Odd-even oscillations of SHG efficiencies in twin NLO chromophores

Twin NLO chromophores having two azobenzene units linked by a flexible polymethylene spacer of varying lengths are shown to exhibit odd-even oscillations in their second harmonic generation (SHG) efficiencies, when measured in the powder form. These twin systems were designed to also exhibit liquid cystallinity, and indeed most of them do exhibit a nematic mesophase. The anticipated odd-even oscillations, in both their isotropization transition temperatures (Ti) and isotropization entropies (Delta Si), were also observed. The odd-even oscillation of the SHG efficiencies has been ascribed to a more effective cancellation of mesogenic dipoles in the even twins as compared to their odd counterparts, due to a preferred centrosymmetric packing in the former case. Based on the behaviour of these twin chromophoric molecules, it may be anticipated that such odd-even oscillations will also be observed in the analogous main chain NLO polymers.

Barriers to plantation activities in different agro-ecological zones of Southern India

This paper analyses environmental and socio-economic barriers for plantation activities on local and regional level and investigates the potential for carbon finance to stimulate the increased rates of forest plantation on wasteland, i.e., degraded lands, in southern India. Building on multidisciplinary field work and results from the model GCOMAP, the aim is to (1) identify and characterize the barriers to plantation activities in four agro-ecological zones in the state of Karnataka and (2) investigate what would be required to overcome these barriers and enhance the plantation rate and productivity. The results show that a rehabilitation of the wasteland based on plantation activities is not only possible but also anticipated by the local population and would lead to positive environmental and socio-economic effects at a local level. However, in many cases, the establishment of plantation activities is hindered by a lack of financial resources, low land productivity and water scarcity. Based on the model used and the results from the field work, it can be concluded that certified emission reductions such as carbon credits or other compensatory systems may help to overcome the financial barrier; however, the price needs to be significantly increased if these measures are to have any large-scale impact.

Triaxial A-value versus swell or collapse for compacted soil - Discussion

A discussion of a technical note with the aforementioned title by Day and Marsh, published in this journal (Volume 121, Number 7, July 1995), is presented. Discussers Robinson and Allam assert that the authors' application of the pore-pressure parameter A to predict and quantify swell or collapse of compacted soils is hard to use because the authors visualize the collapse-swell phenomenon to occur in compacted soils broadly classified as sands and clays. The literature demonstrates that mineralogy has an important role in the volume change behavior of fine-grained soils. Robinson and Allam state that the A-value measurements may not completely predict the type of volume change anticipated in compacted soils on soaking without soil clay mineralogy details. Discussion is followed by closure from the authors.

[n]peristylanes and [n]oxa[n]peristylanes (n = 3-6): A theoretical study

Theoretical studies at the HF and Becke3LYP levels using 6-31G* basis sets were carried out on a series of [n]peristylanes and [n]oxa[n]peristylanes (n = 3-6) to understand their structure and energetics. The structures of the [3]- and [4]peristylanes (1, 2) and their era-derivatives (5, 6) were calculated to have the anticipated high symmetry, C-nv. In contrast, a C-s structure (9) at HF/6-31G* and another (25) at the Becke3LYP/6-31G* level were calculated for the [5]oxa[5]peristylane. The energy difference between them is extremely small even though there are major differences in the structures indicating every soft potential energy surface: On the other hand, the potential energy surface of [6]oxa[6]peristylane is not as soft. Similar structures were also calculated for the top rings. Calculations on the seco-compounds 11-14 and 15-19 (Table 4) indicate that there is no unusual strain involved in the formation of 27 from 19. The Li+ interaction energies of the [n]oxa[n]peristylanes are 61.7 (n = 3), 72.8 (n = 4), 84.2 (n = 5) and 91.7 (n = 6) kcal mol(-1) at the Becke3LYP/6-3IG* level. Dramatic differences between the C-C bond lengths obtained from the solid state X-ray diffraction studies and those from the calculations for the [n]oxa[n]peristylanes were also observed.

Multi-Armed Bandit Mechanisms for Multi-Slot Sponsored Searth Auctions

In pay-per click sponsored search auctions which are currently extensively used by search engines, the auction for a keyword involves a certain number of advertisers (say k) competing for available slots (say m) to display their ads. This auction is typically conducted for a number of rounds (say T). There are click probabilities mu_ij associated with agent-slot pairs. The search engine's goal is to maximize social welfare, for example, the sum of values of the advertisers. The search engine does not know the true value of an advertiser for a click to her ad and also does not know the click probabilities mu_ij s. A key problem for the search engine therefore is to learn these during the T rounds of the auction and also to ensure that the auction mechanism is truthful. Mechanisms for addressing such learning and incentives issues have recently been introduced and would be referred to as multi-armed-bandit (MAB) mechanisms. When m = 1,characterizations for truthful MAB mechanisms are available in the literature and it has been shown that the regret for such mechanisms will be O(T^{2/3}). In this paper, we seek to derive a characterization in the realistic but nontrivial general case when m > 1 and obtain several interesting results.

Some studies on a solid state sulphur probe for coal gasification system

Measurements on the solid electrolyte cell(Ar -b H2 ~ H2S/CaS + CaF2 ~- ( P t ) / / C a F 2 / / ( P t )-~- CaF2 ~ CaS/H2S ~- H2 ~- At) show that the emf of the cell is directly related through the Nernst equation to the difference in sulfur potentials established at the two Ar ~- H2 ~ H2S/electrode interfaces. The electrodes are designed to convert the sulfur potential gradient across the calcium fluoride electrolyte into an equivalent fluorine potential gradient with the aid of the reaction, CaF2(s) ~ 1~ S2(g)-e CaS(s) ~- F2(g). The response time of the probe varies from approximately 9 hr at 990~ to 2.5 hr at 1225~ The conversion of calcium sulfide and/or calcium fluoride into calcium oxide should not be a problem in anticipated commercial coal gasification systems. Suggestions are presented for improving the cell for such commercial applications.

Deviation from 3-D Ising critical behaviour in aqueous electrolyte solutions

The near-critical behaviour in complex fluids, comprising electrolyte solutions, polymer solutions and amphiphilic systems, reveals a marked departure from the 3-D Ising behaviour. This departure manifests itself either in terms of a crossover from Ising to mean-field (or classical) critical behaviour, when moving away from a given critical point (Tc), or by the persistence of only mean-field region in the surprisingly close vicinity of Tc. The ilo,non-Ising features of the osmotic compressibility (chi(T,p)) in solutions of electrolytes, that exhibit orle or many liquid-liquid transitions, will be presented. The underlying cause of the breakdown of the anticipated 3-D Ising behaviour in aqueous electrolyte solutions is traced to the structuring induced by the electrolytes. New evidence constituting, measurements of small-angle X-ray scattering (SAXS) and the excess molar volume, is advanced to support the thesis of the close relationship, between the structuring and the deviation from the 3-D Ising critical behaviour in aqueous electrolyte solutions.

Jatropha cultivation in southern India: assessing farmers' experiences

Together with 106 farmers who started growing Jatropha (Jatropha curcas L.) in 20042006, this research sought to increase the knowledge around the real-life experience of Jatropha farming in the southern India states of Tamil Nadu and Andhra Pradesh. Launched as an alternative for diesel in India, Jatropha has been promoted as a non-edible plant that could grow on poor soils, yield oil-rich seeds for production of bio-diesel, and not compete directly with food production. Through interviews with the farmers, information was gathered regarding their socio-economic situation, the implementation and performance of their Jatropha plantations, and their reasons for continuing or discontinuing Jatropha cultivation. Results reveal that 82% of the farmers had substituted former cropland for their Jatropha cultivation. By 2010, 85% (n = 90) of the farmers who cultivated Jatropha in 2004 had stopped. Cultivating the crop did not give the economic returns the farmers anticipated, mainly due to a lack of information about the crop and its maintenance during cultivation and due to water scarcity. A majority of the farmers irrigated and applied fertilizer, and even pesticides. Many problems experienced by the farmers were due to limited knowledge about cultivating Jatropha caused by poor planning and implementation of the national Jatropha program. Extension services, subsidies, and other support were not provided as promised. The farmers who continued cultivation had means of income other than Jatropha and held hopes of a future Jatropha market. The lack of market structures, such as purchase agreements and buyers, as well as a low retail price for the seeds, were frequently stated as barriers to Jatropha cultivation. For Jatropha biodiesel to perform well, efforts are needed to improve yield levels and stability through genetic improvements and drought tolerance, as well as agriculture extension services to support adoption of the crop. Government programs will -probably be more effective if implementing biodiesel production is conjoined with stimulating the demand for Jatropha biodiesel. To avoid food-biofuel competition, additional measures may be needed such as land-use restrictions for Jatropha producers and taxes on biofuels or biofuel feedstocks to improve the competitiveness of the food sector compared to the bioenergy sector. (c) 2012 Society of Chemical Industry and John Wiley & Sons, Ltd

Determination of C-13 Chemical Shift Anisotropy Tensors and Molecular Order of 4-Hexyloxybenzoic Acid

4-Alkoxy benzoic acids belong to an important class of thermotropic liquid crystals that are structurally simple and often used as starting materials for many novel mesogens. 4-Hexyloxybenzoic acid (HBA) is a homologue of the same series and exhibits an enantiotropic nematic phase. As this molecule could serve as an ideal model compound, high resolution C-13 NMR studies of HEA in solution, solid, and liquid crystalline phases have been undertaken. In the solid state, two-dimensional separation of undistorted powder patterns by effortless recoupling (2D SUPER) experiments have been carried out to estimate the magnitude of the components of the chemical shift anisotropy (GSA) tensor of all the aromatic carbons. These values have been used subsequently for calculating the orientational order parameters in the liquid crystalline phase. The GSA values computed by density functional theory (DFT) calculations showed good agreement with the 2D SUPER values. Additionally, C-13-H-1 dipolar couplings in the nematic phase have been determined by separated local field (SLF) spectroscopy at various temperatures and were used for computing the order parameters, which compared well with those calculated by using the chemical shifts. It is anticipated that the CSA values determined for MBA would be useful for the assignment of carbon chemical shifts and for the study of order and dynamics of structurally similar novel mesogens in their nematic phases.

Crystallization and preliminary X-ray studies of MutT1 (MSMEG_2390) from Mycobacterium smegmatis

MutT1 (MSMEG_2390) from Mycobacterium smegmatis has been crystallized and the crystals have been characterized using X-ray diffraction. The crystals belonged to space group P2(1)2(1)2(1). The Matthews coefficient suggested the possibility of one protein molecule in the asymmetric unit of the orthorhombic unit cell. Solution of the structure using the known three-dimensional structure of a bacterial MutT1 is anticipated.

Femtogram Detection of Explosive Nitroaromatics: Fluoranthene-Based Fluorescent Chemosensors

Herein we report a novel fluoranthene-based fluorescent fluorophore 7,10-bis(4-bromophenyl)-8,9-bis4-(hexyloxy)phenyl]fluoranthene (S-3) and its remarkable properties in applications of explosive detection. The sensitivity towards the detection of nitroaromatics (NACs) was evaluated through fluorescence quenching in solution, vapor, and contact mode approaches. The contact mode approach using thin-layer silica chromatograp- hic plates exhibited a femtogram (1.15 fg cm(-2)) detection limit for trinitrotoluene (TNT) and picric acid (PA), whereas the solution-phase quenching showed PA detection at the 2-20 ppb level. Fluorescence lifetime measurements revealed that the quenching is static in nature and the quenching process is fully reversible. Binding energies between model binding sites of the S-3 and analyte compounds reveal that analyte molecules enter into the cavity created by substituted phenyl rings of fluoranthene and are stabilized by strong intermolecular interactions with alkyl chains. It is anticipated that the sensor S-3 could be a promising material for the construction of portable optical devices for the detection of onsite explosive nitroaromatics.

NMR Analysis of Cross Strand Aromatic Interactions in an 8 Residue Hairpin and a 14 Residue Three Stranded beta-Sheet Peptide

Cross strand aromatic interactions between a facing pair of phenylalanine residues in antiparallel beta-sheet structures have been probed using two structurally defined model peptides. The octapeptide Boc-(LFVPPLFV)-P-D-P-L-OMe (peptide 1) favors the beta-hairpin conformation nucleated by the type II' beta-turn formed by the (D)Pro-(L)Pro segment, placing Phe2 and Phe7 side chains in proximity. Two centrally positioned (D)Pro-(L)Pro segments facilitate the three stranded beta-sheet formation in the 14 residue peptide Boc-LFV(D)P(L)PLFVA(D)P(L)PLFV-OMe (peptide 2) in which the Phe2/Phe7 orientations are similar to that in the octapeptide. The anticipated folded conformations of peptides 1 and 2 are established by the delineation of intramolecularly hydrogen bonded NH groups and by the observation of specific cross strand NOEs. The observation of ring current shifted aromatic protons is a diagnostic of close approach of the Phe2 and Phe7 side chains. Specific assignment of aromatic proton resonances using HSQC and HSQC-TOCSY methods allow an analysis of interproton NOEs between the spatially proximate aromatic rings. This approach facilitates specific assignments in systems containing multiple aromatic rings in spectra at natural abundance. Evidence is presented for a dynamic process which invokes a correlated conformational change about the C-alpha-C-beta(chi(1)) bond for the pair of interacting Phe residues. NMR results suggest that aromatic ring orientations observed in crystals are maintained in solution. Anomalous temperature dependence of ring current induced proton chemical shifts suggests that solvophobic effects may facilitate aromatic ring clustering in apolar solvents.

Truthful multi-armed bandit mechanisms for multi-slot sponsored search auctions

In pay-per-click sponsored search auctions which are currently extensively used by search engines, the auction for a keyword involves a certain number of advertisers (say k) competing for available slots (say m) to display their advertisements (ads for short). A sponsored search auction for a keyword is typically conducted for a number of rounds (say T). There are click probabilities mu(ij) associated with each agent slot pair (agent i and slot j). The search engine would like to maximize the social welfare of the advertisers, that is, the sum of values of the advertisers for the keyword. However, the search engine does not know the true values advertisers have for a click to their respective advertisements and also does not know the click probabilities. A key problem for the search engine therefore is to learn these click probabilities during the initial rounds of the auction and also to ensure that the auction mechanism is truthful. Mechanisms for addressing such learning and incentives issues have recently been introduced. These mechanisms, due to their connection to the multi-armed bandit problem, are aptly referred to as multi-armed bandit (MAB) mechanisms. When m = 1, exact characterizations for truthful MAB mechanisms are available in the literature. Recent work has focused on the more realistic but non-trivial general case when m > 1 and a few promising results have started appearing. In this article, we consider this general case when m > 1 and prove several interesting results. Our contributions include: (1) When, mu(ij)s are unconstrained, we prove that any truthful mechanism must satisfy strong pointwise monotonicity and show that the regret will be Theta T7) for such mechanisms. (2) When the clicks on the ads follow a certain click precedence property, we show that weak pointwise monotonicity is necessary for MAB mechanisms to be truthful. (3) If the search engine has a certain coarse pre-estimate of mu(ij) values and wishes to update them during the course of the T rounds, we show that weak pointwise monotonicity and type-I separatedness are necessary while weak pointwise monotonicity and type-II separatedness are sufficient conditions for the MAB mechanisms to be truthful. (4) If the click probabilities are separable into agent-specific and slot-specific terms, we provide a characterization of MAB mechanisms that are truthful in expectation.

Contaminants removal by bentonite amended slow sand filter

Earlier studies have indicated that variability in size, surface texture and charge greatly influence the contaminant removal process in granular media. Based on surface characteristics of montmorillonite, it is anticipated that small addition of this clay would increase adhesion sites for bacterial growth and extracellular polymer production in the slow sand filter and thereby enhance its contaminant removal ability. Experiments were performed by permeating groundwater contaminated with pathogens (total coliform and E. Coli) and inorganic contaminants through the bentonite amended slow sand filter (BASSF). Surprisingly, the BASSF retained inorganic contaminants besides pathogens. Water-leach tests (pH of water leachate ranged from 2 to 9) with spent BASSF specimen indicated that the inorganic contaminants are irreversibly adsorbed to a large extent. It is considered that the combined effects of enhanced-organic matter mediated adhesion sites and increased hydraulic retention time enables the BASSF specimen to retain inorganic contaminants. It is envisaged that BASSF filters could find use in treating contaminated groundwater for potable needs at household and community level.

Asynchronous Measurement of Transient Phase-Shift Resulting From RF Receiver State-Change

In a wireless receiver, a down-converted RF signal undergoes a transient phase shift, when the gain state is changed to adjust for varying conditions in transmission and propagation. A method is developed, in which such phase shifts are detected asynchronously, and their undesirable effects on the bit error rate are corrected. The method was developed for and used in, the system-level characterization and calibration of a 65-nm CMOS UHF receiver. The phase-shifts associated with specific gain-state transitions were measured within a test framework, and used in the baseband signal processing blocks to compensate for errors, whenever the receiver anticipated a gain-state transition.