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81.
KellyA.Davis KrzysztofMatyjaszewski 《高分子科学》2004,(2):195-204
The polymerization of n-butyl methacrylate was investigated using the Atom Transfer Radical Polymerization technique with CuBr and CuCl/N,N,N‘,N“,N“-pentamethyldiethylenetriamine catalytic systems. Various combinations of catalyst systems and initiators were utilized in order to optimize the polymerization conditions and to obtain well-defined polymers (i.e. controlled molecular weights and low polydispersities). It has been found that the optimal initiator for this system is a chlorine-based initiator, when the catalyst used is a Cu(I) salt in conjunction with the N,N,N‘,N“,N“-pentamethyldiethylenetriamine ligand. Bromine-based initiators tend to result in large amounts of initial termination, leading to polymers with less than ideal chain end functionality, even if CuCI is used as the Cu(I) species to invoke the halogen exchange. Additionally, the effects of the polymerization temperature, copper(I) species and the initiator structure were determined. 相似文献
82.
An investigation of heparinase immobilization 总被引:1,自引:0,他引:1
Bernstein Howard Yang Victor C. Langer Robert 《Applied biochemistry and biotechnology》1987,16(1):129-143
A systematic investigation of the parameters that affect the efficiency of immobilizing heparinase onto cyanogen bromide activated
crosslinked 8% agarose beads was conducted. Two experimental measures, the “fraction bound” and the “fraction retained,” were
used to monitor the coupling efficiency. The fraction bound is the portion of the total initial enzyme that is bound to the
agarose gel. The fraction retained is the fraction of bound enzyme that is active. The product of the two measures indicates
the coupling efficiency. The activity of the immobilized heparinase was measured under conditions free of both internal and
external mass transfer limitations, and thus, the fraction retained represents the true immobilized enzyme activity.
Increasing the degree of activation of the beads results in an increase in the fraction bound, the fraction retained, and
consequently, the coupling efficiency. As the ratio of enzyme solution to gel volume increases from 1.5 to 2.2, the fraction
bound remains constant but the fraction retained decreases (heparinase concentration; 0.15 mg/mL and degree of activation;
9.5 μmol of cyanate esters/g of gel). At volume ratios greater than 2.2, both the fraction bound and the fraction retained
decline continuously. Changing the heparinase concentration in the coupling solution changes the coupling efficiency in a
manner similar to that of the volume ratio change.
When heparin is added during the coupling process, the fraction bound declines as the heparin concentration increases, whereas
the fraction retained increases up to a heparin concentration of 12 mg/mL and decreases thereafter. When arginine, lysine,
and glycine are used to block the unreacted cyanate ester groups after the coupling process, the immobilized heparinase shows
different pH optima of 6.5, 6.9, and 7.2, respectively. Based upon these findings, a protocol to optimize heparinase immobilization
is developed. 相似文献
83.
Acyclic nucleosides of 4‐nitro‐1H‐imidazole and 4‐nitropyrazole have been synthesized by nucleophilic addition of the appropriate 4‐nitroazole to (?)‐(S)‐(hydroxymethyl)oxirane in the presence of a catalytic amount of potassium carbonate. (+)‐(R)‐3‐(4‐nitro‐1H‐imidazol‐1‐yl)propane‐1,2‐diol and (+)‐(R)‐3‐(2‐methyl‐4‐nitro‐1H‐imidazol‐1‐yl)propane‐1,2‐diol were also obtained in an independent reaction starting from appropriate 1,4‐dinitro‐1H‐imidazole and (+)‐(R)‐3‐aminopropane‐1,2‐diol. (+)‐(R)‐3‐(4‐Nitropyrazol‐1‐yl)propane‐1,2‐diol was also obtained by direct noncatalyzed addition of 4‐nitropyrazole to (?)‐(S)‐(hydroxymethyl)oxirane, whereas the (S)‐enantiomer was obtained by reaction of 4‐nitropyrazole with (+)‐(S)‐1,2‐O‐isopropylideneglycerol under Mitsunobu reaction conditions, followed by a cleavage of the isopropylidene group with 80% AcOH. Racemization during any of these syntheses has not been observed. 3‐(4‐Nitroazol‐1‐yl)propane‐1,2‐diols were incorporated into a 26‐mer oligonucleotide. UV Thermal melting studies of duplexes of the oligonucleotides with 4‐nitropyrazole or 4‐nitro‐1H‐imidazole paired with four natural bases showed moderately decreased stabilities of the duplexes. A narrow range of melting temperatures, typically being within 2° for each acyclic nucleoside, fulfill one of the requirements of using acyclic 4‐nitroazoles as general bases. Single incorporation of 4‐nitroazoles into a 14‐mer triplex forming oligonucleotide resulted in considerably decreased triplex stabilities. 相似文献
84.
Krzysztof Matyjaszewski Przemysaw Kubisa Stanisaw Penczek 《Journal of polymer science. Part A, Polymer chemistry》1975,13(4):763-784
Polymerization of THF in CCl4 solvent was initiated with 1,3-dioxolan-2-ylium eations with AsF6?, PF6?, and SbF6? anions as well as with esters of fluorosulfonic and trifluoromethanesulfonic acids. With these esters polymerization proceeds with a marked acceleration period, due to slow initiation. The corresponding rate constants of initiation and their dependence on the polarity of the THF/CCl4 mixture were determined. The rate constant of propagation on the macroion-pairs (kp±) of the polytetrahydrofurylium cation with AsF6?, PF6?, and SbF6? and CF3SO3?, anions was found to be independent in CCl4 solvent on the anion structure and given by the expression: kp± = 2.93 × 10?2 exp {?4.7 × 103/T} at [THF]0 = 8.0M. This constant depends on the polarity of the polymerization mixture, and at 25°C for the THF-CCl4 system, kp± = 1.78 × 10?2 exp {?4.9/D}; thus, in CCl4 at [THF]0 = 8.0M, and at 25° kp± = 4.0 × 10?21/mole-sec. In the polymerization with derivatives of CF3SO3H (able to form the corresponding macroester) the overall polymerization rate is much lower than that with complex anions because of the reversible conversion of the macroion-pairs into the macroester (internal return). The macroester is much less reactive than the macroionpair (102–103 times) in the monomer addition reaction. At [THF]0 = 8.0M and at 25°C, 96.5% of the growing species exists in the macroester form. Polymerization of THF initiated with derivatives of CF3SO3H is a subject of a strong special salt-effect. At a sufficiently high ratio of [AgSbF6] to [I]0, where the initiator I is C2H5OSO2CF3, the overall polymerization rate is equal to that observed for the polymerization of THF on the macroion-pairs, since the internal return within the triflate ion-pair (the macroester formation) is eliminated and polymerization proceeds on the macroion-pairs with SbF6- anions exclusively. 相似文献
85.
Conducting polymer (CP) films, used as ion-sensing membranes under open circuit potentiometric conditions, are usually characterised with rather high detection limit, in the range of 10−4-10−5 mol dm−3. This effect is unfavourable, not only from the point of view of CP applications in potentiometry as ion sensitive membranes, but also when these materials are used as ion-to-electron transducers (solid contacts) for ion-selective electrodes. The theoretical considerations presented underline the crucial role of spontaneous processes of polymer charging/discharging—the source of observed high detection limit of sensors comprising CP layer under zero current conditions. Although the mechanism of occurring process is different from that observed for plastic, solvent polymeric based ion-selective electrodes, the ultimate result—alteration of activity of electrolyte at the membrane/solution interface leading to elevation of the detection limit—is the same.The method of estimation of parameters characterising spontaneous charge transfer processes is presented. The values obtained can be used to calculate the resulting polymer/solution interface activity of electrolyte ions, thus the detection limit of CP membrane can be theoretically predicted.A method of lowering of the detection limit of conducting polymer membranes, applying galvanostatic polarisation to compensate the spontaneous process of polymer charging/discharging, is presented.The experimental results obtained for poly(pyrrole), poly(N-methylpyrrole) and poly(3,4-ethylenedioxythiophene) are in good accordance with predictions of the presented model. 相似文献
86.
The first examples of manipulating stereocontrol solely by reaction topography in radical cyclizations starting from acyclic precursors are reported. The kinetic model for acyclic compound stereoselection is verified experimentally by conducting a series of radical cyclizations of 1,3-dihalo-2-(1-phenyl-3-butynyl)propanes with triphenyltin hydride and measuring the ratios of the products. Monohalide intermediates are observed for the first time, and evidence that bromide- and iodide-substituted radicals have different cyclization rate constants is provided. 相似文献
87.
Summary Analytical peak-shape equations were derived for first-order reversible reactions occurring in a chromatographic reactor by
treating the reversible reactions as consecutive reactions with alternating products. The results of the analytical peak-shape
equations were compared with those from a numerical solution of the partial differential equation system modeling the chromatographic
reactor. For small to medium conversions the correspondence was found to be sufficiently close to enable substitution of the
numerical solution in fitting procedures for the determination of rate constants.
Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996 相似文献
88.
Danuta Slawinska Janusz Slawinski Krzysztof Polewski Wojciech Pukacki 《Photochemistry and photobiology》1979,30(1):71-80
Abstract— Peroxidation of tannins with alkaline H2 O2 is accompanied by weak chemiluminescence in the spectral region 480–800 nm. o-Di and tri-hydroxy groups of polyphenols undergo oxidation by a free-radical mechanism and a green intermediate anion-radical with absorption Δmax = 600 nm is formed. The radical mechanism is supported by the low activation energy 14–20 kJ/mol and the quenching effect of radical scavengers. The reaction of the green intermediate with peroxy anions is the chemiluminescence rate limiting step. In the presence of a-hydroxy-methylperoxide formed from H2 O2 and formaldehyde, the alkaline peroxidation of tannins is accompanied by strong red luminescence (420–800 nm). The base catalyzed decomposition of peroxides gives only a weak red emission (460–800 nm). Light intensity is enhanced in D2 O by a factor 6.5. Quenchers of O2 (1 Δg ) and 1,3-di-phenylisobenzofurane diminish light intensity in non-aqueous solutions. The data suggest 1 O2 participation in the observed chemiluminescence. Thermo-chemical calculations give —ΔH values from 250–1000 kJ/mol for one elementary reaction step which limits the mechanism of chemi-enereization. Chemiexcitation of tannins is relevant to biochemical mechanisms of aerobic degradation of aromatic compounds, energy utilization as well as to defense and resistance processes in plants. 相似文献
89.
The role of different H-bonds in phases II, III, IV, and V of triammonium hydrogen disulfate, (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2), has been studied by X-ray diffraction and (1)H solid-state MAS NMR. The proper space group for phase II is C2/c, for phases III and IV is P2/n, and for phase V is P onemacr;. The structures of phases III and IV seem to be the same. The hydrogen atom participating in the O(-)-H(+).O(-) H-bond in phase II of (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2) at room temperature is split at two positions around the center of the crucial O(-)-H(+).O(-) H-bonding, joining two SO(4)(2)(-) tetrahedra. With decreasing temperature, it becomes localized at one of the oxygen atoms. Further cooling causes additional differentiation of possibly equivalent sulfate dimers. The NH(4)(+) ions participate mainly in bifurcated H-bonds with two oxygen atoms from sulfate anions. On cooling, the major contribution of the bifurcated H-bond becomes stronger, whereas the minor one becomes weaker. This is coupled with rotation of sulfate ions. In all the phases of (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2), some additional, weak but significant, reflections are observed. They are located between the layers of the reciprocal lattice, suggesting possible modulation of the host (NH(4)(+))(3)H(+)(SO(4)(2)(-))(2) structure(s). According to (1)H MAS NMR obtained for phases II and III, the nature of the acidic proton disorder is dynamic, and localization of the proton takes place in a broader range of temperatures, as can be expected from the X-ray diffraction data. 相似文献
90.
Maksymilian Chruszcz Krzysztof Lewinski 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(3):m150-m151
The structural data for sodium 2‐hydroxy‐5‐nitrobenzylsulfonate monohydrate, Na+·C7H6NO6S?·H2O, which mimics an artificial substrate for human arylsulfatase A, viz. p‐nitrocatechol sulfate, reveal that the geometric parameters of the substrate and its analogue are very similar. Two water molecules, the phenolic O atom and three sulfonate O atoms form the coordination sphere of the Na+ ion, which is a distorted octahedron. The Na+ cations and the O atoms join to form a chain polymer. 相似文献