Computational tools for mechanistic discrimination in the reductive and metathesis coupling reactions mediated by titanium(IV) isopropoxide

A theoretical study has been carried out at the B3LYP/LANL2DZ level to compare the reactivity of phenyl isocyanate and phenyl isothiocyanate towards titanium(IV) alkoxides. Isocyanates are shown to favour both mono insertion and double insertion reactions. Double insertion in a head-to-tail fashion is shown to be more exothermic than double insertion in a head-to-head fashion. The head-to-head double insertion leads to the metathesis product, a carbodiimide, after the extrusion of carbon dioxide. In the case of phenyl isothiocyanate, calculations favour the formation of only mono insertion products. Formation of a double insertion product is highly unfavourable. Further, these studies indicate that the reverse reaction involving the metathesis of N,N-'-diphenyl carbodiimide with carbon dioxide is likely to proceed more efficiently than the metathesis reaction with carbon disulphide. This is in excellent agreement with experimental results as metathesis with carbon disulphide fails to occur. In a second study, multilayer MM/QM calculations are carried out on intermediates generated from reduction of titanium(IV) alkoxides to investigate the effect of alkoxy bridging on the reactivity of multinuclear Ti species. Bimolecular coupling of imines initiated by Ti(III) species leads to a mixture of diastereomers and not diastereoselective coupling of the imine. However if the reaction is carried out by a trimeric biradical species, diastereoselective coupling of the imine is predicted. The presence of alkoxy bridges greatly favours the formation of the d,l (+/-) isomer, whereas the intermediate without alkoxy bridges favours the more stable meso isomer. As a bridged trimeric species, stabilized by bridging alkoxy groups, correctly explains the diastereoselective reaction, it is the most likely intermediate in the reaction.

Prediction of Ground Water Levels in the Uplands of a Tropical Coastal Riparian Wetland using Artificial Neural Networks

Artificial Neural Networks (ANNs) have been found to be a robust tool to model many non-linear hydrological processes. The present study aims at evaluating the performance of ANN in simulating and predicting ground water levels in the uplands of a tropical coastal riparian wetland. The study involves comparison of two network architectures, Feed Forward Neural Network (FFNN) and Recurrent Neural Network (RNN) trained under five algorithms namely Levenberg Marquardt algorithm, Resilient Back propagation algorithm, BFGS Quasi Newton algorithm, Scaled Conjugate Gradient algorithm, and Fletcher Reeves Conjugate Gradient algorithm by simulating the water levels in a well in the study area. The study is analyzed in two cases-one with four inputs to the networks and two with eight inputs to the networks. The two networks-five algorithms in both the cases are compared to determine the best performing combination that could simulate and predict the process satisfactorily. Ad Hoc (Trial and Error) method is followed in optimizing network structure in all cases. On the whole, it is noticed from the results that the Artificial Neural Networks have simulated and predicted the water levels in the well with fair accuracy. This is evident from low values of Normalized Root Mean Square Error and Relative Root Mean Square Error and high values of Nash-Sutcliffe Efficiency Index and Correlation Coefficient (which are taken as the performance measures to calibrate the networks) calculated after the analysis. On comparison of ground water levels predicted with those at the observation well, FFNN trained with Fletcher Reeves Conjugate Gradient algorithm taken four inputs has outperformed all other combinations.

Dual band(WLAN & WiMAX) suppressed harmonic microstrip filter with perturbed ground

Design of a dual band pass filter employing microstrip line with defected ground is presented in this paper. A dual band filter at 2.45GHz and 3.5GHz (covering WLAN and WiMAX) with 6% bandwidth has been designed at each frequency. Apertures in ground plane were used to improve the stop band rejection characteristics and coupling levels in the filter. Measured results of the experimental filter were compared against the simulation results for the purpose of validation.

Soil stabilization with waste materials based binder

This paper describes a laboratory trial to study the effectiveness of a waste-based binder to stabilize expansive soils. The proposed binders viz., Fly ash and/or Ground granulated Blast furnace slag (GGBS) were mixed with the expansive soil along with a small amount of lime to increase soil pH and enable pozzolanic reactions. The geotechnical characteristics of the various combinations of samples were investigated through the compaction tests, unconfined compression tests etc. It was found that the addition of GGBS with and without fly ash and lime has significant influence on the geotechnical characteristics of the soil.

Analysis of multi-conductor coupled microstrip lines with an aperture in the ground plane for the design of a broadband filter

Closed-form expressions for the propagation characteristics of coupled microstrip lines with a symmetrical aperture in the ground plane are derived. Expressions for the regular microstrip coupled lines have been modified using physical insights to incorporate the effect of the aperture. The accuracy of these expressions has been verified by full-wave simulations and compared with conformal mapping analysis. These expressions are accurate within 5% for a substrate whose thickness varies from 0.2 to 1.6mm and permittivity in the range of 210. Designing a broadband filter based on planar multi-conductor coupled lines with aperture in the ground plane is demonstrated in this paper using the proposed expressions for its practical use.

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.

Miniaturized Defected Ground High Isolation Crossovers

This letter relates to the design of crossovers for carrying criss crossing signals. Two types of crossovers are proposed in this letter. Both the crossovers are designed using a two layer printed circuit board. An unbroken continuous transmission line is routed in the top layer for carrying signal 1 from one node to another node. Transmission line used for carrying a signal 2 consists of three physically discontinuous, but electrically connected segments. Two end segments of these are located in the top layer while the middle segment is placed in the bottom layer. While Type I crossover offers an isolation of 25 dB, Type II crossover offers isolation better than 35 dB from dc to 10 GHz. These crossovers are compact and measure an actual size of 10 x 10 x 0.78 mm(3).

Nanocomposite based flexible ultrasensitive resistive gas sensor for chemical reactions studies

Room temperature operation, low detection limit and fast response time are highly desirable for a wide range of gas sensing applications. However, the available gas sensors suffer mainly from high temperature operation or external stimulation for response/recovery. Here, we report an ultrasensitive-flexible-silver-nanoparticle based nanocomposite resistive sensor for ammonia detection and established the sensing mechanism. We show that the nanocomposite can detect ammonia as low as 500 parts-per-trillion at room temperature in a minute time. Furthermore, the evolution of ammonia from different chemical reactions has been demonstrated using the nanocomposite sensor as an example. Our results demonstrate the proof-of-concept for the new detector to be used in several applications including homeland security, environmental pollution and leak detection in research laboratories and many others.

An electron rich porous extended framework as a heterogeneous catalyst for Diels-Alder reactions

An electron rich porous metal-organic framework (MOF) has been synthesized, which acts as an effective heterogeneous catalyst for Diels-Alder reactions through encapsulation of the reactants in confined nano-channels of the framework.

Ground motion prediction equation considering combined dataset of recorded and simulated ground motions

Himalayan region is one of the most active seismic regions in the world and many researchers have highlighted the possibility of great seismic event in the near future due to seismic gap. Seismic hazard analysis and microzonation of highly populated places in the region are mandatory in a regional scale. Region specific Ground Motion Predictive Equation (GMPE) is an important input in the seismic hazard analysis for macro- and micro-zonation studies. Few GMPEs developed in India are based on the recorded data and are applicable for a particular range of magnitudes and distances. This paper focuses on the development of a new GMPE for the Himalayan region considering both the recorded and simulated earthquakes of moment magnitude 5.3-8.7. The Finite Fault simulation model has been used for the ground motion simulation considering region specific seismotectonic parameters from the past earthquakes and source models. Simulated acceleration time histories and response spectra are compared with available records. In the absence of a large number of recorded data, simulations have been performed at unavailable locations by adopting Apparent Stations concept. Earthquakes recorded up to 2007 have been used for the development of new GMPE and earthquakes records after 2007 are used to validate new GMPE. Proposed GMPE matched very well with recorded data and also with other highly ranked GMPEs developed elsewhere and applicable for the region. Comparison of response spectra also have shown good agreement with recorded earthquake data. Quantitative analysis of residuals for the proposed GMPE and region specific GMPEs to predict Nepal-India 2011 earthquake of Mw of 5.7 records values shows that the proposed GMPE predicts Peak ground acceleration and spectral acceleration for entire distance and period range with lower percent residual when compared to exiting region specific GMPEs. Crown Copyright (C) 2013 Published by Elsevier Ltd. All rights reserved.

Crevasses detection in Himalayan glaciers using ground-penetrating radar

Identification and mapping of crevasses in glaciated regions is important for safe movement. However, the remote and rugged glacial terrain in the Himalaya poses greater challenges for field data collection. In the present study crevasse signatures were collected from Siachen and Samudra Tapu glaciers in the Indian Himalaya using ground-penetrating radar (GPR). The surveys were conducted using the antennas of 250 MHz frequency in ground mode and 350 MHz in airborne mode. The identified signatures of open and hidden crevasses in GPR profiles collected in ground mode were validated by ground truthing. The crevasse zones and buried boulder areas in a glacier were identified using a combination of airborne GPR profiles and SAR data, and the same have been validated with the high-resolution optical satellite imagery (Cartosat-1) and Survey of India mapsheet. Using multi-sensor data, a crevasse map for Samudra Tapu glacier was prepared. The present methodology can also be used for mapping the crevasse zones in other glaciers in the Himalaya.

Pd-Catalyzed Cross-Coupling Reactions of Hydrazones: Regioselective Synthesis of Highly Branched Dienes

The regioselective formation of highly branched dienes is a challenging task. Design and exploration of alternative working models to achieve such a regioselectivity to accomplish highly branched dienes is considered to be a historical advancement of Heck reaction to construct branched dienes. On the basis of the utility of carbene transfer reactions, in the reaction of hydrazones with Pd(II) under oxidative conditions, we envisioned obtaining a Pd-bis-carbene complex with alpha-hydrogens, which can lead to branched dienes. Herein, we report a novel Pd-catalyzed selective coupling reaction of hydrazones in the presence of t-BuOLi and benzoquinone to form the corresponding branched dienes. The utility of the Pd catalyst for the cross-coupling reactions for synthesizing branched conjugated dienes is rare. The reaction is very versatile and compatible with a variety of functional groups and is useful in synthesizing heterocyclic molecules. We anticipate that this Pd-catalyzed cross-coupling reaction will open new avenues for synthesizing useful compounds.

Insertion Reactions of Six-Membered Cyclopalladated N,N `,N `'-Triarylguanidine, Pd{kappa(2)(C,N)-C6H3Me-3(NHC(NHAr)(=NAr))-2)(mu-Br)](2) (Ar=2-MeC6H4) with PhCC C-C(O)OR (R = Me and Et): A Gateway to Second Orthopalladation through Novel Rearrangements

The reaction of Pd{kappa(2)(C,N)-C6H3Me-3-(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (Ar = 2-MeC6H4; 1) with 4 equiv of PhC C-C(O)OMe in CH2Cl2 afforded Pd{kappa(2)(C,N)-C(Ph)=C(C(O)OMe)C(Ph)=C(C(O)-OMe)C6H3Me-3(N=C(NH Ar)(2))-2}Br] (Ar = 2-MeC6H4; 2) in 70% yield, and the aforementioned reaction carried out with 10 equiv of PhC C-C(O)OR (R = Me, and Et) afforded an admixture of two regioisomers of Pd{kappa(3)(N,C,O)-O=C(OR)-C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)( 2))- 2}Br] (Ar = 2-MeC6H4; R = Me (3a/3b), Et (4a/4b)) in 80 and 87% yields, respectively. In one attempt, the minor regioisomer, 4b, was isolated from the mixture in 6% yield by fractional crystallization. Palladacycles 3a/3b and 4a/4b, upon stirring in CH2Cl2/MeCN (1/1, v/v) mixture at ambient condition for S days, afforded Pd{eta(3)-allyl,(KN)-N-1)-C-5(C(O)OR)(2)Ph3C-(C(O)OR)C6H3Me-3(N=C(NH Ar)(2))(-2)}Br] (Ar = 2-MeC6H4; R = Me (5a/5b), Et (6a/6b)) in 94 and 93% yields, respectively. Palladacycles 3a/3b and 4a/4b, upon reaction with AgOTf in CH2CH2/Me2C(O) (1/1, v/v) mixture at ambient temperature for 15 min, afforded Pd{kappa(3)(N,C,O)-O=C(OR)C5Ph3(C(O)OR)C(C(O)OR)C6H3Me-3(N=C(NHAr)(2 ))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (7a/7b), Et (8a/8b)) in 79 and 77% yields, respectively. Palladacycles 7a/7b and 8a/ 8b, upon reflux in PhC1 separately for 6 h, or palladacycles 5a/5b and 6a/6b, upon treatment with AgOTf in CH2Cl2/Me2C(O) (7/3, v/v) mixture for 15 min, afforded Pd{(eta(2)-Ph)C5Ph2(C(O)OR)kappa(2)(C,N)-C(C(O)OR)C6H3Me-3(N=C(NHAr) (2))-2}(OTf)] (Ar = 2-MeC6H4; R = Me (9a/9h), Et (10a/10b)) in >= 87% yields. Palladacycles 9a/9b, upon stirring in MeCN in the presence of excess NaOAc followed by crystallization of the reaction mixture in the same solvent, afforded Pd{kappa(3)(N,C,C)-(C6H4)C5Ph2(C(O)OMe)(2)C(C(O)OMe)(2)C6H3Me-3(N=C( NHAr)(2))-2}(NCMe)] (Ar = 2-MeC6H4; 11a/11b) in 82% yield. The new palladacycles were characterized by analytical, IR, and NMR (H-1 and C-13) spectroscopic techniques, and the molecular structures of 2, 3a, 4a, 4b, 5a, 6a, 7a, 9a, 10a, and 11a-d(3) were determined by single crystal X-ray diffraction. The frameworks in the aforementioned palladacycles, except that present in 2, are unprecedented. Plausible pathways for the formation of new palladacycles and the influence of the guanidine unit in 1, substituents in alkynes, reaction conditions, and electrophilicity of the bromide and the triflate upon the frameworks of the insertion products have been discussed.

Intelligent prediction of ground vibration in coal formations using ANN

The present paper details the prediction of blast induced ground vibration, using artificial neural network. The data was generated from five different coal mines. Twenty one different parameters involving rock mass parameters, explosive parameters and blast design parameters, were used to develop the one comprehensive ANN model for five different coal bearing formations. A total of 131 datasets was used to develop the ANN model and 44 datasets was used to test the model. The developed ANN model was compared with the USBM model. The prediction capability to predict blast induced ground vibration, of the comprehensive ANN model was found to be superior.

Synergistic electrochemical activity of titanium carbide and carbon towards fuel cell reactions

Titanium carbide (TiC) is an electrically conducting refractory interstitial compound possessing several unique properties. A cost-effective, efficient and non-Pt electrocatalyst based on TiC is explored and the multi-functionality of TiC towards various electrochemical reactions that are of significant interest in low temperature fuel cells is studied. Ameliorated activities towards oxygen reduction reaction (ORR) and borohydride oxidation are observed with TiC-carbon composites. High sensitivity and selectivity towards ORR have been demonstrated with very good methanol tolerance. The charge transfer interactions between TiC and carbon seem to play a vital role in the improved activity as compared to their individual counterparts. The present study opens up a way to realize completely Pt-free borohydride fuel cell architecture.