form collapses easily with evaporation of H2O and part of HCl molecules from crystals. By recrystallizing destroyed form has been obtained stable crystal form 2. 相似文献
The 13C and 119Sn NMR spectra of tri(1-butyl)tin(IV) and triphenyltin(IV) oxinates and 1-naphthoxides in neat liquid and deuteriochloroform, pentadeuteriopyridine and hexamethylphosphortriamide solutions, and the 15N NMR spectra of both the oxinates and 8-methoxyquinoline in deuteriochloroform have been recorded. From the comparison of chemical shifts δ(13C), δ(15N) and δ(119Sn) and coupling constants nJ(119Sn13C) of the compounds it is concluded that the triorganotin(IV) oxinates, both as the neat liquid and in solution, form complexes containing five-coordinate tin atoms. In the neat liquid and in deuteriochloroform (a non-coordinating solvent) oxinates form chelate complexes with a cis-trigonal bipyramid arrangement. In coordinating solvents (pentadeuteriopyridine, hexamethylphosphortriamide) these are equilibria involving the formation of small amounts of oxinate complexes with one solvent molecule. These complexes have trans-trigonal bipyramid geometry with butyl or phenyl groups in equatorial plane and the monodentate oxinate group and a solvent molecule in axial positions. 相似文献
A rapid and sensitive liquid chromatography/tandem mass spectrometry (LC/MS/MS) assay was developed and validated to quantify a novel antineoplastic agent, PM00104, in mouse, rat, dog, and human plasma. The method was validated to demonstrate the specificity, limit of quantification (LOQ), accuracy, and precision of measurements. The calibration range for PM00104 was established using PM00104 standards from 0.01-5.0 ng/mL in blank plasma. The selected reaction monitoring (SRM), based on the m/z 692.2 --> 218.2 transition, was specific for PM00104, and that based on the m/z 697.2 --> 218.2 transition was specific for PM00104 ((13)C(2),(2)H(3)) (the internal standard, IS); no endogenous materials interfered with the analysis of PM00104 and IS from blank plasma. The assay was linear over the concentration range 0.01-5.0 ng/mL. The correlation coefficients for the calibration curves ranged from 0.9981-0.9999. The mean intra-day and inter-day accuracies for all calibration standards (n = 8) ranged from 97-105% (< or =5% bias) in human plasma, and the mean inter-day precision for all calibration standards was less than 8.5%. The mean intra- and inter-day assay accuracy for all quality control (QC) replicates in human plasma (n = 9), determined at each QC level throughout the validated runs, ranged from 96-112% (< or =12% bias) and from 102-105% (< or =5% bias), respectively. The mean intra- and inter-day assay precision was less than 15.0 and 11.8% for all QC levels, respectively. For the QC samples prepared in animal species plasma, the %CV values of the assays ranged from 1.8-8.8% in mouse plasma, from 3.7-13.8% in rat plasma, and from 3.0-7.2% in dog plasma. The assay accuracies ranged from 92-102% (< or =8% bias) for all QC levels prepared in mouse plasma; ranged from 93-106% (< or =7% bias) in rat plasma; and ranged from 95-114% (< or =14% bias) in dog plasma. The assay has been used to support preclinical pharmacokinetic and toxicokinetic studies and is currently used to measure PM00104 plasma concentrations to support clinical trials. 相似文献