Origin of the activation barrier in the process of hydrogen abstraction: the perturbation treatment

The perturbation treatment previously given is extended to explain the process of hydrogen abstraction from the various hydrogen donor molecules by the triplet nπ* state of ketones or the ground state of the alkyl or alkoxy radical. The results suggest that, as the ionization energy of the donor bonds is decreased, the reaction is accelerated and it is not influenced by the bond strength of the donor bonds. The activation barrier in such reactions arises from a weakening of the charge resonance term as the ionization energy of the donor bond increases.

Origin of the activation barrier in the process of hydrogen abstraction: the perturbation treatment

The perturbation treatment previously given is extended to explain the process of hydrogen abstraction from the various hydrogen donor molecules by the triplet nπ* state of ketones or the ground state of the alkyl or alkoxy radical. The results suggest that, as the ionization energy of the donor bonds is decreased, the reaction is accelerated and it is not influenced by the bond strength of the donor bonds. The activation barrier in such reactions arises from a weakening of the charge resonance term as the ionization energy of the donor bond increases.

The perturbational treatment of the process of hydrogen abstraction by ketones

The change in energy during hydrogen abstraction by ketones is estimated for different electronic states as a function of the intermolecular orbital overlap employing perturbation theory. The results suggest that ketones preferentially undergo the in-plane reaction and abstract a hydrogen atom in their triplet nπ* state. For ketones where the triplet ππ* state lies below the triplet nπ* state, hydrogen abstraction can take place in the ππ* state owing to the crossing of the zero order reaction surfaces of the nπ* and ππ* states.

Understanding the folding process of synthetic polymers by small-molecule folding agents

Two acceptor containing polyimides PDI and NDI carrying pyromellitic diimide units and 1,4,5,8-naphthalene tetracarboxy diimide units, respectively, along with hexa(oxyethylene) (EO6) segments as linkers, were prepared from the corresponding dianhydrides and diamines. These polyimides were made to fold by interaction with specifically designed folding agents containing a dialkoxynaphtha-lene (DAN) donor linked to a carboxylic acid group. The alkali-metal counter-ion of the donor carboxylic acid upon complexation with the EO6 segment brings the DAN unit in the right location to induce a charge-transfer complex formation with acceptor units in the polymer backbone. This two-point interaction between the folding agent and the polymer backbone leads to a folding of the polymer chain, which was readily monitored by NMR titrations. The effect of various parameters, such as structures of the folding agent and polymer, and the solvent composition, on the folding propensities of the polymer was studied.

The process of technological innovations in small enterprises: the Indian way

This paper probes how two small foundries in Belgaum, Karnataka State, India, have achieved technological innovations successfully based on their technological capability and customer needs, enabling them to sail through the competitive environment. This study brought out that technically qualified entrepreneurs of both the foundries have carried out technological innovations, mainly due to their self-motivation and self-efforts. Changing product designs, as desired or directed by the customers, cost reduction, quality improvement and import substitution through reverse engineering are the characteristics of these technological innovations. These incremental innovations have enabled the entrepreneurs of the two foundries to enhance competitiveness, grow in the domestic market and penetrate the international market and grow in size over time.

The process of technological innovations in small enterprises: the Indian way

This paper probes how two small foundries in Belgaum, Karnataka State, India, have achieved technological innovations successfully based on their technological capability and customer needs, enabling them to sail through the competitive environment. This study brought out that technically qualified entrepreneurs of both the foundries have carried out technological innovations, mainly due to their self-motivation and self-efforts. Changing product designs, as desired or directed by the customers, cost reduction, quality improvement and import substitution through reverse engineering are the characteristics of these technological innovations. These incremental innovations have enabled the entrepreneurs of the two foundries to enhance competitiveness, grow in the domestic market and penetrate the international market and grow in size over time.

Evidence for supramolecular organization of alkane and surfactant molecules in the process of forming mesoporous silica

Investigations of the pore expansion in mesoporous silica in the presence of n-alkanes suggest a cooperative organization of the surfactant and alkane molecules, involving additivity of chain lengths.

Understanding the building-up process of three dimensional open-framework metal phosphates: Acid degradation of the 3D structures to lower dimensional structures

Acid degradation of 3D zinc phosphates primarily yields a one-dimensional ladder compound, an observation that is significant considering that the latter forms 3D structures on heating in water.

An Empirical Model of the Process of Synthesis of Multiple State Mechanical Devices

Automated synthesis of mechanical designs is an important step towards the development of an intelligent CAD system. Research into methods for supporting conceptual design using automated synthesis has attracted much attention in the past decades. The research work presented here is based on the processes of synthesizing multiple state mechanical devices carried out individually by ten engineering designers. The designers are asked to think aloud, while carrying out the synthesis. The ten design synthesis processes are video recorded, and the records are transcribed and coded for identifying activities occurring in the synthesis processes, as well as for identifying the inputs to and outputs from the activities. A mathematical representation for specifying multi-state design task is proposed. Further, a descriptive model capturing all the ten synthesis processes is developed and presented in this paper. This will be used to identify the outstanding issues to be resolved before a system for supporting design synthesis of multiple state mechanical devices that is capable of creating a comprehensive variety of solution alternatives could be developed.

Simulation of Influence of Bilayer Melting on Dynamics and Thermodynamics of Interfacial Water

We investigate the effect of bilayer melting transition on thermodynamics and dynamics of interfacial water using molecular dynamics simulation with the two-phase thermodynamic model. We show that the diffusivity of interface water depicts a dynamic crossover at the chain melting transition following an Arrhenius behavior until the transition temperature. The corresponding change in the diffusion coefficient from the bulk to the interface water is comparable with experimental observations found recently for water near 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) vesicles Phys. Chem. Chem. Phys. 13, 7732 (2011)]. The entropy and potential energy of interfacial water show distinct changes at the bilayer melting transition, indicating a strong correlation in the thermodynamic state of water and the accompanying first-order phase transition of the bilayer membrane. DOI: 10.1103/PhysRevLett.110.018303

New Ventures’ influence on the Growth of SME Employment, Production and Exports in India: Does Institutional Credit matter?

New ventures are considered to be a major source of small firm growth. In Indian context the contribution of new ventures in terms of new employment, production and exports has largely remained unexplored. It is equally important and unexplored, the significance of the contribution of bank credit to the growth of new ventures in India. This paper is an attempt to throw light on these two aspects. The research is based on secondary data of the liberalized period provided by Ministry of Micro, Small and Medium Enterprises, Government of India and Reserve Bank of India. To analyze the influence of bank credit growth on new ventures and the influence of new ventures on growth of additional employment, additional production and additional exports, we used a Bi-Variate Vector Auto Regression. Based on the model generated, Granger causality tests are conducted to obtain the results. The study found that rate of growth of bank credit causes the number of new ventures, implying any increase in the rate of growth of bank credit will be beneficial to the growth of new ventures. The study also concluded that new ventures are not causing the growth of additional employment or additional production. However new ventures cause the growth of additional exports. This is reasonable as entrepreneurs start their new ventures with minimum possible employment and relatively low rate of capacity utilization and they come up to take advantage of the process of globalization by catering to the international market.

Influence of recombination on acquisition and reversion of immune escape and compensatory mutations in HIV-1

Following transmission, HIV-1 adapts in the new host by acquiring mutations that allow it to escape from the host immune response at multiple epitopes. It also reverts mutations associated with epitopes targeted in the transmitting host but not in the new host. Moreover, escape mutations are often associated with additional compensatory mutations that partially recover fitness costs. It is unclear whether recombination expedites this process of multi-locus adaptation. To elucidate the role of recombination, we constructed a detailed population dynamics model that integrates viral dynamics, host immune response at multiple epitopes through cytotoxic T lymphocytes, and viral evolution driven by mutation, recombination, and selection. Using this model, we compute the expected waiting time until the emergence of the strain that has gained escape and compensatory mutations against the new host's immune response, and reverted these mutations at epitopes no longer targeted. We find that depending on the underlying fitness landscape, shaped by both costs and benefits of mutations, adaptation proceeds via distinct dominant pathways with different effects of recombination, in particular distinguishing escape and reversion. When adaptation at a single epitope is involved, recombination can substantially accelerate immune escape but minimally affects reversion. When multiple epitopes are involved, recombination can accelerate or inhibit adaptation depending on the fitness landscape. Specifically, recombination tends to delay adaptation when a purely uphill fitness landscape is accessible at each epitope, and accelerate it when a fitness valley is associated with each epitope. Our study points to the importance of recombination in shaping the adaptation of HIV-1 following its transmission to new hosts, a process central to T cell-based vaccine strategies. (C) 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license.

Thermal shock characteristics of plasma sprayed mullite coatings

Commercially available mullite (3Al(2)O(3). 2SiO(2)) powders containing oxides of calcium and iron as impurities, have been made suitable for plasma spraying by using an organic binder. Stainless steel substrates covered with Ni-22Cr-10Al-1.0Y bond coat were spray coated with mullite, The 425 mu m thick coatings were subjected to thermal shock cycling under burner rig conditions between 1000 and 1200 degrees C and less than 200 degrees C with holding times of 1, 5, and 30 min. While the coatings withstood as high as 1000 shock cycles without failure between 1000 and 200 degrees C, spallation occurred early at 120 cycles when shocked from 1200 degrees C, The coatings appeared to go through a process of self erosion at high temperatures resulting in loss of material. Also observed were changes attributable to melting of the silicate grains, which smooth down the surface. Oxidation of the bond coat did not appear to influence the failure, These observations were supported by detailed scanning electron microscopy and quantitative chemical composition analysis, differential thermal analysis, and surface roughness measurements.