Stereochemically constrained peptides. Theoretical and experimental studies on the conformations of peptides containing 1-aminocyclohexane carboxylic acid

Conformational energy calculations on the model system N-acetyl- 1 -aminocyclohexanecarboxylic acid N'methylamide (Ac-Acc6-NHMe), using an average geometry derived from 13 crystallographic observations, establish that the Acc6 residue is constrained to adopt conformations in the helical regions of In contrast, the a,a-dialkylated residue with linear hydrocarbon side chains, a,a-di-n-propylglycine favors fully extended backbone structures (6 1= $ = 180'). The crystal structures of two model peptides, Boc-(Acc6),-OMe (type 111 @-turn at -Acc6(1)-Acc6(2)-) and Boc-Pro-Acc6-Ala-OMe (type I1 P-turn at -Pro-Acc6-), establish that Acc6 residues can occupy either position of type 111 P-turns and the i + 2 position of type I1 @-turns. The stereochemical rigidity of these peptides is demonstrated in solution by NMR studies, which establish the presence of one intramolecular hydrogen bond in each peptide in CDCI, and (CDJ2S0. Nuclear Overhauser effects permit characterization of the @-turn conformations in solution and establish their similarity to the solid-state structures. The implications for the use of Acc6 residues in conformational design are considered.

An Experimental and Numerical Study of Calliphora Wing Structure

Experiments are performed to determine the mass and stiffness variations along the wing of the blowfly Calliphora. The results are obtained for a pairs of wings of 10 male flies and fresh wings are used. The wing is divided into nine locations along the span and seven locations along the chord based on venation patterns. The length and mass of the sections is measured and the mass per unit length is calculated. The bending stiffness measurements are taken at three locations, basal (near root), medial and distal (near tip) of the fly wing. Torsional stiffness measurements are also made and the elastic axis of the wing is approximately located. The experimental data is then used for structural modeling of the wing as a stepped cantilever beam with nine spanwise sections of varying mass per unit lengths, flexural rigidity (EI) and torsional rigidity (GJ) values. Inertial values of nine sections are found to approximately vary according to an exponentially decreasing law over the nine sections from root to tip and it is used to calculate an approximate value of Young's modulus of the wing biomaterial. Shear modulus is obtained assuming the wing biomaterial to be isotropic. Natural frequencies, both in bending and torsion, are obtained by solving the homogeneous part of the respective governing differential equations using the finite element method. The results provide a complete analysis of Calliphora wing structure and also provide guidelines for the biomimetic structural design of insect-scale flapping wings.

Correlation of helicopter rotor aeroelastic response with HART-II wind tunnel test data

Purpose - This paper aims to validate a comprehensive aeroelastic analysis for a helicopter rotor with the higher harmonic control aeroacoustic rotor test (HART-II) wind tunnel test data. Design/methodology/approach - Aeroelastic analysis of helicopter rotor with elastic blades based on finite element method in space and time and capable of considering higher harmonic control inputs is carried out. Moderate deflection and coriolis nonlinearities are included in the analysis. The rotor aerodynamics are represented using free wake and unsteady aerodynamic models. Findings - Good correlation between analysis and HART-II wind tunnel test data is obtained for blade natural frequencies across a range of rotating speeds. The basic physics of the blade mode shapes are also well captured. In particular, the fundamental flap, lag and torsion modes compare very well. The blade response compares well with HART-II result and other high-fidelity aeroelastic code predictions for flap and torsion mode. For the lead-lag response, the present analysis prediction is somewhat better than other aeroelastic analyses. Research limitations/implications - Predicted blade response trend with higher harmonic pitch control agreed well with the wind tunnel test data, but usually contained a constant offset in the mean values of lead-lag and elastic torsion response. Improvements in the modeling of the aerodynamic environment around the rotor can help reduce this gap between the experimental and numerical results. Practical implications - Correlation of predicted aeroelastic response with wind tunnel test data is a vital step towards validating any helicopter aeroelastic analysis. Such efforts lend confidence in using the numerical analysis to understand the actual physical behavior of the helicopter system. Also, validated numerical analyses can take the place of time-consuming and expensive wind tunnel tests during the initial stage of the design process. Originality/value - While the basic physics appears to be well captured by the aeroelastic analysis, there is need for improvement in the aerodynamic modeling which appears to be the source of the gap between numerical predictions and HART-II wind tunnel experiments.

An experimental study of suddenly expanded rectangular jet flow field

Flow through a rectangular Passage which is expanded suddenly into another rectangular duct of larger Cross-sectional area has been studied experimentally with stagnation Pressures from 3.5 atmospheres to 1.25 atmospheres. The length to height ratio of the enlarged duct varied from 5.769 to 1.923 and three models with length to height ratios 5.769, 3.846, and 1.923 were studied. The influence of stagnation Pressures and length to height ratio of the enlarged duct on base pressure and flow field mean pressures in the enlarged duct is discussed. The results of the present investigation indicate that the oscillatory nature of the mean pressure flow field in the enlarged portion with rectangular cross-section is appreciably different from that for circular cross-section at similar flow conditions.

Experimental investigation of three-layer electromagnetically coupled circular microstrip antennas

The broadband behaviour of a three-layer electromagnetically coupled circular microstrip antenna is investigated experimentally. The effects of interlayer spacings and the thickness of the parasitic layers on the impedance bandwidth, 3 dB beamwidth and pattern shape, are studied. Experiments show that this structure can provide a frequency bandwidth as high as 20% with a low crosspolarisation level and a moderately high gain.

Indentation of sintered alumina clay composite - an experimental discussion of a combined Boussinesq and blister stress field approach

Surface elastic strain field generated in conical indentation of sintered alumina clay composite was measured to verify the suitability of a superposed combination of Boussinesq and blister stress fields, used previously for analysing the indentation problem. The residual strain measured in the elastic hinterland is used to estimate the blister field strength without any reference to stress relation within that field. The approach may be useful in fracture studies of brittle materials.

A methodology for supporting ``transfer'' in biomimetic design

Biomimetics involves transfer from one or more biological examples to a technical system. This study addresses four questions. What are the essential steps in a biomimetic process? What is transferred? How can the transferred knowledge be structured in a way useful for biologists and engineers? Which guidelines can be given to support transfer in biomimetic design processes? In order to identify the essential steps involved in carrying out biomimetics, several procedures found in the literature were summarized, and four essential steps that are common across these procedures were identified. For identification of mechanisms for transfer, 20 biomimetic examples were collected and modeled according to a model. of causality called the SAPPhIRE model. These examples were then analyzed for identifying the underlying similarity between each biological and corresponding analogue technical system. Based on the SAPPhIRE model, four levels of abstraction at which transfer takes place were identified. Taking into account similarity, the biomimetic examples were assigned to the appropriate levels of abstraction of transfer. Based on the essential steps and the levels of transfer, guidelines for supporting transfer in biomimetic design were proposed and evaluated using design experiments. The 20 biological and analogue technical systems that were analyzed were similar in the physical effects used and at the most abstract levels of description of their functionality, but they were the least similar at the lowest levels of abstraction: the parts involved. Transfer most often was carried out at the physical effect level of abstraction. Compared to a generic set of guidelines based on the literature, the proposed guidelines improved design performance by about 60%. Further, the SAPPhIRE model turned out to be a useful representation for modeling complex biological systems and their functionality. Databases of biological systems, which are structured using the SAPPhIRE model, have the potential to aid biomimetic concept generation.

The influence of lone-pair repulsions on C–C bond lengths: a critical evaluation of the experimental and theoretical evidence

X-Ray structural data, as well as semiempirical and ab initio molecular orbital calculations, reveal no systematic and substantial difference between the C–C bond lengths of cis and trans 1,2-diketones. Additional results on various conformations of 1,2-diimines and 1,2-dithiones follow the same pattern. Therefore, lone-pair repulsions cannot be implicated in the observed lengthening of C–C bonds in isatin and several related molecules. Conjugation in these systems occurs peripherally avoiding the participation of the central C–C bond. Negative hyperconjugative interaction between the oxygen lone pairs and the adjacent C–C σ* orbital is suggested to be the principal reason for the relatively long C–C bond in diketones. This effect is found in both the cis and trans conformations.

Experimental analysis of thermo-physical processes in acoustically levitated heated droplets

An experimental setup using radiative heating has been used to understand the thermo-physical phenomena and chemical transformations inside acoustically levitated cerium nitrate precursor droplets. In this transformation process, through infrared thermography and high speed imaging, events such as vaporization, precipitation and chemical reaction have been recorded at high temporal resolution, leading to nanoceria formation with a porous morphology. The cerium nitrate droplet undergoes phase and shape changes throughout the vaporization process. Four distinct stages were delineated during the entire vaporization process namely pure evaporation, evaporation with precipitate formation, chemical reaction with phase change and formation of final porous precipitate. The composition was examined using scanning and transmission electron microscopy that revealed nanostructures and confirmed highly porous morphology with trapped gas pockets. Transmission electron microscopy (TEM) and high speed imaging of the final precipitate revealed the presence of trapped gases in the form of bubbles. TEM also showed the presence of nanoceria crystalline structures at 70 degrees C. The current study also looked into the effect of different heating powers on the process. At higher power, each phase is sustained for smaller duration and higher maximum temperature. In addition, the porosity of the final precipitate increased with power. A non-dimensional time scale is proposed to correlate the effect of laser intensity and vaporization rate of the solvent (water). The effect of acoustic levitation was also studied. Due to acoustic streaming, the solute selectively gets transported to the bottom portion of the droplet due to strong circulation, providing it rigidity and allows it become bowl shaped. (C) 2010 Elsevier Ltd. All rights reserved.

Experimental evaluation of the aeroacoustic characteristics of a source of pulsating gas flow

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A Convenient Methodology for the Selective Reduction of Carboxylic Acids With Benzyltriethyl-Ammonium Borohydride—Chlorotrimethylsilane

A combination of benzyltriethylammonium borohydride and chlorotrimethylsilane (1:1) in dichloromethane (0-25°C) has been found to be a convenient reagent system for the selective reduction of carboxylic acids to alcohols.