Well-defined higher-molecular-weight polyacrylonitrile via RAFT technique in the presence of disulfide compounds as a source of chain transfer agent

Well-defined polyacrylonitrile with a higher number-average molecular weight (R.) up to 200,000 and a lower polydispersity index (PDI, 1.7-2.0) was firstly obtained via reversible addition-fragmentation chain transfer (RAFT) process. This was achieved by selecting a stable, easy way to prepare disulfide compound intermediates including bis(thiobenzoyl) disulfide (BTBDS) and bis(thiophenylacetoyl) disulfide (BTPADS) to react with azobis(isobutyronitrile) to directly synthesize RAFT agents in situ.

Simulation of Banded Spherulite Patterns by Coupled Logistic Map Lattice Model in Three Dimensions

Banded spherulite patterns are simulated in three dimensions by means of a Coupled Logistic map lattice model. The patterns obtained by numerical calculation are consistent with those in experiments. The simulation results also indicate that the hand spacing is decreased with the increase of parameter mu in the Logistic map and increased with the increase of the coupling parameter e for cube lattices, and increased with the increase of the thickness of the lattice for polymer film, which is quite similar to the results in some experiments. Spiral pattern in three dimensions is also shown in this paper, which helps us understand the form of banded spherulite in polymers.

Bimolecular quadruplexes and their transitions to higher-order molecular structures detected by ESI-FTICR-MS

Four individual quadruplexes, which are self-assembled in ammonium acetate solution from telomeric sequences of closely related DNA strands - d(G(4)T(4)G(4)), d(G(3)T(4)G(4)), d(G(3)T(4)G(3)), and d(G(4)T(4)G(3)) - have been detected in the gas phase using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). The bimolecular quadruplexes associate with the same number of NH4+ in the gas phase as NMR shows that they do in solution. The quadruplex structures formed in solution are maintained in the gas phase. Furthermore, the mass spectra show that the bimolecular quadruplexes generated by the strands d(G(3)T(4)G(3)) and d(G(4)T(4)G(3)) are unstable, being converted into trimolecular and tetramolecular structures with increasing concentrations of NH4+ in the solution. Circular dichroism (CD) spectra reveal structural changes during the process of strand stoichiometric transitions, in which the relative orientation of strands in the quadruplexes changes from an antiparallel to a parallel arrangement. Such changes were observed for the strand d(G(4)T(4)G(3)), but not for the strand d(G(3)T(4)G(3)). The present work provides a significant insight into the formation of various DNA quadruplexes, especially the higher-order species.

2-cyanoprop-2-yl dithiobenzoate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight

The reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2-cyanoprop-2-yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANS were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. H-1 NMR analysis confirmed the high chain-end functionality of the resultant polymers.

Monte Carlo simulation of the grafting of maleic anhydride onto polypropylene at higher temperature

The graft of maleic anhydride (MAH) onto isotactic polypropylene (iPP) initiated by dicumyl peroxide (DCP) at 190 degreesC was studied by means of the Monte Carlo method. The ceiling temperature theory, i.e., no possibility for the homopolymerization of MA-H to occur at higher temperatures, was used in this study. The simulation results show that most MAH monomers were grafted onto the radical chain ends arising from beta scission at a lower MAH concentration, whereas the amount of MAH monomers attached to the tertiary carbons was much larger than that grafted onto the radical chain ends at a higher MAH concentration for various DCP concentrations. This conclusion gives a good interpretation for the disagreement on the grafting sites along a PP chain. Moreover, it was found that the grafting degree increased considerably up to a peak value; thereafter, it decreased continuously with increasing MA-H concentration. The peak shifted in the lower MAH concentration direction and became lower and lower with increasing DCP concentration. When the DCP concentration was below 0.1 wt %, the peak was hardly observed. Those results are in good agreement with the experiments.

Morphologies of metallocene-catalyzed short chain branched polyethylene single crystals formed from the melt at higher temperature

Metallocene-catalyzed short chain branched polyethylene single crystals, formed from the melt at a higher crystallization temperature of 114 degreesC, were obtained. Highly elongated lamellae were formed, which are different from truncated lozenge or lenticular shaped single crystals formed at a lower crystallization temperature. It was found that there existed a definite line in the lamellae along the longitudinal growth direction and two regions were separated by the definite line. The lateral habits of both the regions were asymmetrical about the b-axis due to the chain tilting, which was the same as that at a lower crystallization temperature. Generally, the highly elongated lamellae were not straight, but curved towards the opposite direction with chain tilting direction due to a series of edge dislocation within a lamella. The inner side of a lamella was serrated and the outer side was smooth due to the lamellar curvature. The thickness of both regions of a lamella was different, the broader region was thicker than the narrower region, which was different from the uniform thickness of the lamellae formed at a lower crystallization temperature. The different thicknesses within a lamella were considered as the result of the initial thickness difference and the impact of isothermal thickening. (C) 2001 Elsevier Science Ltd. All rights reserved.

Controlling factors for the occurrence of heteroepitaxy of polyethylene on highly oriented isotactic polypropylene

The controlling factors for the epitaxial crystallization of high-density polyethylene (HDPE) on highly oriented isotactic polypropylene (iPP) substrates have been studied in detail by means of transmission electron microscopy and electron diffraction. The results obtained in this work indicate that the crystallization process must be considered in the investigation of epitaxial growth of polymers on polymeric substrates, because of the unique morphological and crystallization characteristics of polymers. Crystallization rate has an important effect on the epitaxial crystallization of polymers. Higher rates result in the formation of thicker epitaxial layers. Isothermal crystallization temperature is another factor affecting epitaxial growth of polymers. Lower temperatures are favorable to epitaxial crystallization of polymers. There exists a critical epitaxial temperature at given experimental conditions, above which no epitaxial growth occurs at all. The influence of crystal dimensions of both the substrates and the deposited polymers on epitaxial growth confirms that secondary nucleation is an important controlling factor for the occurrence of epitaxial crystallization in polymers. The requirement satisfying the secondary nucleation criterion is that the substrate crystal dimension in the matching direction must be greater than the crystal thickness of the deposited polymer. Once the requirement of the secondary nucleation is satisfied, subsequent epitaxial growth is based on the lamellar growth habit of the deposited polymer itself. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

Higher-order Boussinesq-type equations for interfacial waves in a two-fluid system

Interfacial waves propagating along the interface between a three-dimensional two-fluid system with a rigid upper boundary and an uneven bottom are considered. There is a light fluid layer overlying a heavier one in the system, and a small density difference exists between the two layers. A set of higher-order Boussinesq-type equations in terms of the depth-averaged velocities accounting for stronger nonlinearity are derived. When the small parameter measuring frequency dispersion keeping up to lower-order and full nonlinearity are considered, the equations include the Choi and Camassa's results (1999). The enhanced equations in terms of the depth-averaged velocities are obtained by applying the enhancement technique introduced by Madsen et al. (1991) and Schaffer and Madsen (1995a). It is noted that the equations derived from the present study include, as special cases, those obtained by Madsen and Schaffer (1998). By comparison with the dispersion relation of the linear Stokes waves, we found that the dispersion relation is more improved than Choi and Camassa's (1999) results, and the applicable scope of water depth is deeper.

Higher order response of nonlinear composite in external AC electric field

The fifth-order effective nonlinear responses at fundament frequency and higher-order harmonics are given for nonlinear composites, which obey a current-field relation of the form J = sigmaE + x\E\(2) E, if a sinusoidal alternating current (AC) external field with finite frequency omega is applied. As two examples, we have investigated the cylinder and spherical inclusion embedded in a host and, for larger volume fraction, also derived the formulae of effective nonlinear responses at higher-order harmonics by the aid of the general effective response definition. Furthermore, the relationships between effective nonlinear responses at harmonics are given. (C) 2003 Elsevier Science B.V. All rights reserved.

各向异性与非线性介质中弹性波场传播特征研究

The topic of this study is about the propagation features of elastic waves in the anisotropic and nonlinear media by numerical methods with high accuracy and stability. The main achievements of this paper are as followings: Firstly, basing on the third order elastic energy formula, principle of energy conservation and circumvolved matrix method, we firstly reported the equations of non-linear elastic waves with two dimensions and three components in VTI media. Secondly, several conclusions about some numerical methods have been obtained in this paper. Namely, the minimum suitable sample stepth in space is about 1/8-1/12 of the main wavelength in order to distinctly reduce the numerical dispersion resulted from the numerical mehtod, at the same time, the higher order conventional finite difference (CFD) schemes will give little contribution to avoid the numerical solutions error accumulating with time. To get the similar accuracy with the fourth order center finite difference method, the half truncation length of SFFT should be no less than 7. The FDFCT method can present with the numerical solutions without obvious dispersion when the paprameters of FCT is suitable (we think they should be in the scope from 0.0001 to 0.07). Fortunately, the NADM method not only can reported us with the higher order accuracy solutions (higher than that of the fourth order finite difference method and lower than that of the sixth order finite difference method), but also can distinctly reduce the numerical dispersion. Thirdly, basing on the numerial and theoretical analysis, we reported such nonlinear response accumulating with time as waveform aberration, harmonic generation and resonant peak shift shown by the propagation of one- and two-dimensional non-linear elasticwaves in this paper. And then, we drew the conclusion that these nonlinear responses are controlled by the product between nonlinear strength (SN) and the amplitude of the source. At last, the modified FDFCT numerical method presented by this paper is used to model the two-dimensional non-linear elastic waves propagating in VTI media. Subsequently, the wavelet analysis and polarization are adopted to investigate and understand the numerical results. And then, we found the following principles (attention: the nonlinear strength presented by this paper is weak, the thickness of the -nonlinear media is thin (200m), the initial energy of the source is weak and the anisotropy of the media is weak too): The non-linear response shown by the elastic waves in VTI media is anisotropic too; The instantaneous main frequency sections of seismic records resulted from the media with a non-linear layer have about 1/4 to 1/2 changes of the initial main frequency of source with that resulted from the media without non-linear layer; The responses shown by the elasic waves about the anisotropy and nonlinearity have obvious mutual reformation, namely, the non-linear response will be stronger in some directions because of the anisotropy and the anisotropic strength shown by the elastic waves will be stronger when the media is nonlinear.

艺术学生的感觉寻求人格比较研究

High sensation seekers have unusual creativities. Recent years Furnham Adrian et al, found that the groups have different arts tendency have higher difference in Sensation seeking dimension than in Big 5. Some studies found arts students have higher level in many dimension. Sensation seeking has an important influence to peoples` aesthetic conception. This thesis measured art (including painting, music, dancing) students and non-art students` trait of sensation seeking Personality, and looked for the similarities and differences between art students and non-art students in development of sensation seeking personality. Try to find the influence of different procession of art study to sensation seeking level. The outcome of this study: 1. In non-art students, sensation seeking level has a decrease from Grade 1 to Grade 3 in college students, especially in males. Male has higher sensation seeking level than female, especially in TAS, DIS and GEN. 2. There are differences between art students and non-art students in sensation seeking. In ES and GEN Painting students have higher level than non-art students, but in TAS dancing students have lower level than non-art students, in BS students studied in music have lower level than non-art students. 3. Tendency of arts development in art students and non-art students has difference from grade 1 to grade 3. Tendency in non-art students has a decrease, but in art students is not so obviously. The developments in TAS、ES、GEN of painting students, in ES、BS、GEN of dancing students, in TAS、ES、GEN of music major students have differences towards to non-art students. Different art studies have possibility to improve opening of experiment and normal sensation seeking level. All the Different art kinds may affect the development of ES and GEN, and ES and GEN may become commonness gradually within all kind art groups. But this commonness is not so notable in Grade 1-3. 4. Between different art kinds have differences. TAS Scores of dancing group is notably lower than scores of music and painting groups, score of painting group in ES BS and GEN is remarkably higher than that of music and dancing groups, and painting group in DIS has a higher score than music group and dancing group. Painting group has highest sensation seeking in all art kinds students, and dancing group has lowest score in TAS. 5. For female, development tendency of all art kinds dimensions have no remarkable difference, except DIS. Interaction in female DIS dimension may be aroused by scores increase of painting group. In other scores development tendency of different kinds arts have no notable difference.