Chemical modification of L-asparaginase with N, O-carboxymethyl chitosan and its effects on plasma half-life and other properties

E.coli L-asparaginase,an antitumor enzyme,was chemically modified with N,O-carboxymethyl chitosan to lower its artigenicity and increase its plasma half-life.The results showed that the modified L-asparaginase has almost the same apparent Km value as that of native enzyme.The modified L-asparaginase also showed a higher protease stability against trypsin and a-chymotrypsin.After being modified,the enzyme exhibited the complete loss of antigenicity towards antiasparaginase serum.In addition,the higher the molecular weight of modifying reagents,the better the effects on reduction of antigenicity.When tested in vivo,the plasma half-life of the modified enzyme (t1/2=40 h) was over 33 times longer than that of the native enzyme (t1/2=1.2 h).     

A new method for determination of uric acid by the lactic acid-acetone-BrO(3)(-)-Mn(2+)-H(2)SO(4) oscillating reaction using the analyte pulse perturbation technique

A new analytical method for the determination of uric acid (UA) by the perturbation of UA on the Belousov-Zhabotinsky oscillating reaction is proposed. The method is based on the linear relationship between the changes in the oscillating period and the concentration of UA. The calibration curve is linear over the range of 2.0 × 10⁻⁵ to 5.0 × 10⁻⁴ M, with a detecting limit of 3.28 × 10⁻⁶ M. The method features good precision (R.S.D.: 3.59%) and excellent throughput (10 samples h⁻¹). The possible mechanism of the perturbation of UA on the oscillating reaction is discussed.     

基团的电子效应与单取代苯对位^1H,^13C的化学位移

基团的电子效应与单取代苯对位１Ｈ、１３Ｃ的化学位移＊韩长日冯娇杨钟照平（海南师范学院化学系海口５７１１５８）关键词１Ｈ的化学位移１３Ｃ的化学位移基团电负性共轭效应引言在１Ｈ、１３Ｃ核磁共振谱中，化学位移值的大小主要取决于屏蔽作用的大小，而屏蔽作用的大...     

Parameterization of peptide 13C carbonyl chemical shielding anisotropy in molecular dynamics simulations.

NMR chemical shielding anisotropy (CSA) relaxation is an important tool in the study of dynamical processes in proteins and nucleic acids in solution. Herein, we investigate how dynamical variations in local geometry affect the chemical shielding anisotropy relaxation of the carbonyl carbon nucleus, using the following protocol: 1) Using density functional theory, the carbonyl (13)C' CSA is computed for 103 conformations of the model peptide group N-methylacetamide (NMA). 2) The variations in computed (13)C' CSA parameters are fitted against quadratic hypersurfaces containing cross terms between the variables. 3) The predictive quality of the CSA hypersurfaces is validated by comparing the predicted and de novo calculated (13)C' CSAs for 20 molecular dynamics snapshots. 4) The CSA fluctuations and their autocorrelation and cross correlation functions due to bond-length and bond-angle distortions are predicted for a chemistry Harvard molecular mechanics (CHARMM) molecular dynamics trajectory of Ca(2+)-saturated calmodulin and GB3 from the hypersurfaces, as well as for a molecular dynamics (MD) simulation of an NMA trimer using a quantum mechanically correct forcefield. We find that the fluctuations can be represented by a 0.93 scaling factor of the CSA tensor for both R(1) and R(2) relaxations for residues in helix, coil, and sheet alike. This result is important, as it establishes that (13)C' relaxation is a valid tool for measurement of interesting dynamical events in proteins.     

XPS and XAES analysis of copper,arsenic and sulfur chemical state in enargites

Enargite, a copper arsenic sulfide with the formula Cu₃AsS₄ is of environmental concern due to its potential to release toxic arsenic species. The oxidation and dissolution of enargite are governed by the composition and chemical state of the outermost surface layer. Qualitative and quantitative analysis of the enargite surface can be initially obtained on the basis of X‐ray photoelectron spectroscopy (XPS) binding energy and intensity data. However, a more precise determination of the chemical state of the principal elements of enargite (copper, arsenic and sulfur) in the altered surface layer and in the bulk of the mineral requires a combined analysis based on XPS photoelectron lines and the corresponding X‐ray excited Auger lines. On the basis of results obtained on natural and synthetic enargite samples and on standards of sulfides and oxides, the Auger parameter α′ of different compounds was calculated and the Wagner chemical state plots were drawn for arsenic, copper and sulfur. Arsenic in enargite is found to be in a chemical environment similar to that of arsenides or elemental arsenic, whereas copper in enargite is in a chemical state that corresponds to copper sulfide, Cu₂S, for all samples irrespective of surface treatment (natural or freshly cleaved). Only sulfur changed from a chemical state similar to that of copper or iron sulfide in freshly cleaved samples to another state in natural enargite in the as‐received state. Thus, it is the sulfur atom at the surface of enargite that is most susceptible to changes in the enargite surface state and composition. A more detailed interpretation of this behavior, based on differences in the initial and final state effects, is proposed here. The concept of Auger parameter and chemical state plot, used here for the first time for investigating enargite, has proved to be a method to unambiguously assign the chemical state of the principal elements copper, arsenic and sulfur in these minerals. Copyright © 2006 John Wiley & Sons, Ltd.     

纳米TiO2膜用于光催化氧化测定化学需氧量的研究

A photocatalytic oxidation method for determination of chemical oxygen demand （COD） using nano-TiO2 film, based on the use of a nano-TiO2-Ce（SO4）2 system and electrochemical detection, was proposed. The technique was originated from the direct determination of the Ce（Ⅲ） concentration change resulting from photocatalytic oxidation of organic compounds. Ce（Ⅲ）, which was produced by photocatalytic reduction of Ce（SO4）2, could be measured at a multi-walled carbon nanotubes （MWNT） chemically modified electrode （CME）. The COD values by this method were calculated from the differential pulse voltammetry （DPV） current of Ce（Ⅲ） at the CME. Under the optimal operation conditions, the detection limit of 0.5 mg·L^-1 COD with the linear range of 1-600 mg·L^-1 was achieved. This method was also applied to determination of various COD of ground water and wastewater samples. The resuits were in good agreement with those from the conventional COD methods, i.e., permanganate and dichromate ones.     

Chemischer Transport von Cr2O3 mit CrI3/I2 – Experimente und Modellrechnungen zur Beteiligung von CrOI2,g

On the Chemical Transport of Cr₂O₃ with CrI₃/I₂ – Experiments and Model-Calculations for Participation of CrOI_2,g Gaseous chromium oxyiodides that were unknown up to now cause the migration of Cr₂O₃ in the temperature gradient 1 000°C→900°C when iodine (e. g. 0.1 mmol/ml) and CrI₃ is added (eq. (1)). Transport agent for Cr₂O₃ is gaseous CrI₄. With a smaller concentration of iodine (D(I₂) ? 0.016 mmol/ml) and lower temperatures (e.g. T? = 850°C) the influence of H₂O (from the wall of the silica ampoule) becomes more important. Under these conditions the transport of Cr₂O₃ is a result from the endothermic reactions (2), (3) and (4). H_2,g has on the basis of the decomposition of HI_g a positive difference of the solubility and H_2,g should not to be considered as a transport agent. Because of the range of equilibrium-values the reaction 4 has to be taken into consideration. Estimated value of the enthalpie for CrOI_2,g is fixed more precisely by thermodynamic model calculation to Δ_fH°₂₉₈(CrOI_2,g) = ?51.4 kcal/mol. The estimated limit of error for the enthalpie of formation is smaller than ± 5 kcal/mol. Without an addition of CrI₃ is in the system Cr₂O₃/I₂ a migration of Cr₂O₃ not observable.     

Perfluoropoly-ether/peroxide compounds: spectroscopic studies and quantum chemical calculations

Perfluoropolyethers (PFPEs) are a class of high performance materials used in a wide range of applications (refrigeration, lubrication, semiconductor industry, etc.). PFPEs containing peroxidic units are intermediate materials for the preparation of commercial end products. In this work we study the spectroscopic properties of ether and peroxides linkages in this class of compounds; nuclear magnetic resonance (NMR) spectra are discussed, FT-Raman data presented. Quantum chemical calculations on model molecules were used as a tool for the interpretation of the Raman experimental data and physical-chemical properties.     

Capillary electrophoretic determination of lignin degradation products obtained by permanganate oxidation

A new capillary electrophoretic (CE) technique was developed for the separation of lignin degradation products after permanganate oxidation, yielding information about quality and quantity of various linkages in the lignin molecule. This CE method is a promising alternative to existing gas chromatographic (GC) methods. An advantage in comparison with GC is the short separation time and the fact that the oxidation products (aromatic acids) can be analyzed without derivatization. The selectivity and sensitivity of CE combined with UV detection is adequate and makes it suited for fast routine characterization of lignins. If necessary, the CE method can be coupled with electrospray ionization mass spectrometry in order to make a clear assignment of the peaks.     

Reduced parabolic model for radical addition reactions

The transition state of addition of free radicals and atoms to multiple bonds is considered as a result of intersecting of two parabolic potential curves. One of them characterizes the stretching vibration of the attacked multiple bond, and another curve characterizes the stretching vibration of the bond formed in the transition state. The force constant of the latter is calculated by an empirical equation that correlates the force constant with the bond dissociation energy. In the framework of this model, the thermally neutral activation energy (E _e0) and the elongation of the attacked and formed bonds (r _e) in the transition state were calculated from the experimental data (activation energy (E _e) and enthalpy of reaction (H _e)) for the addition of an H atom and methyl, alkoxyl, aminyl, triethylsilyl, and peroxyl radicals to the C=C bond and the addition of H and CH₃ to the C=O and CC bonds. Analysis of the data obtained showed that E _e0 depends linearly on the |H _e| + E_e sum, i.e., E_e0/kJ mol^–1 = 14.2 + 0.61 · (E_e – H _e), and the bond elongation in the transition state for addition of the most part of radicals to ethylene and acetylene vary within (0.65–0.87)·10_–10 m. The factors affecting the activation energy of the radical addition reactions are discussed.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1542–August, 2004.