Vibrational assignments of five-membered heterocyclic compounds. Normal vibrations of oxazolidine-2-one and -2-thione

Infrared spectra of oxazolidine-2-one (Oxo), -2-thione (Oxt) and their N-deuteriated derivatives have been measured over the range 4000-20 cm−1. The fundamental frequencies of these molecules have been assigned on the basis of normal coordinate calculations carried out using a Urey-Bradley potential function supplemented with valence type constants for the out-of-plane modes of the planar skeleton. The results of the vibrational analyses are discussed and correlated with the assignments available for the other related five membered heterocyclic molecules.

Understanding solvent effects on structure and reactivity of organic intermediates: a Raman study

The effect of solvent on chemical reactivity has generally been explained on the basis of the dielectric constant and viscosity. However a number of spectroscopic studies, including UV-VIS, IR and Raman, has led to numerous empirical parameters to define solvent effect based on either solvating ability or polarity scale. These parameters include solvent polarizability, dipolarity, Lewis acidity and Lewis basicity, E-T(30), pi*, alpha, beta etc. However, from a structural point of view, we can separate solvation as static and dynamic processes. The static solvation basically relates to stabilization of the molecular structure by the solvent to attain the equilibrium structure, both in the intermediate and ground state. Dynamic solvation relates to solvent reorganization-induced dynamics prior to the structural reorganization to reach the equilibrium state. In this paper, we present (a) structural distortions induced by the solvent due to preferential solvation of the triplet excited state, and (b) the importance of dynamic solvation induced by vibronic coupling (pseudo-Jahn-Teller coupling). The examples include the effect of solvent on structure and reactivity of excited states of 2,2,2-trifluoroacetophenone (TFA). Based on the comparison of time resolved resonance Raman (TR3) data of TFA and other substituted acetophenone systems, it was found that change in solvent polarity indeed results in electronic state switching and structural changes in the excited state, which explains the trend in reactivity. Further, a TR3 study of fluoranil (FA) in the triplet excited state in solvents of varying polarities indicates that the structure of FA in the triplet excited state is determined by vibronic coupling effects and thus distorted structure. These experimental results have been well supported by density functional theoretical computational studies.

Drive current boosting of n-type tunnel FET with strained SiGe layer at source

Though silicon tunnel field effect transistor (TFET) has attracted attention for sub-60 mV/decade subthreshold swing and very small OFF current (IOFF), its practical application is questionable due to low ON current (ION) and complicated fabrication process steps. In this paper, a new n-type classical-MOSFET-alike tunnel FET architecture is proposed, which offers sub-60 mV/decade subthreshold swing along with a significant improvement in ION. The enhancement in ION is achieved by introducing a thin strained SiGe layer on top of the silicon source. Through 2D simulations it is observed that the device is nearly free from short channel effect (SCE) and its immunity towards drain induced barrier lowering (DIBL) increases with increasing germanium mole fraction. It is also found that the body bias does not change the drive current but after body current gets affected. An ION of View the MathML source and a minimum average subthreshold swing of 13 mV/decade is achieved for 100 nm channel length device with 1.2 V supply voltage and 0.7 Ge mole fraction, while maintaining the IOFF in fA range.

Comparative measurements of HV impulses to evaluate different sets of response parameters

Results are reported of comparative measurements made in 14 HV (high-voltage) laboratories in ten different countries. The theory of the proposed methods of characterizing the dynamic behavior is given, and the parameters to be used are discussed. Comparative measurements made using 95 systems based on 53 dividers are analyzed. This analysis shows that many of the system now in use, even though they fulfil the basic response requirements of the standards, do not meet the accuracy requirements. Because no transfer measurements were made between laboratories, there is no way to detect similar errors in both the system under test and the reference system. Hence, the situation may be worse than reported. This has led to the recommendation that comparative measurements should be the main route for quantifying industrial impulse measuring systems

Synthesis of Trilaurin by Developing Pisa Seeds (Actinodaphne hookeri)

The developing seeds of Actinodaphne hookeri were investigated to delineate their ability to synthesize large amounts of trilaurin. Until 88 days after flowering the embryos contained 71% neutral lipids (NL) and 29% phospholipids (PL) and both these components contained C-16:0, C-18:0, C-18:2, and C-18:3 as the major fatty acids (FA). At 102 days after flowering the seeds began to accumulate triacylglycerols (TAG) and to synthesize lauric acid (C-12:0). By 165 days after flowering, when the seeds were mature, they contained about 99% NL and 1% FL. At this stage the TAG contained exclusively C-12:0, while the PL consisted of long-chain fatty acids (LCFA) only. Leaf lipids in contrast did not contain any C-12:0. Experiments on [1-C-14]acetate incorporation into developing seed slices showed that at 88 days after flowering only 4% of the label was in TAG, 1% in diacylglycerols (DAG), and 87% in FL. One hundred two days after flowering seeds incorporated only 2% of the label into TAG, 30% into DAG, and 64% into FL. In contrast at 114 days after flowering 71% of the label was incorporated into TAG, 25% into DAG, and only 2% into FL. Analysis of labeled FA revealed that up to 102 days after flowering it was incorporated only into LCFA, whereas at 114 days after flowering it was incorporated exclusively into C-12:0. Furthermore, 67% of the label in PL at 114 days after flowering was found to be dilaurylglycerophosphate. Analysis of the label in DAG at this stage showed that it was essentially in dilaurin species. These observations indicate the induction of enzymes of Kennedy pathway for the specific synthesis of trilaurin at about 114 days after flowering, Homogenates of seeds (114 days after flowering) incubated with labeled FA in the presence of glycerol-3-phosphate and coenzymes A and ATP incorporated 84% of C-12:0 and 61% of C-14:0, but not C-16:0, C-18:2, and C-18:3, into TAG. In contrast the LCFA were incorporated preferentially into FL. It is concluded that, between 102 and 114 days after flowering, a switch occurs in A. hookeri for the synthesis of C-12:0 and trilaurin which is tissue specific. Since the seed synthesizes exclusively C-12:0 at 114 days after flowering onwards and incorporates specifically into TAG, this system appears to be ideal for identifying the enzymes responsible for medium-chain fatty acid as well as trilaurin synthesis and for exploiting them for genetic engineering. (C) 1994 Academic Press, Inc.

Diurnal variation of atmospheric CO2 concentration and delta C-13 in an urban atmosphere during winter-role of the Nocturnal Boundary Layer

The paper presents the importance of the Nocturnal Boundary Layer in driving the diurnal variability of the atmospheric CO2 mixing ratio and the carbon isotope ratio at ground level from an urban station in India. Our observations are the first of their kind from this region. The atmospheric CO2 mixing ratio and the carbon isotopic ratio were measured for both the morning (05:30-07:30 IST) and afternoon time (16:00-18:00 IST) air samples at 5 m above ground level in Bangalore city, Karnataka State (12 degrees 58' N, 77 degrees 38' E, masl = 920 m) for a 10 day period during the winter of 2008. We observed a change of similar to 7% the in CO2 mixing ratio between the morning and afternoon time air samples. A stable isotope analysis of CO2 from morning samples showed a depletion in the carbon isotope ratio by similar to 2 parts per thousand compared to the afternoon samples. Along with the ground-based measurement of air samples, data of radiosonde measurements were also obtained from the Indian Meteorological Department to identify the vertical atmospheric structure at different time in a day. We proposed the presence or absence of the NBL as a controlling factor for the observed variability in the mixing ratio as well as its isotopic composition. Here we used the Keeling model approach to find out the carbon isotope ratio for the local sources. The local sources have further been characterized as anthropogenic and biological respiration (in %) using a two-component mixing model. We also used a vertical mixing model based on the concept of the mixing of isotopically depleted (carbon isotope) ``polluted air'' (PA) with isotopically enriched ``free atmospheric air'' (FA) above. Using this modeling approach, the contribution of FA at ground level is being estimated for both the morning and afternoon time air samples.

``Clickable'', Trifunctional Magnetite Nanoparticles and Their Chemoselective Biofunctionalization

A multifunctional iron oxide based nanoformulation for combined cancer-targeted therapy and multimodal imaging has been meticulously designed and synthesized using a chemoselective ligation approach. Novel superparamagnetic magnetite nanoparticles simultaneously functionalized with amine, carboxyl, and azide groups were fabricated through a sequence of stoichiometrically controllable partial succinylation and Cu (II) catalyzed diazo transfer on the reactive amine termini of 2-aminoethylphosphonate grafted magnetite nanoparticles (MNPs). Functional moieties associated with MNP surface were chemoselectively conjugated with rhodamine B isothiocyanate (RITC), propargyl folate (FA), and paclitaxel (PTX) via tandem nucleophic addition of amine to isothithiocyanates, Cu (I) catalyzed azide-alkyne click chemistry and carbodiimide-promoted esterification. An extensive in vitro study established that the bioactives chemoselectively appended to the magnetite core bequeathed multifunctionality to the nanoparticles without any loss of activity of the functional molecules. Multifunctional nanoparticles, developed in the course of the study, could selectively target and induce apoptosis to folate-receptor (FR) overexpressing cancer cells with enhanced efficacy as compared to the free drug. In addition, the dual optical and magnetic properties of the synthesized nanoparticles aided in the real-time tracking of their intracellular pathways also as apoptotic events through dual fluorescence and MR-based imaging.

Time delay to firing of a triggered vacuum gap with barium titanate in trigger gap

The time delay to the firing of a triggered vacuum gap (t.v.g.) containing barium titanate in the trigger gap is investigated as a function of the main gap voltage, main gap length, trigger pulse duration, trigger current and trigger voltage. The time delay decreases steadily with increasing trigger current and trigger voltage until it reaches saturation. The effect of varying the main gap length and voltage on the time delay is not strong. Before `conditioning�¿ the t.v.g. two groups of time delays, long (>100�¿s) and short (<10�¿s), are simultaneously observed when a large number of trials are conducted. After conditioning, only the group of short time delays are present. This is attributed to the marked reduction of the resistance of the trigger gap across the surface of the solid dielectric resulting directly from the conditioning effect.

Distinct Roles of FANCO/RAD51C Protein in DNA Damage Signaling and Repair Implications for Fanconi Anemia and Breast Cancer Susceptibility

RAD51C, a RAD51 paralog, has been implicated in homologous recombination (HR), and germ line mutations in RAD51C are known to cause Fanconi anemia (FA)-like disorder and breast and ovarian cancers. The role of RAD51C in the FA pathway of DNA interstrand cross-link (ICL) repair and as a tumor suppressor is obscure. Here, we report that RAD51C deficiency leads to ICL sensitivity, chromatid-type errors, and G(2)/M accumulation, which are hallmarks of the FA phenotype. We find that RAD51C is dispensable for ICL unhooking and FANCD2 monoubiquitination but is essential for HR, confirming the downstream role of RAD51C in ICL repair. Furthermore, we demonstrate that RAD51C plays a vital role in the HR-mediated repair of DNA lesions associated with replication. Finally, we show that RAD51C participates in ICL and double strand break-induced DNA damage signaling and controls intra-S-phase checkpoint through CHK2 activation. Our analyses with pathological mutants of RAD51C that were identified in FA and breast and ovarian cancers reveal that RAD51C regulates HR and DNA damage signaling distinctly. Together, these results unravel the critical role of RAD51C in the FA pathway of ICL repair and as a tumor suppressor.

Assessment of the Relationships Among Design Methods, Design Activities, and Creativity

This paper presents an experimental study that was conducted to compare the results obtained from using different design methods (brainstorming (BR), functional analysis (FA), and SCAMPER) in design processes. The objectives of this work are twofold. The first was to determine whether there are any differences in the length of time devoted to the different types of activities that are carried out in the design process, depending on the method that is employed; in other words, whether the design methods that are used make a difference in the profile of time spent across the design activities. The second objective was to analyze whether there is any kind of relationship between the time spent on design process activities and the degree of creativity in the solutions that are obtained. Creativity evaluation has been done by means of the degree of novelty and the level of resolution of the designed solutions using creative product semantic scale (CPSS) questionnaire. The results show that there are significant differences between the amounts of time devoted to activities related to understanding the problem and the typology of the design method, intuitive or logical, that are used. While the amount of time spent on analyzing the problem is very small in intuitive methods, such as brainstorming and SCAMPER (around 8-9% of the time), with logical methods like functional analysis practically half the time is devoted to analyzing the problem. Also, it has been found that the amount of time spent in each design phase has an influence on the results in terms of creativity, but results are not enough strong to define in which measure are they affected. This paper offers new data and results on the distinct benefits to be obtained from applying design methods. DOI: 10.1115/1.4007362]

Surface modification and paclitaxel drug delivery of folic acid modified polyethylene glycol functionalized hydroxyapatite nanoparticles

Nanoparticles are used for a number of biomedical applications. In this work we report the synthesis of folic acid (FA) modified polyethylene glycol (PEG) functionalized hydroxyapatite (HAp) nanoparticles. The anticancer drug, paclitaxel, is attached to the folic acid modified polyethylene glycol functionalized hydroxyapatite nanoparticles and the in vitro drug release is analyzed. The surface modification and functionalization is confirmed by Fourier transform infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA) and UV spectroscopy. The importance of the paper is the investigation of the release behavior of paclitaxel conjugated folic acid modified polyethylene glycol functionalized hydroxyapatite nanoparticles. The results show an initial rapid release and then a sustained release. (C) 2012 Elsevier B.V. All rights reserved.

Role of Fly Ash Pozzolanic Reactions in Controlling Fluoride Release from Phosphogypsum

Phosphogypsum is added to building materials to accelerate fly ash pozzolanic reaction and contributes to early strength development of concrete. The release of unacceptable fluoride levels by phoshogypsum on contact with water is a major impediment in its usage to manufacture building products because excess fluoride consumption causes dental and skeletal fluorosis. This paper examines the efficacy of fly ash pozzolanic reactions in controlling fluoride release by phosphogypsum. Fly ash (FA), sand (S), lime (L), and phosphogypsum (G) (FA-S-L-G) slurries are cured for various periods, and the fluoride released by the mix is monitored as a function of time. A substantial reduction in fluoride release was observed and is attributed to entrapment of phosphogypsum particles in a cementious matrix formed by fly ash-lime pozzolanic reactions coupled with consumption of fluoride in formation of insoluble compounds. The compressive strength developed by compacted FA-S-L-G specimens with time was observed to be a three-stage process; maximum strength mobilization occurred during 14 and 28days of curing at room temperature. Exposure of the compacted FA-S-L-G specimens to acidic and alkaline environments for 9 days did not impact their compressive strengths. (C) 2013 American Society of Civil Engineers.

Flexibility in flapping foil suppresses meandering of induced jet in absence of free stream

Thrust-generating flapping foils are known to produce jets inclined to the free stream at high Strouhal numbers St = fA/U-infinity, where f is the frequency and A is the amplitude of flapping and U-infinity is the free-stream velocity. Our experiments, in the limiting case of St —> infinity (zero free-stream speed), show that a purely oscillatory pitching motion of a chordwise flexible foil produces a coherent jet composed of a reverse Benard-Karman vortex street along the centreline, albeit over a specific range of effective flap stiffnesses. We obtain flexibility by attaching a thin flap to the trailing edge of a rigid NACA0015 foil; length of flap is 0.79 c where c is rigid foil chord length. It is the time-varying deflections of the flexible flap that suppress the meandering found in the jets produced by a pitching rigid foil for zero free-stream condition. Recent experiments (Marais et al., J. Fluid Mech., vol. 710, 2012, p. 659) have also shown that the flexibility increases the St at which non-deflected jets are obtained. Analysing the near-wake vortex dynamics from flow visualization and particle image velocimetry (PIV) measurements, we identify the mechanisms by which flexibility suppresses jet deflection and meandering. A convenient characterization of flap deformation, caused by fluid-flap interaction, is through a non-dimensional effective stiffness', EI* = 8 EI/(rho V-TEmax(2) s(f) c(f)(3)/2), representing the inverse of the flap deflection due to the fluid-dynamic loading; here, EI is the bending stiffness of flap, rho is fluid density, V-TEmax is the maximum velocity of rigid foil trailing edge, s(f) is span and c(f) is chord length of the flexible flap. By varying the amplitude and frequency of pitching, we obtain a variation in EI* over nearly two orders of magnitude and show that only moderate EI*. (0.1 less than or similar to EI * less than or similar to 1 generates a sustained, coherent, orderly jet. Relatively `stiff' flaps (EI* greater than or similar to 1), including the extreme case of no flap, produce meandering jets, whereas highly `flexible' flaps (EI* less than or similar to 0.1) produce spread-out jets. Obtained from the measured mean velocity fields, we present values of thrust coefficients for the cases for which orderly jets are observed.

X-Ha center dot center dot center dot C hydrogen bonds in n-alkane-HX (X = F, OH) complexes are stronger than C-Ha <-X hydrogen bonds

Computational study of X-Ha <-C and C-Ha <-X hydrogen bonds in n-alkane-HX complexes (X =F,OH, alkane =propane, butane, pentane) has been carried out in this work. Ab initio and density functional theories were used for this study. For n-alkane-H2O complexes both Oa <-H-C and O-Ha <-C hydrogen bonded complex have been found, while for n-alkane-HF complexes, our attempt to optimize Fa <-H-C H-bond was not successful. Like most of the hydrogen bonded systems, strong correlation between binding energy and stretching frequency of H-F and O-H stretching mode was observed. The values of electron density and Laplacian of electron density are within the accepted range for hydrogen bonds. In all these cases, X-Ha <-C hydrogen bonds are found to be stronger than C-Ha <-X hydrogen bonds.

Mammalian RAD51 paralogs protect nascent DNA at stalled forks and mediate replication restart

Mammalian RAD51 paralogs are implicated in the repair of collapsed replication forks by homologous recombination. However, their physiological roles in replication fork maintenance prior to fork collapse remain obscure. Here, we report on the role of RAD51 paralogs in short-term replicative stress devoid of DSBs. We show that RAD51 paralogs localize to nascent DNA and common fragile sites upon replication fork stalling. Strikingly, RAD51 paralogs deficient cells exhibit elevated levels of 53BP1 nuclear bodies and increased DSB formation, the latter being attributed to extensive degradation of nascent DNA at stalled forks. RAD51C and XRCC3 promote the restart of stalled replication in an ATP hydrolysis dependent manner by disengaging RAD51 and other RAD51 paralogs from the halted forks. Notably, we find that Fanconi anemia (FA)-like disorder and breast and ovarian cancer patient derived mutations of RAD51C fails to protect replication fork, exhibit under-replicated genomic regions and elevated micro-nucleation. Taken together, RAD51 paralogs prevent degradation of stalled forks and promote the restart of halted replication to avoid replication fork collapse, thereby maintaining genomic integrity and suppressing tumorigenesis.