Effect of pore medium chemistry on hydraulic conductivity of fine grained soils

Hydraulic conductivity of fine-grained soils has assumed greater importance in waste disposal facilities. It is necessary to understand better the factors controlling hydraulic conductivity of fine-grained soils which are used as liners in waste disposal facilities. Hydraulic Conductivity study with ten soils with two fluids having extreme dielectric constants(epsilon) namely water and CCl4 has shown that intrinsic permeability (K) increases drastically with decrease in epsilon. These changes are attributed to the significant reduction in the thickness of diffuse double layer which in turn mainly dependent on the epsilon of the permeant. Hydraulic Conductivity with water of each pair of soils having nearly same liquid limit but different plasticity properties is found to be vastly different, but found to correlate well with shrinkage index, defined as difference between the liquid and the shrinkage limits. Also the ratio Kccl(4)/K-w is found to significantly increase with the increase in the shrinkage index.

Atmospheric chemistry and climate

Atmospheric chemistry is a branch of atmospheric science where major focus is the composition of the Earth's atmosphere. Knowledge of atmospheric composition is essential due to its interaction with (solar and terrestrial) radiation and interactions of atmospheric species (gaseous and particulate matter) with living organisms. Since atmospheric chemistry covers a vast range of topics, in this article the focus is on the chemistry of atmospheric aerosols with special emphasis on the Indian region. I present a review of the current state of knowledge of aerosol chemistry in India and propose future directions.

The relevance of metal organic frameworks (MOFs) in inorganic materials chemistry

The metal organic frameworks (MOFs) have evolved to be an important family and a corner stone for research in the area of inorganic chemistry. The progress made since 2000 has attracted researchers from other disciplines to actively engage themselves in this area. This cooperative synergy of different scientific believes have provided important edge and spread to the chemistry of metal-organic frameworks. The ease of synthesis coupled with the observation of properties in the areas of catalysis, sorption, separation, luminescence, bioactivity, magnetism, etc., are a proof of this synergism. In this article, we present the recent developments in this area.

Tribology of soot suspension in hexadecane as distinguished by the physical structure and chemistry of soot particles

Ethylene gas is burnt to generate soot which is collected thermophoretically from different locations of the flame. Tribological performance of the collected soot in hexadecane suspension is compared with that of carbon black and diesel soot. The soots are analysed to yield a range of mechanical properties, physical structures and chemistry. The paper correlates these property variations with the corresponding variations in friction and wear when the soot suspended in hexadecane is used to lubricate a steel on steel sliding interaction. The particles are dispersed in hexadecane by a non-ionic surfactant, poly-isobutylene succinimide (PIBS), which is mono-functional with no free amine group. The grafting of the surfactant on the soot particles is found to have a profound effect on the dispersion of the soot, in general, while, between the different soot types, the tribology is differentiated by the physical structure and chemistry.

Recent Developments in the Chemistry and Biology of G-Quadruplexes with Reference to the DNA Groove Binders

DNA is the chemotherapeutic target for treating diseases of genetic origin. Besides well-known double-helical structures (A, B, Z, parallel stranded-DNA etc.), DNA is capable of forming several multi-stranded structures (triplex, tetraplex, i-motif etc.) which have unique biological significance. The G-rich 3'-ends of chromosomes, called telomeres, are synthesized by telomerase, a ribonucleoprotein, and over-expression of telomerase is associated with cancer. The activity of telomerase is suppressed if the G-rich region is folded into the four stranded structures, called G-quadruplexes (G4-DNAs) using small synthetic ligands. Thus design and synthesis of new G4-DNA ligands is an attractive strategy to combat cancer. G4-DNA forming sequences are also prevalent in other genomic regions of biological significance including promoter regions of several oncogenes. Effective gene regulation may be achieved by inducing a G4-DNA structure within the G-rich promoter sequences. To date, several G4-DNA stabilizing ligands are known. DNA groove binders interact with the duplex B-DNA through the grooves (major and minor groove) in a sequence-specific manner. Some of the groove binders are known to stabilize the G4-DNA. However, this is a relatively under explored field of research. In this review, we focus on the recent advances in the understanding of the G4-DNA structures, particularly made from the human telomeric DNA stretches. We summarize the results of various investigations of the interaction of various organic ligands with the G4-DNA while highlighting the importance of groove binder-G4-DNA interactions.

Crystal Engineering in the Desiraju Research Group in Bangalore

Over the years, crystal engineering has transformed into a mature and multidisciplinary subject. New understanding, challenges, and opportunities have emerged in the design of complex structures and structure-property evaluation. Revolutionary pathways adopted by many leaders have shaped and directed this subject. In this short essay to celebrate the 60th birthday of Prof. Gautam R. Desiraju, we, his current research group members, contemplate the development of some of the topics explored by our group in the context of the overall subject. These topics, though not entirely new, are of significant interest to the crystal engineering community.

Preparation and characterization chemistry of nano-crystalline Ni-Cu-Zn ferrite

In submitted research; nanocrystalline powders having elements Ni0.5Cu0.25Zn0.25Fe2 xInxO4 with varied amounts of indium ( x = 0.0, 0.1, 0.2, 0.3 and 0.4) were grown-up by modified citrate to nitrate alchemy. The realism of single phase cubic spinel creation of the synthesized ferrite samples was studied by the DTA-TGA, XRD, SEM, EDX, FT-IR, VSM and dielectric measurements. SEM was applied to inspect the morphological variations and EDX was used to determine the compositional mass ratios. The studies on the dielectric constant (epsilon'), dielectric loss (epsilon `'), loss tangent (tan delta), ac conductivity (sigma(ac)), resistive and reactive parts of the impedance analysis (Z' and Z `') at room temperature were also carried out. The saturation magnetizations (Ms) were determined using the vibrating sample magnetometer (VSM). Ms. decreased with the increase In3+ doping content, as Fe3+ of 5(mu B) ions are replaced by In3+ of 5 mu(B) ions. (C) 2012 Elsevier B. V. All rights reserved.

Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies

Four dinuclear bis(mu-Cl) bridged copper(II) complexes, Cu-2(mu-Cl)(2)(L-X)(2)](ClO4)(2) (L-X = N,N-bis(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L-X ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH2) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu-t-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.

Impact of pit-toilet leachate on groundwater chemistry and role of vadose zone in removal of nitrate and E-coli pollutants in Kolar District, Karnataka, India

Assessment of chemistry of groundwater infiltrated by pit-toilet leachate and contaminant removal by vadose zone form the focus of this study. The study area is Mulbagal Town in Karnataka State, India. Groundwater level measurements and estimation of unsaturated permeability indicated that the leachate recharged the groundwater inside the town at the rate of 1 m/day. The average nitrate concentration of groundwater inside the town (148 mg/L) was three times larger than the permissible limit (45 mg/L), while the average nitrate concentration of groundwater outside the town (30 mg/L) was below the permissible limit. The groundwater inside the town exhibited E. coli contamination, while groundwater outside the town was free of pathogen contamination. Infiltration of alkalis (Na+, K+) and strong acids (Cl-, SO4 (2-)) caused the mixed Ca-Mg-Cl type (60 %) and Na-Cl type (28 %) facies to predominate groundwater inside the town, while, Ca-HCO3 (35 %), mixed Ca-Mg-Cl type (35 %) and mixed Ca-Na-HCO3 type (28 %) facies predominated groundwater outside/periphery of town. Reductions in E. coli and nitrate concentrations with vadose zone thickness indicated its participation in contaminant removal. A 4-m thickness of unsaturated sand + soft, disintegrated weathered rock deposit facilitates the removal of 1 log of E. coli pathogen. The anoxic conditions prevailing in the deeper layers of the vadose zone (> 19 m thickness) favor denitrification resulting in lower nitrate concentrations (28-96 mg/L) in deeper water tables (located at depths of -29 to -39 m).

Influence of anthropogenic contamination on groundwater chemistry in Mulbagal town, Kolar District, India

Geochemical studies are performed to examine the impact of leachate infiltration from on-site sewage disposal systems on the groundwater chemistry in Mulbagal town, Kolar District, Karnataka State, India. The leachate infiltration imposed nitrate concentrations ranging from 4 mg/L to 388 mg/L in the groundwater samples; it was observed that 79% of the samples exhibited nitrate concentrations in excess of drinking water permissible limit (45 mg/L). The average (of 43 measurements) E. coli levels in the groundwater samples corresponded to 189 MPN/100 mL and 55% of the samples tested exhibit pathogen contamination. Results also showed that the groundwater in the study area is characterized by acidic pH, large calcium + magnesium ion and Na/Cl ratios of < unity causing majority of the ground water samples to classify as Ca-Mg-Cl type and Na-Cl type. Saturation index (SI) computation using Visual MINTEQ program showed that the groundwater samples are under-saturated with respect to calcite. The theoretical SI values (of calcite) however suggested that the groundwater samples ought to be over-saturated with calcite. Under-saturation of the groundwater samples with calcite is attributed to increased dissolution of the mineral in the acidic environment of the groundwater.

Chromite-silicate chemistry of the Neoarchean Sittampundi Complex, southern India: Implications for subduction-related arc magmatism

The Neoarchean layered anorthositic complex at Sittampundi in southern India is known for its chromitite layers that are mostly associated with anorthosite (An(90-100)). The chromitites contain FeAl-rich chromites concentrated in layers between amphibole-rich layers with a dominant mineralogy of amphibole-spinel-plagiocase+/-sapphirine. The chromite-rich layers contain only amphibole and plagioclase. Mineral compositions illustrated by X-ray composition maps and profiles show subtle chemical differences. The chrome spinels are of refractory grade with Cr2O3 and Al2O3 contents varying between 34-40 wt.% and 23-28 wt.%. The chromite compositions are noticeably different from those in layered igneous intrusions of the Bushveld-Stillwater type. The existence of original highly calcic plagioclase, FeAl-rich chromite, and magmatic amphibole is consistent with derivation from a parental magma of hydrous tholeiitic composition that was most likely generated in a supra-subduction zone arc setting. In terms of mineralogy and field relations, the Sittampundi chromitites are remarkably similar to anorthosite-hosted chromitites in the Neoarchean Fiskensset anorthositic complex, Greenland. We propose that the Sittampundi chromitites formed by partial melting of unusually aluminous harzburgite in a hydrated mantle wedge above a subduction zone. This melting process produced hydrous, aluminous basalt, which fractionated at depth to give rise to a variety of high-alumina basalt compositions from which the anorthositic complex with its cumulate chromite-rich and amphibole-rich layers formed within the magma chamber of a supra-subduction zone arc. (C) 2011 Elsevier B.V. All rights reserved.

Influence of physical structure and chemistry of diesel soot suspended in hexadecane on lubrication of steel-on-steel contact

Soot generated from the combustion process in diesel engines affect engine tribology. In this paper, two diesel soot samples; from engine exhaust and oil filter are suspended in hexadecane oil and the suspension is used to lubricate a steel ball on steel flat sliding contact at a contact pressure of 1.3 GPa. The friction and wear of the steel flat are recorded. The data are compared with those recorded when the soot is generated by burning ethylene gas. The rationale for the comparatively poor tribology of diesel soot is explored by quantifying the size and shape of primary particles and agglomerates, hardness of single primary soot particles, the crystallinity and surface and near surface chemistry of soot and interparticle adhesion.

Performance evaluation of chemistry transport models over India

Using continuous and near-real time measurements of the mass concentrations of black carbon (BC) aerosols near the surface, for a period of 1 year (from January to December 2006) from a network of eight observatories spread over different environments of India, a space-time synthesis is generated. The strong seasonal variations observed, with a winter high and summer low, are attributed to the combined effects of changes in synoptic air mass types, modulated strongly by the atmospheric boundary layer dynamics. Spatial distribution shows much higher BC concentration over the Indo-Gangetic Plain (IGP) than the peninsular Indian stations. These were examined against the simulations using two chemical transport models, GOCART (Goddard Global Ozone Chemistry Aerosol Radiation and Transport) and CHIMERE for the first time over Indian region. Both the model simulations significantly deviated from the measurements at all the stations; more so during the winter and pre-monsoon seasons and over mega cities. However, the CHIMERE model simulations show better agreement compared with the measurements. Notwithstanding this, both the models captured the temporal variations; at seasonal and subseasonal timescales and the natural variabilities (intra-seasonal oscillations) fairly well, especially at the off-equatorial stations. It is hypothesized that an improvement in the atmospheric boundary layer (ABL) parameterization scheme for tropical environment might lead to better results with GOCART.

Investigation of phase separation in bulk heterojunction solar cells via supramolecular chemistry

In this work, we have prepared two donor-acceptor-donor (D-A-D) pi-conjugated oligomers to investigate the effect of phase separation on the performance of bulk heterojunction (BHJ) solar cells. These charge transfer low band gap pi-conjugated oligomers (TTB and NMeTTB) were synthesized by Knoevenagel condensation of terthiophenecarbaldehyde and barbiturate appended pyran derivative. The thin film morphology of both the oligomers and along with electron acceptor 6,6]-phenyl-C60-butyric acid methyl ester (PC61BM) was investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The blend of NMeTTB and PC61BM thin film yield highly ordered thin film, whereas there was clear phase separation between TTB and PC61BM in thin film. The BHJ solar cell was fabricated using a blend of NMeTTB and TTB with PC61BM acceptor in 1:1 ratio as active layer, and a power conversion efficiency of 1.8% was obtained. This device characteristic was compared with device having TTB:PC61BM as active layer, and large difference is observed in photocurrents. This poor performance of TTB in BHJ devices was attributed to the difference in the nanoscale morphology of the corresponding derivatives. We rationalize our findings based on the low charge carrier mobility in organic field-effect transistors and miscibility/phase separation parameter of binary components (oligomers and PC61BM) in the active layer of bulk heterojunction solar cells.