Conformational Choices for the Stereochemically Constrained gamma-Amino Acid Residue Gabapentin: Theoretical Studies and Correlation With Experimental Results

Gabapentin (1-aminomethylcyclohexaneacetic acid, Gpn) is an achiral, conformationally constrained gamma amino acid residue. A survey of available crystal structures of Gpn peptides reveals that the torsion angles about the C-gamma-C-beta (theta(1)) and C-beta-C-alpha(theta(2)) bonds are overwhelmingly limited to gauche, gauche (g(+)g(+)/g(-)g(-)) conformations. The Gpn residue forms C-7 and C-9 hydrogen bonds in which the donor and acceptor atoms come from the flanking peptide units. In combination with alpha amino acid residues alpha gamma and gamma alpha segments can adopt C-12 hydrogen bonded structures. The conformational choices available to the Gpn residue have been probed using energy calculations, adopting a grid search strategy. Ramachandran phi-psi maps have been constructed for fixed values of theta(1) and theta(2), corresponding to the gauche and trans conformations. The sterically allowed and energetically favorable regions of conformational space have been defined and experimental observations compared. C-7 and C-9 hydrogen bonded conformational families have been identified using a grid search approach in which theta(1) and theta(2) values are varied over a range of +/- 10 degrees about ideal values at 1 degrees intervals. The theoretical analysis together with experimental observations for 59 Gpn residues from 35 crystal structures permits definition of the limited range of conformational possibilities at this gamma amino acid residue. .

Experimental studies of lipped channel beams subject to web crippling under two-flange load cases

Lipped channel beams (LCBs) are commonly used as flexural members such as floor joists and bearers in the construction 6 industry. These thin-walled LCBs are subjected to specific buckling and failure modes, one of them being web crippling. Despite considerable 7 research in this area, some recent studies have shown that the current web crippling design rules are unable to predict the test capacities under 8 end-two-flange (ETF) and interior-two-flange (ITF) load conditions. In many instances, web crippling predictions by the available design 9 standards such as AISI S100, AS/NZS 4600 and Eurocode 3 Part 1-3 are inconsistent, i.e., unconservative in some cases, although they 10 are conservative in other cases. Hence, experimental studies consisting of 36 tests were conducted in this research to assess the web crippling 11 behavior and capacities of high-strength LCBs under two-flange load cases (ETF and ITF). Experimental results were then compared with the 12 predictions from current design rules. Comparison of the ultimate web crippling capacities from tests showed that the design equations are 13 very unconservative for LCB sections under the ETF load case and are conservative for the ITF load case. Hence, improved equations were 14 proposed to determine the web crippling capacities of LCBs based on the experimental results from this study. Current design equations do 15 not provide the direct strength method (DSM) provisions for web crippling. Hence, suitable design rules were also developed under the DSM 16 format using the test results and buckling analyses using finite-element analyses.

Experimental studies on web crippling strength of hollow flange channels under EOF and IOF load cases

LiteSteel beam (LSB) is a hollow flange channel made from cold-formed steel using a patented manufacturing process involving simultaneous cold-forming and dual electric resistance welding. LSBs are currently used as floor joists and bearers in buildings. However, there are no appropriate design standards available due to its unique hollow flange geometry, residual stress characteristics and initial geometric imperfections arising from manufacturing processes. Recent research studies have focused on investigating the structural behaviour of LSBs under pure bending, predominant shear and combined actions. However, web crippling behaviour and strengths of LSBs still need to be examined. Therefore, an experimental study was undertaken to investigate the web crippling behaviour and strengths of LSBs under EOF (End One Flange) and IOF (Interior One Flange) load cases. A total of 23 web crippling tests were performed and the results were compared with the current AS/NZS 4600 and AISI S100 design standards, which showed that the cold-formed steel design rules predicted the web crippling capacity of LSB sections very conservatively under EOF and IOF load cases. Therefore, suitably improved design equations were proposed to determine the web crippling capacity of LSBs based on experimental results. In addition, new design equations were also developed under the Direct Strength Method format. This paper presents the details of this experimental study on the web crippling behaviour and strengths of LiteSteel beams under EOF and IOF load cases and the results.

Experimental and numerical studies of hollow flange channel beams subject to web crippling under ETF and ITF load cases

This paper presents the details of experimental and numerical studies on the web crippling behaviour of hollow flange channel beams, known as LiteSteel beams (LSB). The LSB has a unique shape of a channel beam with two rectangular hollow flanges, made using a unique manufacturing process. Experimental and numerical studies have been carried out to evaluate the behaviour and design of LSBs subject to pure bending actions, predominant shear actions and combined actions. To date, however, no investigation has been conducted into the web crippling behaviour and strength of LSB sections under ETF and ITF load conditions. Hence experimental studies consisting of 28 tests were first conducted in this research to assess the web crippling behaviour and strengths of LSBs under two flange load cases (ETF and ITF). Experimental web crippling capacity results were then compared with the predictions from AS/NZS 4600 and AISI S100 design rules, which showed that AS/NZS 4600 and AISI S100 design equations are very unconservative for LSBs under ETF and ITF load cases. Hence improved equations were proposed to determine the web crippling capacities of LSBs. Finite element models of the tested LSBs were then developed, and used to determine the elastic buckling loads of LSBs under ETF and ITF load cases. New equations were proposed to determine the corresponding elastic buckling coefficients of LSBs. Finally suitable design rules were also developed under the Direct Strength Method format using the test results and buckling analysis results from finite element analyses.

Light and heat induced interdiffusion in Sb/As2S3 nano-multilayered film

The light and heat induced changes in the optical band gap of Sb/As2S3 nanomultilayered chalcogenide film has been studied. Even though the changes in optical bandgap are attributed to the light and heat induced interdiffusion, the diffusional intermixing between the layers is rather different with light and heat. The observed difference in the light and heat induced interdiffusion is due to unequal diffusion coefficients of light and heat predicted by thermal spike model.

In situ pump probe optical absorption studies on Sb/As2S3 nanomultilayered film

We report the in situ optical transmission change in the complete visible region of the electromagnetic spectrum to asses the kinetics of photo induced interdiffusion in Sb/As2S3 nanomultilayered film. The interdiffusion of Sb into As2S3 matrix results in the formation of Sb-As2S3 ternary solid solutions which is explained by the change in optical band gap, absorption coefficients and Tauc parameter (B-1/2) with evolution of time. The wavelength dependence of the time constants provides a better description of photo induced effects. The time evolution of the absorption coefficients and optical band gap are significantly faster in this process. (C) 2009 Elsevier B.V. All rights reserved.

Experimental investigation of die wear in small-batch hammer-forging under unlubricated conditions

Wear of dies is a serious problem in the forging industry. The materials used for the dies are generally expensive steel alloys and the dies require costly heat treatment and surface finishing operations. Degeneration of the die profile implies rejection of forged components and necessitates resinking or replacement of the die. Measures which reduce wear of the die can therefore aid in the reduction of production costs. The work reported here is the first phase of a study of the causes of die wear in forging production where the batch size is small and the machine employed is a light hammer. This is a problem characteristic of the medium and small scale area of the forging industry where the cost of dies is a significant proportion of the total capital investment. For the same energy input and under unlubricated conditions, die wear has been found to be sensitive to forging temperature; in cold forging the yield strength of the die material is the prime factor governing the degeneration of the die profile, whilst in hot forging the wear resistance of the die material is the main factor which determines the rate of die wear. At an intermediate temperature, such as that characteristic of warm forging, the die wear is found to be less than that in both cold and hot forging. This preliminary study therefore points to the fact that the forging temperature must be taken into account in the selection of die material. Further, the forging industry must take serious note of the warm forging process, as it not only provides good surface finish, as claimed by many authors, but also has an inherent tendency to minimize die wear.

Design and characterization of in-plane MEMS yaw rate sensor

In this paper, we present the design and characterization of a vibratory yaw rate MEMS sensor that uses in-plane motion for both actuation and sensing. The design criterion for the rate sensor is based on a high sensitivity and low bandwidth. The required sensitivity of the yawrate sensor is attained by using the inplane motion in which the dominant damping mechanism is the fluid loss due to slide film damping i.e. two-three orders of magnitude less than the squeeze-film damping in other rate sensors with out-of-plane motion. The low bandwidth is achieved by matching the drive and the sense mode frequencies. Based on these factors, the yaw rate sensor is designed and finally realized using surface micromachining. The inplane motion of the sensor is experimentally characterized to determine the sense and the drive mode frequencies, and corresponding damping ratios. It is found that the experimental results match well with the numerical and the analytical models with less than 5% error in frequencies measurements. The measured quality factor of the sensor is approximately 467, which is two orders of magnitude higher than that for a similar rate sensor with out-of-plane sense direction.

Which One Is Preferred: Myers-Saito Cyclization of Ene-Yne-Allene or Garratt-Braverman Cyclization of Conjugated Bisallenic Sulfone? A Theoretical and Experimental Study

A competitive scenario between Myers-Saito (MS) and Garraff-Braverman (GB) cyclization has been created in a molecule. High-level computations indicate a preference for GB over MS cyclization. The activation energies for the rate-determining steps of the GB and MS cyclizations were found to be the same (24.4 kcal/mol) at the B3LYP/6-31G* level of theory; thus, from the kinetic point of view, both reactions are feasible. However, the main biradical intermediate GB2 of the GB reaction is 6.2 kcal/mol lower in energy than the biradical MS2, which is the main intermediate of MS reaction, so GB cyclization is thermodynamically favored over MS cyclization. To verify the prediction by computational techniques, bisenediynyl sulfones 1-4 and bisenediynyl sulfoxide 17 were synthesized. Under basic conditions, these molecules isomerized to a system possessing both the ene-yne-allene and the bisallenic sulfone. The isolation of only one product, identified as the corresponding naphthalene- or benzene-fused sulfone 8-11, indicated the occurrence of GB cyclization as the sole reaction pathway. No product corresponding to the MS cyclization pathway could be isolated. Though the theoretical prediction showed a preference for the GB pathway over the MS pathway, the exclusive preference for GB over MS cyclization is very striking. Further analysis showed that the intramolecular self-quenching nature of the GB pathway may play an important role in the complete preference for this reaction. Apart from the mechanistic studies, these sulfones showed DNA cleavage activity that had an inverse relation with the reactivity order. Our findings are important for the design of artificial DNA-cleaving agents.

Simple theoretical analysis of the Einstein's photoemission from quantum confined superlattices

In this paper, we study the Einstein's photoemission from III-V, II-VI, IV-VI and HgTe/CdTe quantum well superlattices (QWSLs) with graded interfaces and quantum well effective mass superlattices in the presence of a quantizing magnetic field on the basis of newly formulated dispersion relations in the respective cases. Besides, the same has been studied from the afore-mentioned quantum dot superlattices and it appears that the photoemission oscillates with increasing carrier degeneracy and quantizing magnetic field in different manners. In addition, the photoemission oscillates with film thickness and increasing photon energy in quantum steps together with the fact that the solution of the Boltzmann transport equation will introduce new physical ideas and new experimental findings under different external conditions. The influence of band structure is apparent from all the figures and we have suggested three applications of the analyses of this paper in the fields of superlattices and microstructures.