Study on the structure and vibrational spectra of efavirenz conformers using DFT: Comparison to experimental data

Efavirenz, (S)-6-chloro-4-(cyclopropylethynyl)-1,4-dihydro-4-(trifluoromethyl)-2H-3 ,1-benzoxazin-2-one, is an anti HIV agent belonging to the class of the non-nucleoside inhibitors of the HIV-1 virus reverse transcriptase. A systematic quantum chemical study of the possible conformations, their relative stabilities and vibrational spectra of efavirenz has been reported. Structural and spectral characteristics of efavirenz have been studied by vibrational spectroscopy and quantum chemical methods. Density functional theory (DFT) calculations for potential energy curve, optimized geometries and vibrational spectra have been carried out using 6-311++G(d,p) basis sets and B3LYP functionals. Based on these results, we have discussed the correlation between the vibrational modes and the crystalline structure of the most stable form of efavirenz. A complete analysis of the experimental infrared and Raman spectra has been reported on the basis of wavenumber of the vibrational bands and potential energy distribution. The infrared and the Raman spectra of the molecule based on OFT calculations show reasonable agreement with the experimental results. The calculated HOMO and LUMO energies shows that charge transfer occur within the molecule. (C) 2011 Elsevier B.V. All rights reserved.

Experimental Studies on High-Pressure Spray Structure of Biofuels

The high-pressure spray characteristics of biofuels, specifically, Pongamia oil and its blends with diesel are studied for various gas pressures. Two single-hole solenoid injectors with nozzle diameters of 200 and 260 mu m are used along with a high-pressure common-rail direct-injection system to inject fuel into a high-pressure spray visualization chamber. The spray structure is characterized using a high-speed laser-based shadowgraphy technique. The spray structure of Pongamia oil revealed the presence of an intact liquid core at low gas pressure. At high gas pressures, the spray atomization of the Pongamia oil showed marked improvement. The spray tip penetration of Pongamia oil and its blends with diesel is higher compared to that of diesel for all test conditions. The spray cone angle of Pongamia oil and 50% Pongamia oil blend with diesel is lower as compared to that of diesel. Both these observations are attributed to the presence of large droplets carrying higher momentum in oil and blend. The droplet size is measured at an injection pressure of 1000 bar and gas pressure of 30 bar at 25 mm below the nozzle tip using the particle/droplet image.analysis (PDIA) method. The droplet size measurements have shown that the Sauter mean diameter (SMD) in the spray core of Pongamia oil is more than twice that of diesel. The spray tip penetration of the 20% blend of Pongamia with diesel (P20) is similar to that of diesel but the SMD is 50% higher. Based on experimental data, appropriate spray tip penetration correlation is proposed for the vegetable oil fuels such as Pongamia.

Experimental and Theoretical Studies of Unusual Four-Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)-acetylene Complexes with the Sulfurdiimide Me3SiN=S=NSiMe3

The use of the sulfurdiimide RN=S=NR' (R = R' = SiMe3, 3) in reactions with group 4 metallocene bis(trimethylsilyl)-acetylene complexes of the type [Cp2M(L (eta(2)-Me3Si-C2SiMe3)] (1: M = Ti, no L; 2: M = Zr, L = pyridine) has led to the formation of four-membered metallacycles 4M containing the group 4 metal, nitrogen and sulfur. DFT calculations performed on compound 4Ti indicate that this complex is best described as a sigma-complex with cyclic delocalisation of the ring electrons. Moreover, pseudo-Jahn-Teller distortion plays a significant role in stabilising this complex.

Measurement and Applications of Long-Range Heteronuclear Scalar Couplings: Recent Experimental and Theoretical Developments

The use of long-range heteronuclear couplings, in association with 1H1H scalar couplings and NOE restraints, has acquired growing importance for the determination of the relative stereochemistry, and structural and conformational information of organic and biological molecules. However, the routine use of such couplings is hindered by the inherent difficulties in their measurement. Prior to the advancement in experimental techniques, both long-range homo- and heteronuclear scalar couplings were not easily accessible, especially for very large molecules. The development of a large number of multidimensional NMR experimental methodologies has alleviated the complications associated with the measurement of couplings of smaller strengths. Subsequent application of these methods and the utilization of determined J-couplings for structure calculations have revolutionized this area of research. Problems in organic, inorganic and biophysical chemistry have also been solved by utilizing the short- and long-range heteronuclear couplings. In this minireview, we discuss the advantages and limitations of a number of experimental techniques reported in recent times for the measurement of long-range heteronuclear couplings and a few selected applications of such couplings. This includes the study of medium- to larger-sized molecules in a variety of applications, especially in the study of hydrogen bonding in biological systems. The utilization of these couplings in conjunction with theoretical calculations to arrive at conclusions on the hyperconjugation, configurational analysis and the effect of the electronegativity of the substituents is also discussed.

A unified view of the apriori-based algorithms for frequent episode discovery

Frequent episode discovery framework is a popular framework in temporal data mining with many applications. Over the years, many different notions of frequencies of episodes have been proposed along with different algorithms for episode discovery. In this paper, we present a unified view of all the apriori-based discovery methods for serial episodes under these different notions of frequencies. Specifically, we present a unified view of the various frequency counting algorithms. We propose a generic counting algorithm such that all current algorithms are special cases of it. This unified view allows one to gain insights into different frequencies, and we present quantitative relationships among different frequencies. Our unified view also helps in obtaining correctness proofs for various counting algorithms as we show here. It also aids in understanding and obtaining the anti-monotonicity properties satisfied by the various frequencies, the properties exploited by the candidate generation step of any apriori-based method. We also point out how our unified view of counting helps to consider generalization of the algorithm to count episodes with general partial orders.

Dual-Stage Power Management Algorithms for Energy Harvesting Sensors

In this paper, we propose power management algorithms for maximizing the utility of energy harvesting sensors (EHS) that operate purely on the basis of energy harvested from the environment. In particular, we consider communication (i.e., transmission and reception) power management issues for EHS under an energy neutrality constraint. We also consider the fixed power loss effects of the circuitry, the battery inefficiency and its storage capacity, in the design of the algorithms. We propose a two-stage structure that exploits the inherent difference in the timescales at which the energy harvesting and channel fading processes evolve, without loss of optimality of the resulting solution. The outer stage schedules the power that can be used by an inner stage algorithm, so as to maximize the long term average utility and at the same time maintain energy neutrality. The inner stage optimizes the communication parameters to achieve maximum utility in the short-term, subject to the power constraint imposed by the outer stage. We optimize the algorithms for different transmission schemes such as the truncated channel inversion and retransmission strategies. The performance of the algorithms is illustrated via simulations using solar irradiance data, and for the case of Rayleigh fading channels. The results demonstrate the significant performance benefits that can be obtained using the proposed power management algorithms compared to the energy efficient (optimum when there is no storage) and the uniform power consumption (optimum when the battery has infinite capacity and is perfectly efficient) approaches.

Applying Genetic Algorithms to Optimize Power in Tiled SNUCA Chip Multicore Architectures

We propose a novel technique for reducing the power consumed by the on-chip cache in SNUCA chip multicore platform. This is achieved by what we call a "remap table", which maps accesses to the cache banks that are as close as possible to the cores, on which the processes are scheduled. With this technique, instead of using all the available cache, we use a portion of the cache and allocate lesser cache to the application. We formulate the problem as an energy-delay (ED) minimization problem and solve it offline using a scalable genetic algorithm approach. Our experiments show up to 40% of savings in the memory sub-system power consumption and 47% savings in energy-delay product (ED).

Applying Genetic Algorithms to Optimize Power in Tiled SNUCA Chip Multicore Architectures

We propose a novel technique for reducing the power consumed by the on-chip cache in SNUCA chip multicore platform. This is achieved by what we call a "remap table", which maps accesses to the cache banks that are as close as possible to the cores, on which the processes are scheduled. With this technique, instead of using all the available cache, we use a portion of the cache and allocate lesser cache to the application. We formulate the problem as an energy-delay (ED) minimization problem and solve it offline using a scalable genetic algorithm approach. Our experiments show up to 40% of savings in the memory sub-system power consumption and 47% savings in energy-delay product (ED).

Compiler-assisted energy optimization for clustered VLIW processors

Clustered architecture processors are preferred for embedded systems because centralized register file architectures scale poorly in terms of clock rate, chip area, and power consumption. Although clustering helps by improving the clock speed, reducing the energy consumption of the logic, and making the design simpler, it introduces extra overheads by way of inter-cluster communication. This communication happens over long global wires having high load capacitance which leads to delay in execution and significantly high energy consumption. Inter-cluster communication also introduces many short idle cycles, thereby significantly increasing the overall leakage energy consumption in the functional units. The trend towards miniaturization of devices (and associated reduction in threshold voltage) makes energy consumption in interconnects and functional units even worse, and limits the usability of clustered architectures in smaller technologies. However, technological advancements now permit the design of interconnects and functional units with varying performance and power modes. In this paper, we propose scheduling algorithms that aggregate the scheduling slack of instructions and communication slack of data values to exploit the low-power modes of functional units and interconnects. Finally, we present a synergistic combination of these algorithms that simultaneously saves energy in functional units and interconnects to improves the usability of clustered architectures by achieving better overall energy-performance trade-offs. Even with conservative estimates of the contribution of the functional units and interconnects to the overall processor energy consumption, the proposed combined scheme obtains on average 8% and 10% improvement in overall energy-delay product with 3.5% and 2% performance degradation for a 2-clustered and a 4-clustered machine, respectively. We present a detailed experimental evaluation of the proposed schemes. Our test bed uses the Trimaran compiler infrastructure. (C) 2012 Elsevier Inc. All rights reserved.