Mechanism of interaction of the antileukemic drug cytosine arabinoside with aromatic peptides : role of sugar conformation and peptide backbone

Interaction of the antileukemic drugs, cytosine-arabinoside (Ara-C) and adenosine-arabinoside (Ara-A) and a structural analogue, cytidine, with aromatic dipeptides has been studied by fluorescence and NMR spectroscopy. Ara-C and cytidine bind tryptophanyl and histidyl dipeptides but not tyrosyl dipeptides, while Ara-A does not bind to any of them. Both studies indicate association involving stacking of aromatic moieties. NMR spectra also indicate a protonation of the histidine moiety by Ara-C. In case of cytidine, the chemical shifts observed on binding to His-Phe imply that the backbone protons of the dipeptide participate in the binding. The conformation of the sugar and the base seem to play a very important role in the binding phenomenon as three similar molecules, Ara-C, Ara-A and cytidine bind in totally different ways.

Climate change and forests in India

Forests play a critical role in addressing climate change concerns in the broader context of global change and sustainable development. Forests are linked to climate change in three ways. i) Forests are a source of greenhouse gas (GHG) emissions: ii) Forests offer mitigation opportunities to stabilise GHG concentrations: iii) Forests are impacted by climate change. This paper reviews studies related to climate change and forests in India: first, the studies estimating carbon inventory for the Indian land use change and forestry sector (LUCF), then the different models and mitigation potential estimates for the LUCF sector in India. Finally it reviews the studies on the impact of climate change on forest ecosystems in India, identifying the implications for net primary productivity and bio-diversity. The paper highlights data, modelling and research gaps relevant to the GHG inventory, mitigation potential and vulnerability and impact assessments for the forest sector in India.

Thermodynamic and kinetic analysis of carbohydrate binding to the basic lectin from winged bean (Psophocarpus tetragonolobus)

A basic lectin (pI approximately 10.0) was purified to homogeneity from the seeds of winged bean (Psophocarpus tetragonolobus) by affinity chromatography on Sepharose 6-aminocaproyl-D-galactosamine. The lectin agglutinated trypsinized rabbit erythrocytes and had a relative molecular mass of 58,000 consisting of two subunits of Mr 29,000. The lectin binds to N-dansylgalactosamine, leading to a 15-fold increase in dansyl fluorescence with a concomitant 25-nm blue shift in the emission maximum. The lectin has two binding sites/dimer for this sugar and an association constant of 4.17 X 10(5) M-1 at 25 degrees C. The strong binding to N-dansylgalactosamine is due to a relatively positive entropic contribution as revealed by the thermodynamic parameters: delta H = -33.62 kJ mol-1 and delta S0 = -5.24 J mol-1 K-1. Binding of this sugar to the lectin shows that it can accommodate a large hydrophobic substituent on the C-2 carbon of D-galactose. Studies with other sugars indicate that a hydrophobic substituent in alpha- conformation at the anomeric position increases the affinity of binding. The C-4 and C-6 hydroxyl groups are critical for sugar binding to this lectin. Lectin difference absorption spectra in the presence of N-acetylgalactosamine indicate perturbation of tryptophan residues on sugar binding. The results of stopped flow kinetics with N- dansylgalactosamine and the lectin are consistent with a simple one- step mechanism for which k+1 = 1.33 X 10(4) M-1 s-1 and k-1 = 3.2 X 10(- 2) s-1 at 25 degrees C. This k-1 is slower than any reported for a lectin-monosaccharide complex so far. The activation parameters indicate an enthalpically controlled association process.

Immunologic studies on nucleic acids and their components. I. An analysis of the specificity of anti-deoxyadenylate antibodies by a membrane-binding technique

Anti-deoxyadenylate antibodies were produced in rabbits by injecting a conjugate of deoxyadenosine 5′-phosphate with bovine serum albumin. The antisera, as analyzed by double diffusion in agar and the quantitative precipitin reaction, showed hapten-specific antibodies. The specific interaction between [3H]deoxyadenylate and antiserum was studied by a sensitive nitrocellulose membrane-binding assay. The specificity of the antibodies was analyzed by measuring the effectiveness of other nucleotides or derivatives to inhibit the hapten-antibody binding. The requirements for recognition by the antibody sites were studied by using a series of naturally occurring nucleic acid components as well as some synthetic derivatives as inhibitors. The antibodies were found to show a high degree of specificity for the whole nucleotide, the base, sugar and phosphate playing almost equally important roles. There was cross reactivity with other mononucleotides, although of a low order. The antibodies were able to react with DNA and tRNA.

Synthesis of Thioesters by Simultaneous Activation of Carboxylic Acids and Alcohols Using PPh3/NBS with Benzyltriethylammonium Tetrathiomolybdate as the Sulfur Transfer Reagent

A new and simple route for the synthesis of thioesters starting from carboxylic acids and alcohols is reported by using tetrathiomolybdate as the key sulfur transfer reagent. Triphenylphosphane and N-bromosuccinimide were used for the activation of the carboxylic acid and alcohol in the same pot followed by the transfer of sulfur from tetrathiomolybdate. Thioesters were obtained in good to moderate yields. Primary alcohols show excellent reactivity and gave good yields of the corresponding thioesters, whereas secondary alcohols gave moderate yields and tertiary alcohols were very less reactive and gave poor yields of the corresponding thioesters.

Effect of Chain Length of Alcohol on the Lipase-Catalyzed Esterification of Propionic Acid in Supercritical Carbon Dioxide

The esterification of propionic acid was investigated using three different alcohols, namely, isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol. The variation of conversion with time for the synthesis of isoamyl propionate was investigated in the presence of five enzymes. Novozym 435 showed the highest activity, and this was used as the enzyme for investigating the various parameters that influence the esterification reaction. The Ping-Pong Bi-Bi model with inhibition by both acid and alcohol was used to model the experimental data and determine the kinetics of the esterification reaction.

Modification of the sugar specificity of a plant lectin: structural studies on a point mutant of Erythrina corallodendron lectin

A mutant of Erythrina corallodendron lectin was generated with the aim of enhancing its affinity for N-acetylgalactosamine. A tyrosine residue close to the binding site of the lectin was mutated to a glycine in order to facilitate stronger interactions between the acetamido group of the sugar and the lectin which were prevented by the side chain of the tyrosine in the wild-type lectin. The crystal structures of this Y106G mutant lectin in complex with galactose and N-acetylgalactosamine have been determined. A structural rationale has been provided for the differences in the relative binding affinities of the wild-type and mutant lectins towards the two sugars based on the structures. A hydrogen bond between the O6 atom of the sugars and the variable loop of the carbohydrate-binding site of the lectin is lost in the mutant complexes owing to a conformational change in the loop. This loss is compensated by an additional hydrogen bond that is formed between the acetamido group of the sugar and the mutant lectin in the complex with N-acetylgalactosamine, resulting in a higher affinity of the mutant lectin for N-acetylgalactosamine compared with that for galactose, in contrast to the almost equal affinity of the wild-type lectin for the two sugars. The structure of a complex of the mutant with a citrate ion bound at the carbohydrate-binding site that was obtained while attempting to crystallize the complexes with sugars is also presented.

Renewable surface electrodes based on dopamine functionalized exfoliated graphite: NADH oxidation and ethanol biosensing

Exfoliated graphite (EG) was modified by covalently attaching dopamine (DA) (3,4-dihydroxyphenethylamine) through amide linkages, using -COOH groups introduced on the EG surface. The modified material was characterized by FT-IR spectroscopy, Xray photoelectron spectroscopy and electrochemical techniques. Composites of DA modified EG dispersed in organically modified silicates were prepared by a sol-get process. Electrodes were fabricated by casting the composites in glass tubes. The sol-gel based electrodes were found to be active for the electrocatalytic oxidation of NADH and biosensing of ethanol in presence of NAD(+) and alcohol dehydrogenase enzyme. The modified composite electrodes were found to be stable for several months. The surface of the electrode could be renewed just by mechanically polishing the electrode using emery sheets. The modified EG was also pressed and restacked in the form of a pellet and the use of this material as a binderless bulk-modified electrode was also demonstrated. The performance of sol-gel derived composite EG electrodes with binderless bulk-modified EG electrodes was compared. (C) 2002 Elsevier Science B.V. All rights reserved.

Composition of Extrafloral Nectar Influences Interactions between the Myrmecophyte Humboldtia brunonis and its Ant Associates

Ant-plant interactions often are mediated by extrafloral nectar (EFN) composition that may influence plant visitation by ants. Over a 300 km range in the Indian Western Ghats, we investigated the correlation between the EFN composition of the myrmecophytic ant-plant Humboldtia brunonis (Fabaceae) and the number and species of ants visiting EFN. EFN composition varied among H. brunonis populations and between plant organs (floral bud vs. young leaf EFN). In general, EFN was rich in sugars with small quantities of amino acids, especially essential amino acids, and had moderate invertase activity. In experiments at the study sites with sugar and amino acid solutions and with leaf or floral bud EFN mimics, dominant EFN-feeding ants differentiated between solutions as well as between mimics. The castration parasite Crematogaster dohrni (northern study site) was the least selective and did not exhibit any clear feeding preferences, while the largely trophobiont-tending non-protective Myrmicaria brunnea (middle study site) preferred higher sucrose concentrations and certain essential/non-essential amino acid mixtures. The mutualistic Technomyrmex albipes (southern study site) preferred sucrose over glucose or fructose solutions and consumed the leaf EFN mimic to a greater extent than the floral bud EFN mimic. This young leaf EFN mimic had low sugar concentrations, the lowest viscosity and sugar: amino acid ratio, was rich in essential amino acids, and appeared ideally suited to the digestive physiology of T. albipes. This preference for young leaf EFN may explain the greater protection afforded to young leaves than to floral buds by T. albipes, and may also help to resolve ant-pollinator conflicts. The differential response of dominant ants to sugar, amino acids, or solution viscosity suggests that plants can fine-tune their interactions with local ants via EFN composition. Thus, EFN can mediate local partner-choice mechanisms in ant-plant interactions.

Thermoluminescence response in gamma and UV irradiated Dy2O3 nanophosphor

Low temperature solution combustion method was employed to synthesize Dy2O3 nanophosphors using two different fuels (sugar and oxalyl dihydrazine (ODH)). Powder X-ray diffraction confirm pure cubic phase and the estimated particle size from Scherrer's method in sugar and ODH fuel was found to be 26 and 78 nm, respectively, and are in close agreement with those obtained using TEM and W-H plot analysis. SEM micrographs reveal porous, irregular shaped particles with large agglomeration in both the fuels. An optical band gap of 5.24 eV and 5.46 eV was observed for Dy2O3 for sugar and ODH fuels, respectively. The blueshift observed in sugar fuel is attributed to the particles size effect. Thermoluminescence (TL) response of cubic Dy2O3 nanophosphors prepared by both fuels was examined using gamma and UV radiations. The thermoluminescence of sugar used samples shows a single glow peak at 377 degrees C for 1-4 kGy gamma irradiations. When dose is increased to 5 kGy, two more shouldered peaks were observed at 245 and 310 degrees C. However, in TL of ODH used samples, a single glow peak at 376 degrees C was observed. It is observed that TL intensity is found to be more in sugar used samples. In UV irradiated samples a single glow peak at 365 degrees C was recorded in both the fuels with a little variation in TL intensity. The trapping parameters were estimated by different methods and the results are discussed. (C) 2012 Elsevier B.V. All rights reserved.

A possible connection between antidiabetic and antilipemic properties of psoralea corylifolia seeds and the trace elements present: a LIBS based study

Psoralea corylifolia (PC), a medicinal plant, is used in traditional medicine to treat diabetes. Purpose of the research was to examine the antidiabetic and antilipemic potential of PC and to determine the relationship between its antidiabetic potential and the trace elements present. Wistar rats (150-200 g) with fasting blood glucose (FBG) of 80-110 mg dl(-1)(sub-diabetic) and 150-200 mg dl(-1)(mild diabetic) were selected for the short term antidiabetic studies and severely diabetic rats (FBG > 300 mg dl(-1)) were chosen for the long term antidiabetic and hypolipemic studies of PC seed extract. Laser induced breakdown spectroscopy (LIBS) was used to detect trace elements in the PC extract and the intensity ratios of trace elements were estimated. The dose of 250 mg kg(-1) of PC extract was found to be the most effective in lowering blood glucose level (BGL) of normal, sub, mild and severely diabetic rats during FBG and glucose tolerance test (GTT) studies. Lipid profile studies on severely diabetic rats showed substantial reduction in total cholesterol, triglycerides, very low density lipoprotein, and low density lipoprotein and an increase in the total protein, body weight, high density lipoprotein, and hemoglobin after 28 days of treatment. Significant reduction in urine sugar and protein levels was also observed. LIBS analysis of the PC extract revealed the presence of Mg, Si, Na, K, Ca, Zn and Cl. The study validates the traditional use of PC in the treatment of diabetes and confirms its antilipemic potential. The antidiabetic activity of PC extract may partly be due to the presence of appreciable amounts of insulin potentiating elements like Mg, Ca, and K.

The knight of sugar industry: T. S. Venkatraman (1884-1963)

Tiruvadi Sambasiva Venkatraman (TSV) was a plant breeder. In response to a call from Pundit Madan Mohan Malaviya, he made it his mission to develop high-yielding varieties of sugarcane for manufacturing sugar and making it available as a sweetening agent and an energy source for the malnourished children of India. Using Saccharum officinarum, then under cultivation in India, as the female parent, he artificially fertilized it with pollen from S. barberi, which grew wild in Coimbatore. After 4-5 recurrent backcrossings of S. officinarum Chi wild Sorghum spontaneum with S. officinarum as the female parent, TSV selected the `rare' interspecies hybrid cane varieties that resembled sugarcane and had approximately 2.5 cm thick juicy stems containing 16-18% sucrose - nearly 35 times more than what occurred in parent stocks. The hybrid canes matured quickly, were resistant to waterlogging, drought, and to the red-rot disease caused by Glomerella tucumanensis (Sordariomycetes: Glomerellaceae), and to the sereh-virus disease. Most importantly, they were amenable for propagation using stem cuttings. In recognition of the development of high-yielding sugarcane varieties, TSV was conferred the titles Rao Bahadur, Rao Sahib, and Sir by the British Government, and Padma Bhushan by the Republic of India. In the next few decades, consequent to TSV's work, India turned into the second largest sugar producer in the world, after Brazil. The hybrid sugarcane varieties developed are the foundational stocks for new sugarcane x bamboo hybrids, and for possible resistance to Puccinia megalocephala (Pucciniomycetes: Pucciniaceae) and Ustilago scitaminea (Ustilaginomycetes: Ustilaginaceae) using molecular techniques.

Investigation of selective sensing of a diamine for aldehyde by experimental and simulation studies

An organic molecule-o-phenylene diamine (OPD)-is selected as an aldehyde sensing material. It is studied for selectivity to aldehyde vapours both by experiment and simulation. A chemiresistor based sensor for detection of aldehyde vapours is fabricated. An o-phenylene diamine-carbon black composite is used as the sensing element. The amine groups in the OPD would interact with the carbonyl groups of the aldehydes. The selectivity and cross-sensitivity of the OPD-CB sensor to VOCs aldehyde, ketone and alcohol-are studied. The sensor shows good response to aldehydes compared to other VOCs. The higher response for aldehydes is attributed to the interaction of the carbonyl oxygen of aldehydes with-NH2 groups of OPD. The surface morphology of the sensing element is studied by scanning electron microscopy. The OPD-CB sensor is responsive to 10 ppm of formaldehyde. The interaction of the VOCs with the OPD-CB nanocomposite is investigated by molecular dynamics studies. The interaction energies of the analyte with the OPD-CB nanocomposite were calculated. It is observed that the interaction energies for aldehydes are higher than those for other analytes. Thus the OPD-CB sensor shows selectivity to aldehydes. The simulated radial distribution function is calculated for the O-H pair of analyte and OPD which further supports the finding that the amine groups are involved in the interaction. These results suggest that it is important and easy to identify appropriate sensing materials based on the understanding of analyte interaction properties.