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.     

Optimization of on-chip elongation for fabricating double-stranded DNA microarrays

The sequence-specific recognitions between DNA and proteins are playing important roles in many biological functions. The double-stranded DNA microarrays (dsDNA microarrays) can be used to study the sequence-specific recognitions between DNAs and proteins in highly parallel way. In this paper, two different elongation processes in forming dsDNA from the immobilized oligonucleotides have been compared in order to optimize the fabrication of dsDNA microarrays: (1) elongation from the hairpins formed by the self-hybridized oligonucleatides spotted on a glass; (2) elongation from the complementary primers hybridized on the spotted oligonucleatides. The results suggested that the dsDNA probes density produced by the hybridized-primer extension was about four times lower than those by the self-hybridized hairpins. Meanwhile, in order to reduce the cost of dsDNA microarrays, we have replaced the Klenow DNA polymerase with Taq DNA polymerase, and optimized the reaction conditions of on-chip elongation. Our experiements showed that the elongation temperature of 50 °C and the Mg²⁺ concentration of 2.5 mM are the optimized conditions in elongation with Taq DNA polymerase. A dsDNA microarray has been successfully constructed with the above method to detect NF-kB protein.     

Elongation method with intermediate mechanical and electrostatic embedding for geometry optimizations of polymers

The elongation method with intermediate mechanical and electrostatic embedding (ELG-IMEE) is proposed. The electrostatic embedding uses atomic charges generated by a charge sensitivity analysis (CSA) method and parameterized for three different population analyses, namely, the Merz–Singh–Kollman scheme, the charge model 5, and the atomic polar tensor. The obtained CSA models were tested on two model systems. Test calculations show that the electrostatic embedding provides several times of decrease in the difference of energies of testing and reference calculations in comparison with the conventional elongation approach (ELG). The mechanical embedding is implemented in a combination of the conventional elongation method and the ONIOM approach. Moreover, it was demonstrated that the geometry optimization with the ELG-IMEE reduces the errors in the optimized structures by about one order in root-mean-square deviation, when compared to ELG.     

Real-Time Detection of Polymerase Activity Using Supercritical Angle Fluorescence

We investigated the incorporation efficiencies of different fluorescently labelled dNTPs with polymerases by complementary strand synthesis. For this reason single stranded DNA was immobilized on a coverslip and the increase of fluorescence due to the synthesis of the corresponding strand with tagged dNTPs was detected with a supercritical angle fluorescence biosensor in real-time. By comparison of the observed signal intensities it was possible to conclude that the system Cy5-dCTP-Klenow (exonuclease free) fragment gives the best incorporation yield of the investigated enzymes and dNTPs.     

Rolling of a Rigid Cylinder over a Half-Plane with Initial Stresses (Harmonic and Bartenev–Khazanovich Potentials)

An asymmetric quasistationary problem for a prestressed half-plane with harmonic and Bartenev–Khazanovich potentials is solved based of the linearized theory of elasticity. The Mehler–Fock integral transform is used to solve the differential equations that describe the stress–strain state of the half-plane. The dependences of the normal and tangential stresses and stress intensity factors on the elongation are plotted     

Contact Stress Distribution Under a Rigid Cylinder Rolling Over a Prestressed Strip

A nonsymmetric quasistationary problem for a strip with initial stresses is solved under the linearized theory of elasticity for harmonic and Bartenev–Khazanovich potentials. The Hankel integral transform is used to solve the differential equations that describe the stress–strain state of the strip. The dependences of the normal and tangential stresses and stress intensity factors on the elongation are plotted     

A failure of a class of K-BKZ equations based on principal stretches

The invariants in the K-BKZ constitutive equation for an incompressible viscoelastic fluid are usually taken to be the trace of the Finger strain tensor and its inverse. The basis for this choice of invariants is not derived from the K-BKZ theory, but rather is due to the perception that this is the most natural choice. Research into using other sets of invariants in the K-BKZ equation, such as the principal stretches or the eigenvalues of the Finger strain tensor (i.e., the squares of the principal stretches) is relatively new. We attempt here to derive a K-BKZ equation based on the squares of the principal stretches that models the behavior of a low-density polyethylene melt in simple shear and uniaxial elongational deformation. In doing so, two assumptions are made as to the form of the strain-dependent energy function: first, that there is a function f(q) such that the energy function can be written as the sum of f(q _i ),i = 1, 2, 3, where the q _i 'sare the squares of the principal stretches, and second that f is a power law. We find that the K-BKZ equation resulting from these two assumptions is inadequate to describe both the shear and elongational behavior of our material and we conclude that the second of the above assumptions is not valid. Further investigation, including predictions of the second normal stress difference and some finite element calculations reveals that the first assumption is also invalid for our material.     

聚醚环酰胺固体推进剂用键合剂的合成及使用性能

以丙三醇、环氧乙烷、环氧丙烷、氯化亚砜、异氰脲酸等为原料,合成了聚醚环酰胺键合剂。将其应用到推进剂(GAP/HMX/Al/AP)配方中,对成型后的推进剂进行力学性能测试和断面电子显微镜分析。结果表明,此类键合剂可以改善与推进剂中氧化剂的界面粘结性能,有效地提高成型后的推进剂在不同温度下的最大延伸率,但对抗拉伸强度的提高作用不明显。     

Rheological studies on the phase separation of hydroxypropylcellulose solution systems

Phase behavior of hydroxypropylcellulose (HPC) in a mixed solvent of glycerol and water was investigated by two different rheological methods: rheooptical birefringence measurement in an elongational flow field and viscometric measurement in a shear flow field. The association process of the HPC chain during phase separation observed by the elongational flow birefringence method was also investigated by the shear viscometric method. The temperature dependence of chain rigidity was determined by measuring the intrinsic viscosity, and change in the conformation was investigated by observing elongational flow birefringence over the temperature range from the one‐phase to inside a phase boundary. The results focus on the molecular process of phase separation. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1976–1986, 2001