Aromatic claisen rearrangements in carbohydrates: stereocontrol of rearrangement rates in unsaturated sugar substrates

A remarkable difference is observed in the rates of [3,3]-sigmatropic rearrangement of aryl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranosides 1 and 2; the slower reactivity of the alpha-isomers is consistent with AM1 calculated transition state energetics of model systems.

Prediction of reaeration rates in square, stirred tanks

Experiments were conducted on the oxygen transfer coefficient, k(L)a(20), through surface aeration in geometrically similar square tanks, with a rotor of diameter D fitted with six flat blades. An optimal geometric similarity of various linear dimensions, which produced maximum k(L)a(20) for any rotational speed of rotor N by an earlier study, was maintained. A simulation equation uniquely correlating k = k(L)a(20)(nu/g(2))(1/3) (nu and g are kinematic viscosity of water and gravitational constant, respectively), and a parameter governing the theoretical power per unit volume, X = (ND2)-D-3/(g(4/3)nu(1/3)), is developed. Such a simulation equation can be used to predict maximum k for any N in any size of such geometrically similar square tanks. An example illustrating the application of results is presented. Also, it has been established that neither the Reynolds criterion nor the Froude criterion is singularly valid to simulate either k or K = k(L)a(20)/N, simultaneously in all the sizes of tanks, even through they are geometrically similar. Occurrence of "scale effects" due to the Reynolds and the Froude laws of similitude on both k and K are also evaluated.

Analysis of Strain Rates and Microstructural Evaluation during Metal Forming: Role of Surface Texture and Friction

The surface texture of a die plays an important role in friction during metal forming. In the present study, unidirectional and random surface finishes were produced on hardened steel plate surfaces. To understand the influence of surface texture on friction, experiments were conducted using Al-Mg alloy pins that slid against steel plates of different surface textures. In the sliding experiments, a high coefficient of friction was observed when the pins slid perpendicular to the unidirectional grinding marks and low friction occurred when the pins slid on the random surfaces. Finite element simulations were performed using the measured friction values to understand the stress and strain evolutions in the deforming material using dies with various friction. The numerical results showed that the states of stress and strain rates are strongly influenced by the friction at the interface and hence would influence the final material microstructure. To substantiate the numerical results, laboratory compression tests were conducted. Different surface textures were obtained in order to experience different friction values at different locations. A large variation in the microstructure at these locations was observed during experiments, verifying that surface texture and die friction significantly influence fundamental material formation behavior.

A divide and conquer strategy for scaling weather simulations with multiple regions of interest

Accurate and timely prediction of weather phenomena, such as hurricanes and flash floods, require high-fidelity compute intensive simulations of multiple finer regions of interest within a coarse simulation domain. Current weather applications execute these nested simulations sequentially using all the available processors, which is sub-optimal due to their sub-linear scalability. In this work, we present a strategy for parallel execution of multiple nested domain simulations based on partitioning the 2-D processor grid into disjoint rectangular regions associated with each domain. We propose a novel combination of performance prediction, processor allocation methods and topology-aware mapping of the regions on torus interconnects. Experiments on IBM Blue Gene systems using WRF show that the proposed strategies result in performance improvement of up to 33% with topology-oblivious mapping and up to additional 7% with topology-aware mapping over the default sequential strategy.

Region-of-interest diffuse optical tomography system

Diffuse optical tomography (DOT) using near-infrared light is a promising tool for non-invasive imaging of deep tissue. This technique is capable of quantitative reconstruction of absorption (mu(a)) and scattering coefficient (mu(s)) inhomogeneities in the tissue. The rationale for reconstructing the optical property map is that the absorption coefficient variation provides diagnostic information about metabolic and disease states of the tissue. The aim of DOT is to reconstruct the internal tissue cross section with good spatial resolution and contrast from noisy measurements non-invasively. We develop a region-of-interest scanning system based on DOT principles. Modulated light is injected into the phantom/tissue through one of the four light emitting diode sources. The light traversing through the tissue gets partially absorbed and scattered multiple times. The intensity and phase of the exiting light are measured using a set of photodetectors. The light transport through a tissue is diffusive in nature and is modeled using radiative transfer equation. However, a simplified model based on diffusion equation (DE) can be used if the system satisfies following conditions: (a) the optical parameter of the inhomogeneity is close to the optical property of the background, and (b) mu(s) of the medium is much greater than mu(a) (mu(s) >> mu(a)). The light transport through a highly scattering tissue satisfies both of these conditions. A discrete version of DE based on finite element method is used for solving the inverse problem. The depth of probing light inside the tissue depends on the wavelength of light, absorption, and scattering coefficients of the medium and the separation between the source and detector locations. Extensive simulation studies have been carried out and the results are validated using two sets of experimental measurements. The utility of the system can be further improved by using multiple wavelength light sources. In such a scheme, the spectroscopic variation of absorption coefficient in the tissue can be used to arrive at the oxygenation changes in the tissue. (C) 2016 AIP Publishing LLC.

Long-term Accelerated Multistress Aging of Composite Outdoor Polymeric Insulators

Polymeric outdoor insulators are being increasingly used for electrical power transmission and distribution in the recent years. One of the current topics of interest for the power transmission community is the aging of such outdoor polymeric insulators. A few research groups are carrying out aging studies at room temperature with wet period as an integral part of multistress aging cycle as specified by IEC standards. However, aging effect due to dry conditions alone at elevated temperatures and electric stress in the presence of radiation environment has probably not been explored. It is interesting to study and understand the insulator performance under dry conditions where wet periods are either rare or absent and to estimate the extent of aging caused by multiple stresses. This paper deals with the long-term accelerated multistress aging on full-scale 11 kV distribution class composite silicone rubber insulators. In order to assess the long-term synergistic effect of electric stress, temperature and UV radiation on insulators, they are subjected to accelerated aging in a specially designed multistress-aging chamber for 3800 hours. All the stresses are applied at an accelerated level. Using a data acquisition system developed for the work, leakage current has been monitored in LabVIEW environment. Chemical changes due to degradations have been studied using Energy Dispersive X-Ray analysis, Scanning Electron Microscope and Fourier transform Infrared Spectroscopy. Periodically different parameters like low molecular weight (LMW) molecular content, hydrophobicity, leakage current and surface morphology were monitored. The aging study is under progress and only intermediate results are presented in this paper.

Long-term Accelerated Weathering of Outdoor Silicone Rubber Insulators

Multistress aging/weathering of outdoor composite polymeric insulators has been a topic of interest for power transmission research community in the last few decades. This paper deals with the long-term accelerated weathering of full-scale distribution class silicone rubber composite insulators. To evaluate the long-term synergistic effect of electric stress, temperature and UV radiation on insulators, they were subjected to accelerated weathering in a specially designed multistress-aging chamber for 30,000 h. All the insulators were subjected to the same level of electrical and thermal stresses but different UV radiation levels. Chemical, physical and electrical changes due to degradation have been assessed using various techniques. It was found that there was a monotonous reduction of the content of low molecular weight (LMW) molecules with the duration of the weathering. Further, due to oxidation and weathering there is an appreciable increase in surface roughness and atomic percentage of oxygen. There is no change in the leakage current of new and aged insulators under both wet and dry conditions at the end of the aging. The results also indicate that there is no influence of UV radiation on the silicone rubber for the durations and conditions under which the studies were made.

On the achievable rates of sources having a group alphabet in a distributed source coding setting

We consider the problem of compression via homomorphic encoding of a source having a group alphabet. This is motivated by the problem of distributed function computation, where it is known that if one is only interested in computing a function of several sources, then one can at times improve upon the compression rate required by the Slepian-Wolf bound. The functions of interest are those which could be represented by the binary operation in the group. We first consider the case when the source alphabet is the cyclic Abelian group, Zpr. In this scenario, we show that the set of achievable rates provided by Krithivasan and Pradhan [1], is indeed the best possible. In addition to that, we provide a simpler proof of their achievability result. In the case of a general Abelian group, an improved achievable rate region is presented than what was obtained by Krithivasan and Pradhan. We then consider the case when the source alphabet is a non-Abelian group. We show that if all the source symbols have non-zero probability and the center of the group is trivial, then it is impossible to compress such a source if one employs a homomorphic encoder. Finally, we present certain non-homomorphic encoders, which also are suitable in the context of function computation over non-Abelian group sources and provide rate regions achieved by these encoders.

Numerical prediction of load-displacement behaviors of adhesively bonded joints at different extension rates and temperatures

The present work focuses on simulation of nonlinear mechanical behaviors of adhesively bonded DLS (double lap shear) joints for variable extension rates and temperatures using the implicit ABAQUS solver. Load-displacement curves of DLS joints at nine combinations of extension rates and environmental temperatures are initially obtained by conducting tensile tests in a UTM. The joint specimens are made from dual phase (DP) steel coupons bonded with a rubber-toughened adhesive. It is shown that the shell-solid model of a DLS joint, in which substrates are modeled with shell elements and adhesive with solid elements, can effectively predict the mechanical behavior of the joint. Exponent Drucker-Prager or Von Mises yield criterion together with nonlinear isotropic hardening is used for the simulation of DLS joint tests. It has been found that at a low temperature (-20 degrees C), both Von Mises and exponent Drucker-Prager criteria give close prediction of experimental load-extension curves. However. at a high temperature (82 degrees C), Von Mises condition tends to yield a perceptibly softer joint behavior, while the corresponding response obtained using exponent Drucker-Prager criterion is much closer to the experimental load-displacement curve.

Accelerated Multistress Aging of Outdoor Polymeric Insulators

Multistress aging of outdoor composite polymeric insulators continues to be a topic of interest for power transmission research community. Aging due to dry conditions alone at elevated temperatures and electric stress in the presence of UV radiation environment probably has not been explored. This paper deals with long-term accelerated multistress aging under the above conditions on full-scale 11 kV distribution class composite silicone rubber insulators. To evaluate the long-term synergistic effect of electric stress, temperature and UV radiation on insulators, they were subjected to accelerated aging in a specially designed multistress-aging chamber for 12000 hours. Chemical, physical and electrical changes due to degradation have been assessed using various techniques. It has been found that the content of low molecular weight molecules and hydrophobicity reduced significantly. Also, due to oxidation and aging there is appreciable increase in surface roughness and weight percentage of oxygen. Study is under progress and only intermediate results are presented in this paper.

A new kinetic model for bulk polymerization of vinyl chloride based on two-phase hypothesis

A kinetic model has been developed for the bulk polymerization of vinyl chloride using Talamini's hypothesis of two-phase polymerization and a new concept of kinetic solubility which assumes that rapidly growing polymer chains have considerably greater solubility than the thermodynamic solubility of preformed polymer molecules of the same size and so can remain in solution even under thermodynamically unfavourable conditions. It is further assumed that this kinetic solubility is a function of chain length. The model yields a rate expression consistent with the experimental data for vinyl chloride bulk polymerization and moreover is able to explain several characteristic kinetic features of this system. Application of the model rate expression to the available rate data has yielded 2.36 × 108l mol−1 sec−1 for the termination rate constant in the polymer-rich phase; as expected, this value is smaller than that reported for homogenous polymerization by a factor of 10–30.

BER analysis of space-time block codes from generalized complex orthogonal designs for M-PSK

In this paper, we present an analysis for the bit error rate (BER) performance of space-time block codes (STBC) from generalized complex orthogonal designs for M-PSK modulation. In STBCs from complex orthogonal designs (COD), the norms of the column vectors are the same (e.g., Alamouti code). However, in generalized COD (GCOD), the norms of the column vectors may not necessarily be the same (e.g., the rate-3/5 and rate-7/11 codes by Su and Xia in [1]). STBCs from GCOD are of interest because of the high rates that they can achieve (in [2], it has been shown that the maximum achievable rate for STBCs from GCOD is bounded by 4/5). While the BER performance of STBCs: from COD (e.g., Alamouti code) can be simply obtained from existing analytical expressions for receive diversity with the same diversity order by appropriately scaling the SNR, this can not be done for STBCs from GCOD (because of the unequal norms of the column vectors). Our contribution in this paper is that we derive analytical expressions for the BER performance of any STBC from GCOD. Our BER analysis for the GCOD captures the performance of STBCs from COD as special cases. We validate our results with two STBCs from GCOD reported by Su and Xia in [1], for 5 and 6 transmit antennas (G(5) and G(6) in [1]) with rates 7/11 and 3/5, respectively.

BER analysis of space-time block codes from generalized complex orthogonal designs for M-PSK

In this paper, we present an analysis for the bit error rate (BER) performance of space-time block codes (STBC) from generalized complex orthogonal designs for M-PSK modulation. In STBCs from complex orthogonal designs (COD), the norms of the column vectors are the same (e.g., Alamouti code). However, in generalized COD (GCOD), the norms of the column vectors may not necessarily be the same (e.g., the rate-3/5 and rate-7/11 codes by Su and Xia in [1]). STBCs from GCOD are of interest because of the high rates that they can achieve (in [2], it has been shown that the maximum achievable rate for STBCs from GCOD is bounded by 4/5). While the BER performance of STBCs: from COD (e.g., Alamouti code) can be simply obtained from existing analytical expressions for receive diversity with the same diversity order by appropriately scaling the SNR, this can not be done for STBCs from GCOD (because of the unequal norms of the column vectors). Our contribution in this paper is that we derive analytical expressions for the BER performance of any STBC from GCOD. Our BER analysis for the GCOD captures the performance of STBCs from COD as special cases. We validate our results with two STBCs from GCOD reported by Su and Xia in [1], for 5 and 6 transmit antennas (G(5) and G(6) in [1]) with rates 7/11 and 3/5, respectively.

BER analysis of space-time block codes from generalized complex orthogonal designs for M-PSK

In this paper, we present an analysis for the bit error rate (BER) performance of space-time block codes (STBC) from generalized complex orthogonal designs for M-PSK modulation. In STBCs from complex orthogonal designs (COD), the norms of the column vectors are the same (e.g., Alamouti code). However, in generalized COD (GCOD), the norms of the column vectors may not necessarily be the same (e.g., the rate-3/5 and rate-7/11 codes by Su and Xia in [1]). STBCs from GCOD are of interest because of the high rates that they can achieve (in [2], it has been shown that the maximum achievable rate for STBCs from GCOD is bounded by 4/5). While the BER performance of STBCs: from COD (e.g., Alamouti code) can be simply obtained from existing analytical expressions for receive diversity with the same diversity order by appropriately scaling the SNR, this can not be done for STBCs from GCOD (because of the unequal norms of the column vectors). Our contribution in this paper is that we derive analytical expressions for the BER performance of any STBC from GCOD. Our BER analysis for the GCOD captures the performance of STBCs from COD as special cases. We validate our results with two STBCs from GCOD reported by Su and Xia in [1], for 5 and 6 transmit antennas (G(5) and G(6) in [1]) with rates 7/11 and 3/5, respectively.

Distributed Storage Codes With Repair-by-Transfer and Nonachievability of Interior Points on the Storage-Bandwidth Tradeoff

Regenerating codes are a class of recently developed codes for distributed storage that, like Reed-Solomon codes, permit data recovery from any subset of k nodes within the n-node network. However, regenerating codes possess in addition, the ability to repair a failed node by connecting to an arbitrary subset of d nodes. It has been shown that for the case of functional repair, there is a tradeoff between the amount of data stored per node and the bandwidth required to repair a failed node. A special case of functional repair is exact repair where the replacement node is required to store data identical to that in the failed node. Exact repair is of interest as it greatly simplifies system implementation. The first result of this paper is an explicit, exact-repair code for the point on the storage-bandwidth tradeoff corresponding to the minimum possible repair bandwidth, for the case when d = n-1. This code has a particularly simple graphical description, and most interestingly has the ability to carry out exact repair without any need to perform arithmetic operations. We term this ability of the code to perform repair through mere transfer of data as repair by transfer. The second result of this paper shows that the interior points on the storage-bandwidth tradeoff cannot be achieved under exact repair, thus pointing to the existence of a separate tradeoff under exact repair. Specifically, we identify a set of scenarios which we term as ``helper node pooling,'' and show that it is the necessity to satisfy such scenarios that overconstrains the system.