Dark cure studies of cationic photopolymerizations of epoxides: Characterization of kinetic rate constants at high conversions

The effective propagation rate constant (k_p; averaged over all the propagating active centers) was characterized for solvent‐free cationic photopolymerizations of phenyl glycidyl ether over the entire range of conversions, including the high conversion regime in which mass transfer limitations become important. The profile for the k_p as a function of conversion was found to exhibit a constant plateau value at low to intermediate conversions, followed by a monotonic increase above a threshold value of conversion. To explain this trend, it is proposed that at high conversion the diffusional mobility of the photoinitiator counterion is reduced whereas the mobility of the cationic active center remains high because of reactive diffusion. Therefore, with increasing conversion, the average distance between the active centers and counterions may increase, resulting in an increase in the propagation rate constant. The profiles for the k_p values were investigated as a function of the temperature, photoinitiator anion, and photoinitiator concentration. As the photoinitiator concentration was increased, the plateau value of the effective propagation rate constant decreased whereas the threshold conversion increased. All of the experimental trends are consistent with the proposed increase in ion separation at high conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4409–4416, 2004     

下一代SONET/SDH对网络部署的冲击

面对电信业的低迷,运营商和设备制造商都捏紧了钱袋,想方设法少花钱多办事。这就意味着,必须改进现有传输网(见图1),使话音和数据传输效率更高。从网络部署的角度来看,运营商需要:用一些有效的方法,将多协议数据转换到SONET/SDH信道上;用一种灵活的带宽适应机制,使SONET/SDH信道大小与在其中传输的数据的需求相一致;用一种机制,灵活并以理想的动态方式改变整个SONET/SDH网络的信道带宽。这就要求集成电路供应商提供有助于在SONET/SDH上有效传输数据的芯片。虽然现在有多种SONET/SDH信息包(PoS)产品,但是它们的转换效率都太…     

Perceptual image hashing via feature points: performance evaluation and tradeoffs.

We propose an image hashing paradigm using visually significant feature points. The feature points should be largely invariant under perceptually insignificant distortions. To satisfy this, we propose an iterative feature detector to extract significant geometry preserving feature points. We apply probabilistic quantization on the derived features to introduce randomness, which, in turn, reduces vulnerability to adversarial attacks. The proposed hash algorithm withstands standard benchmark (e.g., Stirmark) attacks, including compression, geometric distortions of scaling and small-angle rotation, and common signal-processing operations. Content changing (malicious) manipulations of image data are also accurately detected. Detailed statistical analysis in the form of receiver operating characteristic (ROC) curves is presented and reveals the success of the proposed scheme in achieving perceptual robustness while avoiding misclassification.     

Molecular dynamics simulation of titanium dioxide nanoparticle sintering

Nanoparticles have been an area of active research in recent years due to their properties, which can be greatly different from the bulk. In this work, we study the sintering of TiO2 nanoparticles using molecular dynamics simulations. Such sintering occurs in flame reactors where nanotitania is prepared via the chloride process. Decrease in free energy due to reduction in surface area is the main driving force for sintering of particles. Simulations, at various starting temperatures and orientations, indicate that the process of sintering is strongly affected by temperature and initial orientation. Extremely high diffusion of ions in the neck region of sintering nanoparticles supports the idea that solid-state diffusion is significant in metal-oxide nanoparticle sintering. It is found that the dipole-dipole interaction between sintering nanoparticles plays a very important role at temperatures away from the melting point. The duration of the simulation is not enough to observe the complete sintering process, but important initial stages are well studied.     

A novel bit permutation-based image encryption algorithm

Nonlinear Dynamics - In recent years, substantial work has been done for developing image encryption algorithms. Image encryption requires handling of large data, which needs computationally...     

Fusion of multi-exposure images using recursive and Gaussian filter

Multidimensional Systems and Signal Processing - This paper proposes a novel technique to create a high-resolution image by combining the bracketed exposure sequence without a priori...     

DNA polymerase template interactions probed by degenerate isosteric nucleobase analogs

The development of novel artificial nucleobases and detailed X-ray crystal structures for primer/template/DNA polymerase complexes provide opportunities to assess DNA-protein interactions that dictate specificity. Recent results have shown that base pair shape recognition in the context of DNA polymerase must be considered a significant component. The isosteric azole carboxamide nucleobases (compounds 1-5; ) differ only in the number and placement of nitrogen atoms within a common shape and therefore present unique electronic distributions that are shown to dictate the selectivity of template-directed nucleotide incorporation by DNA polymerases. The results demonstrate how nucleoside triphosphate substrate selection by DNA polymerase is a complex phenomenon involving electrostatic interactions in addition to hydrogen bonding and shape recognition. These azole nucleobase analogs offer unique molecular tools for probing nonbonded interactions dictating substrate selection and fidelity of DNA polymerases.     

Photocatalysed eosin Y mediated C(sp3)-H alkylation of amine substrates via direct HAT

A visible light promoted, photoredox catalysed, green one-pot approach for the alkylation of amine substrates with sp² carbon has been developed. This eosin Y based organic transformations, can behave as an effective direct hydrogen-atom transfer catalyst for coupling reaction. The proposed strategy includes simple procedure which can make adduct product with sp² carbon. This eosin Y based photocatalytic hydrogen-atom transfer strategy may hold great potential for diverse functionalization of a wide range of native CH bonds in an economical and sustainable manner.     

Characterization of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][Tf2N])∕TX-100∕cyclohexane ternary microemulsion: investigation of photoinduced electron transfer in this RTIL containing microemulsion

In this study we have characterized a ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethyl- sulfonyl)imide containing ternary nonaqueous microemulsion ([Emim][Tf(2)N]∕∕TX-100∕cyclo- hexane). The phase behavior and dynamic light scattering study show that the [Emim][Tf(2)N]∕TX-100∕cyclohexane three component system can form microemulsion with [Emim][Tf(2)N] as polar core at suitable condition. We have investigated photoinduced electron transfer (PET) using dimethyl aniline as electron donor and several Coumarin dyes as electron acceptor molecules at two different R values (R = [ionic liquid]∕[surfactant]) to observe how the dynamics of the PET rate is affected in this type of confined microenvironment compared to that of the PET dynamics in neat ionic liquid and other pure solvent media. The plot of observed k(q) values with the free energy change (ΔG(0)) for electron transfer reaction shows an apparent inversion in the observed rate as predicted by the Marcus theory.