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.

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.

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

Amongv arioums ethodtsh,e t ransmissliionne o r thei mpedantcueb em ethohda sb eenm ospt opulafro r thee xperimenetavla luatioonf thea cousticiaml pedanocef a terminatioTnh. ee xistinmg ethodisn,c luding theo nesre porteeda rlierb, y thea uthorrse quirleo catioonf thes oundp ressumrei nima nd/orm axima, or elsem akeu se0 f somei terativep rocedureTsh. e presenpt aperd ealsw ith a methodo f analysios f standinwga vews hichd oesn otd epenodn anyo f thesein volvepdr ocedureIts i.s applicabtloe thec aseo f stationarays w ella sm ovingm ediaI.t enableosn to evaluatteh e impedancoef anyp assivbel ackb ox,a s well as the aeroacoustcich aracteristicosf a sourceo f pulsatingg asf low, with the leaste xperimentawl ork andc omputatiotinm ea ndw itht hee xtraa dvantagoef usinga givenim pedanctueb ef or wavelengtahss largea s fourt imesit s lengthA. methodo f externaml easuremenntost, involvinugs eo f anyi mpedance tubef, or evaluatintgh ea eroacouscthica racteristoicf as sourcoef pulsatingga sf lowi s alsod ealtw ith, based on the definition of attenuation or insertion loss of a muffler.

Nature of Cl center dot center dot center dot Cl Intermolecular Interactions via Experimental and Theoretical Charge Density Analysis:Correlation of Polar Flattening Effects with Geometry

The experimental charge density distribution in three compounds, 2-chloro-3-quinolinyl methanol, 2-chloro-3-hydroxypyridine, and 2-chloro-3-chloromethyl-8-methylquinoline, has been obtained using high-resolution X-ray diffraction data collected at 100 K based on the aspherical multipole modeling of electron density. These compounds represent type I (cis), type I (trans), and type II geometries, respectively, as defined for short Cl center dot center dot center dot Cl interactions. The experimental results are compared with the theoretical charge densities using theoretical structure factors obtained from a periodic quantum calculation at the B3LYP/6-31G** level. The topological features derived from the Bader's theory of atoms in molecules (AIM) approach unequivocally suggest that both cis and trans type I geometries show decreased repulsion, whereas type II geometry is attractive based on the nature of polar flattening of the electron density around the Cl atom.

Numerical and experimental study of the thermal behaviour of coining and upsetting processes

A numerical simulation technique has been employed to study the thermal behavior of hot-forging type forming processes. Experiments on the coining and upsetting of an aluminum billet were conducted to validate the numerical predictions. Typical forming conditions for both the coining and upsetting processes were then studied in detail. an electrical analogy scheme was used to determine the thermal contact resistance. This scheme can conviniently provide the interface characteristics for typical processing conditions, which normally involve high pressures and temperatures. A single forging cycle was first considered, and then a batch of twenty-five forgings was studied. Each forging cycle includes the billet mounting, ascent, loading, dwelling, unloading, descent, and billet removal stages. The temperature distribution in the first forging to be formed is found to be significantly different from that at the end of the batch. In industry, forging is essentially a batch operation. The influence of forming speed and reduction on thermal characteristics was investigated also. The variations that can occur in the process design by considering differences in temperature characteristics are discussed also.