A Case Study of the Conformation of Poly(alpha-aminoisobutyric acid): alpha- or 310-Helix

The relative stabilities of a- and Blo-helical structures for polymers of a-aminoisobutyric acid (Aib) have been worked out, using the classical potential energy functions. To make a comparative study, we have used Buckingham "6-exp" and Kitaigorodsky's potential functions. Conformational analysis of the dipeptide segment with Aib residue indicates the necessity for nonplanar distortion of the peptide unit, which is a common feature in the observed crystal structures with Aib residues. In the range of Aw -10 to +loo studied, a-helical conformations are preferred in the region -3" < Aw < +loo, and Blo-helical conformations are preferred in the region -3" > Aw > -10'. Minimum energy conformations for right-handed structures are found in the +ue region of Aw and correspondingly for left-handed structures in the -ue region of Aw. For Aw - 6", a-helical structures have four- or near fourfold symmetry with h - 1.5 A. Such a helix with n = 4 and h = 1.5 A is termed an a'-helix. This structure is found to be consistent with the electron diffraction data of Malcolm3 and energetically more favorable than the standard 310-helix.

Significance of Branching Angles in Streamer Discharges

The phenomenon of branching at specific angles in streamer breakdown studies is found to be more universal than was ever thought. The angles measured in the breakdown of gases show that the coefficient of field distortion, K, lies in the range from 1 to less than 0.1. The values of K, so obtained agree well with those envisaged in the criterion of the streamer mechanism. It is hoped that branching angles observed in various types of breakdown may, possibly, be explained similarly.

ESR study of copper diethyldithiophosphate

ESR investigations are reported in single crystals of copper diethyldithiophosphate, magnetically diluted with the corresponding diamagnetic nickel complex. The spectrum at normal gain shows hyperfine components from 63Cu, 65Cu, and 31P nuclei. At much higher gain, hyperfine interaction from 33S nuclei in the ligand is detected. The spin Hamiltonian parameters relating to copper show tetragonal symmetry. The measured parameters are g|| = 2.085, g[perpendicular]=2.025, A63Cu = 149.6 × 10−4 cm−1, A65Cu = 160.8 × 10−4 cm−1, BCu = 32.5 × 10−4 cm−1 and QCu [infinity] 5.5 × 10−4cm−1. The 31P interaction is isotropic with a coupling constant AP = 9.6 × 10−4 cm−1. Angular variation of the 33S lines shows two different hyperfine tensors indicating the presence of two chemically inequivalent Cu[Single Bond]S bonds. The experimentally determined hyperfine constants are A ₁^s=34.9×10−4 cm−1, B ₁^s=26.1×10−4 cm−1, A ₂^s=60.4×10−4 cm−1, B₂^s=55.5×10−4 cm−1. The hyperfine parameters show that the hybridization of the ligand orbitals is very sensitive to the symmetry around the ligand. The g values and Cu hyperfine parameters are not much affected by the distortions occurring in the ligand. The energies of the d-d transitions are determined by optical absorption measurements on Cu diethyldithiophosphate in solution. Using the spin Hamiltonian parameters together with optical absorption results, the MO parameters for the complex are calculated. It is found that in addition to the sigma bond, the pi bonds are also strongly covalent. ©1973 The American Institute of Physics.

Chemistry and biology of DNA methyltransferases

Recognition of a specific DNA sequence by a protein is probably the best example of macromolecular interactions leading to various events. It is a prerequisite to understanding the basis of protein-DNA interactions to obtain a better insight into fundamental processes such as transcription, replication, repair, and recombination. DNA methyltransferases with varying sequence specificities provide an excellent model system for understanding the molecular mechanism of specific DNA recognition. Sequence comparison of cloned genes, along with mutational analyses and recent crystallographic studies, have clearly defined the functions of various conserved motifs. These enzymes access their target base in an elegant manner by flipping it out of the DNA double helix. The drastic protein-induced DNA distortion, first reported for HhaI DNA methyltransferase, appears to be a common mechanism employed by various proteins that need to act on bases. A remarkable feature of the catalytic mechanism of DNA (cytosine-5) methyltransferases is the ability of these enzymes to induce deamination of the target cytosine in the absence of S-adenosyl-L-methionine or its analogs. The enzyme-catalyzed deamination reaction is postulated to be the major cause of mutational hotspots at CpG islands responsible for various human genetic disorders. Methylation of adenine residues in Escherichia coli is known to regulate various processes such as transcription, replication, repair, recombination, transposition, and phage packaging.

Tied aid, unemployment and welfare

The effect of foreign aid on the welfare levels of both the recipient and the donor country has been a much analysed topic for research in both the theory of international trade and development economics. In the development economics literature, concerns have been raised since the 1960s on the possible adverse effect of foreign aid on domestic savings and growth.1 The trade theory literature in this respect is much older and dates back to the 1920s when Professors Keynes and Ohlin debated on the effect of foreign aid on international terms of trade.2 Ever since, the terms of trade effect has been the cornerstone in the analysis of the welfare effect of foreign aid in the trade theory literature.3 After some early confusion, it is now well established that in a Walrasian stable world economy with two countries, a necessary condition for foreign aid to have perverse effects is that there is some distortion in either of the two countries.4 It is also known that, under normality and substitutability of goods, untied aid cannot be strictly Pareto-improving in a tariff distorted world.5

In vitro demonstration of the heavy-atom effect for photodynamic therapy

Photodynamic therapy (PDT) is an emerging treatment modality for a range of disease classes, both cancerous and noncancerous. This has brought about an active pursuit of new PDT agents that can be optimized for the unique set of photophysical characteristics that are required for a successful clinical agent. We now describe a totally new class of PDT agent, the BF2-chelated 3,5-diaryl-1H-pyrrol-2-yl-3,5-diarylpyrrol-2-ylideneamines (tetraarylazadipyrromethenes). Optimized synthetic procedures have been developed to facilitate the generation of an array of specifically substituted derivatives to demonstrate how control of key therapeutic parameters such as wavelength of maximum absorbance and singlet-oxygen generation can be achieved. Photosensitizer absorption maxima can be varied within the body's therapeutic window between 650 and 700 nm, with high extinction coefficients ranging from 75,000 to 85,000 M(-1) cm(-1). Photosensitizer singlet-oxygen generation level was modulated by the exploitation of the heavy-atom effect. An array of photosensitizers with and without bromine atom substituents gave rise to a series of compounds with varying singlet-oxygen generation profiles. X-ray structural evidence indicates that the substitution of the bromine atoms has not caused a planarity distortion of the photosensitizer. Comparative singlet-oxygen production levels of each photosensitizer versus two standards demonstrated a modulating effect on singlet-oxygen generation depending upon substituent patterns about the photosensitizer. Confocal laser scanning microscopy imaging of 18a in HeLa cervical carcinoma cells proved that the photosensitizer was exclusively localized to the cellular cytoplasm. In vitro light-induced toxicity assays in HeLa cervical carcinoma and MRC5-SV40 transformed fibroblast cancer cell lines confirmed that the heavy-atom effect is viable in a live cellular system and that it can be exploited to modulate assay efficacy. Direct comparison of the efficacy of the photosensitizers 18b and 19b, which only differ in molecular structure by the presence of two bromine atoms, illustrated an increase in efficacy of more than a 1000-fold in both cell lines. All photosensitizers have very low to nondeterminable dark toxicity in our assay system.

ESR Study of a Cr5+ Centre in Ferroelectric Ammonium Sulphate

X-band electron spin resonance (ESR) studies of (CrO4)2- doped, X-irradiated single crystals of ferroelectric ammonium sulphate ((NH4)2SO4, TC = 223 K) at 300 and 208 K are reported. The paramagnetic centre responsible for the ESR spectrum is identified to be Cr5+. Superhyperfine interaction of the unpaired electron with two equivalent protons is observed. The spin-Hamiltonian parameters which are nearly axial at 300 K, with g < g indicating a dx2-y2 orbital ground state, acquired rhombic character below TC indicating a distortion of the sulphate tetrahedron. An increase in the value of the proton superhyperfine constant in the ferroelectric phase is indicative of stronger hydrogen bonding.

Dark Mess

In a world consumed by quests for happiness and personal growth, Grant Stevens’ new exhibition, Dark Mess, delves into the psychic troubles that sometimes lie below the canopy. Working predominantly with video, photography and installation, Stevens’ practice explores how the verbal and non-verbal languages of popular screen culture interface with contemporary subjectivity. This exhibition continues Stevens’ interest in the natural environment as a catalyst and proxy for introspection and self-discovery. Pushing sound and image to distortion, Dark Mess offers a disquieting journey through the undergrowth.

Two temperature viscous accretion flows around rotating black holes: Description of under-fed systems to ultra-luminous X-ray sources

We discuss two temperature accretion disk flows around rotating black holes. As we know that to explain observed hard X-rays the choice of Keplerian angular momentum profile is not unique, we consider the sub-Keplerian regime of the disk. Without any strict knowledge of the magnetic field structure, we assume the cooling mechanism is dominated by bremsstrahlung process. We show that in a range of Shakura-Sunyaev viscosity parameter 0.2 greater than or similar to alpha greater than or similar to 0.0005, flow behavior varies widely, particularly by means of the size of disk, efficiency of cooling and corresponding temperatures of ions and electrons. We also show that the disk around a rotating black hole is hotter compared to that around a Schwarzschild black hole, rendering a larger difference between ion and electron temperatures in the former case. With all the theoretical solutions in hand, finally we reproduce the observed luminosities (L) of two extreme cases-the under-fed AGNs and quasars (e.g. Sgr A') with L greater than or similar to 10(33) erg/s to ultra-luminous X-ray sources with L similar to 10(41) erg/s, at different combinations of mass accretion rate, ratio of specific heats, Shakura-Sunyaev viscosity parameter and Kerr parameter, and conclude that Sgr A' may be an intermediate spinning black hole.

Total hip arthroplasty in young patients : with special references to patients under 55 years of age and to patients with developmental dysplasia of the hip

There is an ongoing controversy as to which methods in total hip arthroplasty (THA) could provide young patients with best long-term results. THA is an especially demanding operation in patients with severely dysplastic hips. The optimal surgical treatment for these patients also remains controversial. The aim of this study was to evaluate the long-term survival of THA in young patients (<55 years at the time of the primary operation) on a nation-wide level, and to analyze the long-term clinical and radio-graphical outcome of uncemented THA in patients with severely dysplastic joints. Survival of 4661 primary THAs performed for primary osteoarthritis (OA), 2557 primary THAs per-formed for rheumatoid arthritis (RA), and modern uncemented THA designs performed for primary OA in young patients, were analysed from the Finnish Arthroplasty Register. A total of 68 THAs were per-formed in 56 consecutive patients with high congenital hip dislocation between 1989-1994, and 68 THAs were performed in 59 consecutive patients with severely dysplastic hips and a previous Schanz osteotomy of the femur between 1988-1995 at the Orton Orthopaedic Hospital, Helsinki, Finland. These patients underwent a detailed physical and radiographical evaluation at a mean of 12.3 years and 13.0 years postoperatively, respectively. The risk of stem revision due to aseptic loosening in young patients with primary OA was higher for cemented stems than for proximally porous-coated or HA-coated uncemented stems implanted over the 1991-2001 period. There was no difference in the risk of revision between all-poly cemented-cups and press-fit porous-coated uncemented cups implanted during the same period, when the end point was defined as any revision (including exchange of liner). All uncemented stem designs studied in young patients with primary OA had >90% survival rates at 10 years. The Biomet Bi-Metric stem had a 95% (95% CI 93-97) survival rate even at 15 years. When the end point was defined as any revision, 10 year survival rates of all uncemented cup designs except the Harris-Galante II decreased to <80%. In young patients with RA, the risk of stem revision due to aseptic loosening was higher with cemented stems than with proximally porous-coated uncemented stems. In contrast, the risk of cup revision was higher for all uncemented cup concepts than for all-poly cemented cups with any type of cup revision as the end point. The Harris hip score increased significantly (p<0.001) both in patients with high con-genital hip dislocation and in patients with severely dysplastic hips and a previous Schanz osteotomy, treated with uncemented THA. There was a negative Trendelenburg sign in 92% and in 88% of hips, respectively. There were 12 (18%) and 15 (22%) perioperative complications. The rate of survival for the CDH femoral components, with revision due to aseptic loosening as the end point, was 98% (95% CI 97-100) at 10 years in patients with high hip dislocation and 92% (95% CI, 86-99) at 14 years in patients with a previous Schanz osteotomy. The rate of survival for press-fit, porous-coated acetabular components, with revision due to aseptic loosening as the end point, was 95% (95% CI 89-100) at 10 years in patients with high hip dislocation, and 98% (95% CI 89-100) in patients with a previous Schanz osteotomy. When revision of the cup for any reason was defined as the end point, 10 year sur-vival rates declined to 88% (95% CI 81-95) and to 69% (95% CI, 56-82), respectively. For young patients with primary OA, uncemented proximally circumferentially porous- and HA-coated stems are the implants of choice. However, survival rates of modern uncemented cups are no better than that of all-poly cemented cups. Uncemented proximally circumferentially porous-coated stems and cemented all-poly cups are currently the implants of choice for young patients with RA. Uncemented THA, with placement of the cup at the level of the true acetabulum, distal advancement of the greater trochanter and femoral shortening osteotomy provided patients with high congenital hip dislocation good long-term outcomes. Most of the patients with severely dysplastic hips and a previous Schanz osteotomy can be successfully treated with the same method. However, the subtrochanteric segmental shortening with angular correction gives better leg length correction for the patients with a previous low-seated unilateral Schanz osteotomy.

W physics at the ILC with polarized beams as a probe of the Littlest Higgs model

We study the possibility of using W pair production and leptonic decay of one of the W's at the ILC with polarized beams as a probe of the Littlest Higgs Model. We consider cross-sections, polarization fractions of the W's, leptonic decay energy and angular distributions, and left-right polarization asymmetry as probes of the model. With parameter values allowed by present experimental constraints detectable effects on these observables at typical ILC energies of 500 GeV and 800 GeV will be present. Beam polarization is further found to enhance the sensitivity.

Compact fiber Bragg grating dynamic strain sensor cum broadband thermometer for thermally unstable ambience

An instrument for simultaneous measurement of dynamic strain and temperature in a thermally unstable ambience has been proposed, based on fiber Bragg grating technology. The instrument can function as a compact and stand-alone broadband thermometer and a dynamic strain gauge. It employs a source wavelength tracking procedure for linear dependence of the output on the measurand, offering high dynamic range. Two schemes have been demonstrated with their relative merits. As a thermometer, the present instrumental configuration can offer a linear response in excess of 500 degrees C that can be easily extended by adding a suitable grating and source without any alteration in the procedure. Temperature sensitivity is about 0.06 degrees C for a bandwidth of 1 Hz. For the current grating, the upper limit of strain measurement is about 150 mu epsilon with a sensitivity of about 80 n epsilon Hz(-1/2). The major source of uncertainty associated with dynamic strain measurement is the laser source intensity noise, which is of broad spectral band. A low noise source device or the use of optical power regulators can offer improved performance. The total harmonic distortion is less than 0.5% up to about 50 mu epsilon, 1.2% at 100 mu epsilon and about 2.3% at 150 mu epsilon. Calibrated results of temperature and strain measurement with the instrument have been presented. Traces of ultrasound signals recorded by the system at 200 kHz, in an ambience of 100-200 degrees C temperature fluctuation, have been included. Also, the vibration spectrum and engine temperature of a running internal combustion engine has been recorded as a realistic application of the system.

Juvenile rheumatoid knee : Management of knee growth disturbances in children with juvenile idiopathic arthritis

Juvenile idiopathic arthritis (JIA) is associated with growth disturbances, especially leg length discrepancy (LLD) and knee valgus deformity (KVD). Studies have demonstrated growth plate stimulation with chronic arthritis. In the context of surgical treatment of LLD or KVD of a growing knee, the less invasive procedures, which allow immediate mobilisation, are preferred. Establishment of the skeletal age and the correction potential in the knees of rheumatic children is difficult due to rheumatic changes. In this present work, an analysis of the efficacy, safety and long-term results of temporary epiphyseal arrests performed in Rheumatism Foundation Hospital (Heinola, Finland). The distribution of diagnoses among children (n=71) with JIA and LLD (68 knees) was consistent with the normal oligoarthritis-predominated population of children with JIA. A higher male:female ratio (1:1.7 vs. 1:2.4 in population-based studies (PBS)) and earlier mean onset age (4 vs. 7 years in PBSs) were, however, distinct features in the study population. In most cases the correction was reliable and temporary arrest produced a mean correction of 1mm per month. The time of arrest required, however, varied significantly, probably due to the effect of underlying diseases and medication, and the age of the child. All complications encountered (10%) were minor. The correction achieved persisted in long-term follow-up. KVD (n=112, 177 knees) was associated with a high proportion of polyarthritic disease subtype (45% vs. 12-31% in PBSs), and the male:female distribution was grossly female-dominated (1:4.9 vs. 1:2.4 in PBSs). The early mean onset age (3 vs. 7 years in PBSs) was also notable in this cohort. Successful correction was achieved in 2/3 cases and the mean angular correction was 0.7 degrees per month. The required time of arrest, however, varied considerably. In 13% of knees the paucity of follow-up visits resulted in over-correction to varus. The complication rate (3%) in the knees operated for KVD was considerably lower compared to ten per cent in the management of LLD. Most of the complications related to epiphyseal stapling were reversible. However, the risk of premature closure of growth plates does exist. The number of over-corrections was notably high, with 13% knees turning to varus. The correction achieved persisted in long-term follow-up.

Two-temperature accretion around rotating black holes: a description of the general advective flow paradigm in the presence of various cooling processes to explain low to high luminous sources

We investigate viscous two-temperature accretion disc flows around rotating black holes. We describe the global solution of accretion flows with a sub-Keplerian angular momentum profile, by solving the underlying conservation equations including explicit cooling processes self-consistently. Bremsstrahlung, synchrotron and inverse Comptonization of soft photons are considered as possible cooling mechanisms. We focus on the set of solutions for sub-Eddington, Eddington and super-Eddington mass accretion rates around Schwarzschild and Kerr black holes with a Kerr parameter of 0.998. It is found that the flow, during its infall from the Keplerian to sub-Kepleria transition region to the black hole event horizon, passes through various phases of advection: the general advective paradigm to the radiatively inefficient phase, and vice versa. Hence, the flow governs a much lower electron temperature similar to 10(8)-10(9.5) K, in the range of accretion rate in Eddington units 0.01 less than or similar to (M) over dot less than or similar to 100, compared to the hot protons of temperature similar to 10(10.2)-10(11.8) K. Therefore, the solution may potentially explain the hard X-rays and gamma-rays emitted from active galactic nuclei (AGNs) and X-ray binaries. We then compare the solutions for two different regimes of viscosity. We conclude that a weakly viscous flow is expected to be cooling dominated, particularly at the inner region of the disc, compared to its highly viscous counterpart, which is radiatively inefficient. With all the solutions in hand, we finally reproduce the observed luminosities of the underfed AGNs and quasars (e. g. Sgr A*) to ultraluminous X-ray sources (e. g. SS433), at different combinations of input parameters, such as the mass accretion rate and the ratio of specific heats. The set of solutions also predicts appropriately the luminosity observed in highly luminous AGNs and ultraluminous quasars (e. g. PKS 0743-67).

Zr4+ doping in Li4Ti5O12 anode for lithium-ion batteries: Open Li+ diffusion paths through structural imperfection

One-dimensional nanomaterials have short Li+ diffusion paths and promising structural stability, which results in a long cycle life during Li+ insertion and extraction processes in lithium rechargeable batteries. In this study, we fabricated one-dimensional spinel Li 4Ti5O12 (LTO) nanofibers using an electrospinning technique and studied the Zr4+ doping effect on the lattice, electronic structure, and resultant electrochemical properties of Li-ion batteries (LIBs). Accommodating a small fraction of Zr4+ ions in the Ti4+ sites of the LTO structure gave rise to enhanced LIB performance, which was due to structural distortion through an increase in the average lattice constant and thereby enlarged Li+ diffusion paths rather than changes to the electronic structure. Insulating ZrO2 nanoparticles present between the LTO grains due to the low Zr4+ solubility had a negative effect on the Li+ extraction capacity, however. These results could provide key design elements for LTO anodes based on atomic level insights that can pave the way to an optimal protocol to achieve particular functionalities. Distorted lattice: Zr4+ is doped into a 1 D spinel Li4Ti5O12 (LTO) nanostructure and the resulting electrochemical properties are explored through a combined theoretical and experimental investigation. The improved electrochemical performance resulting from incorporation of Zr4+ in the LTO is due to lattice distortion and, thereby, enlarged Li+ diffusion paths rather than to a change in the electronic structure.