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We investigate triplet pair dynamics in pentacene dimers that have varying degrees of coplanarity (pentacene-pentacene twist angle). The fine-tuning of the twist angle was achieved by alternating connectivity at the 1-position or 2-positions of pentacene. This mix-and-match connectivity leads to tunable twist angles between the two covalently linked pentacenes. These twisted dimers allow us to investigate the subtle effects that the dihedral angle between the covalently linked pentacenes imparts on singlet fission and triplet pair recombination dynamics. We observe that as the dihedral angle between the two bonded pentacenes is increased, the rates of singlet fission decrease, while the accompanying decrease in triplet recombination rates is stark. Temperature-dependent transient optical studies combined with theoretical calculations show that the triplet pair recombination proceeds primarily through a direct multiexciton internal conversion process. Calculations further show that the significant decrease in recombination rates can be directly attributed to a corresponding decrease in the magnitude of the nonadiabatic coupling between the singlet multiexcitonic state and the ground state. These results highlight the importance of the twist angle in designing systems that exhibit rapid singlet fission, while maintaining long triplet pair lifetimes in pentacene dimers.

Amino acid supplementation may be indicated to correct for insufficient amino acid intake in healthy individuals, and in specific physiological or pathophysiological situations. However, there is a concern to not supplement beyond the tolerable upper intake level (UL) by determining parameters of no-observed-adverse-effect level (NOAEL) or lowest-observed-adverse-effect level (LOAEL) for each amino acid. Since the NOAEL and LOAEL values are at least one order of magnitude different when comparing the values obtained in rats and humans, the aim of this review is to evaluate to what extent the amino acid UL measured in the rat model, when referenced to the dietary usual consumption (UC) and dietary requirement (RQ) for indispensable amino acids, may be used as an approximation of the UL in humans. This review then compares the ratios of the NOAEL or LOAEL over UC and RQ in the rat model with the same ratios calculated in humans for the nine amino acids (arginine, serine, glycine, histidine, leucine, lysine, methionine, phenylalanine, and tryptophan) for which this comparison can be done. From the calculations made, it appears that for these 9 amino acids, the calculated ratios for rats and humans, although rather different for several amino acids, remains for all of them in the same order of magnitude. For tryptophan, tyrosine, and valine, the ratios calculated in rats are markedly different according to the sex of animals, raising the view that it may be also the case in humans.

In diabetic condition, endogenous glucose synthesis will be elevated due to defect in the action of vital enzymes involved in carbohydrate metabolism, which is the main cause for hyperglycemia. The current study was designed to explore the anti-hyperglycemic efficacy of Sesbania grandiflora flower (SGF) extract by evaluating the concentration of C-peptide, insulin, glucose, glycosylated hemoglobin (HbA1C), hemoglobin (Hb), glycogen and carbohydrate metabolic enzymes activities in diabetic rats. The study found to lower the level of glucose, HbA1C and simultaneously ameliorated concentrations of C-peptide, insulin, hemoglobin (Hb), glycogen and carbohydrate metabolic enzymes activities in SGF treated (250 mg/kg body weight for 45 days) diabetic rats. Moreover, SGF administered diabetic rats showed diminished consumption of food and water at the same time improved body weight. The results obtained from the present study were compared with glibenclamide treated (600 µg/kg body weight) diabetic rats. SGF were supplemented to normal rats to rule out toxic effect of SGF, to explore any significant alteration in the above parameters. Hence, the results depict that SGF modulated the carbohydrate metabolic enzymes activities through ameliorating the secretion of insulin and diminishing the level of glucose concentration in STZ-induced diabetic rats by its bioactive compounds.

Background Propionic acidemia (PROP) is an autosomal recessive inherited deficiency of propionyl‐CoA carboxylase (PCC) which is involved in the catalytic breakdown of the amino acids valine, isoleucine, methionine, and threonine. PROP nutritional management is based on dietary protein restriction and use of special medical formulas which are free of the offending amino acids, but are enriched in leucine. The resulting imbalance among branched‐chain amino acids negatively impacts plasma concentrations of valine and isoleucine, which might impact growth in children with PROP. Objective and Methods Our primary objective was to describe dietary protein and calorie intake and their impact on long‐term growth outcomes of four PROP patients. This was accomplished through a longitudinal retrospective chart review following the cohort from birth to 18 years. Results All children (n = 4) had poor growth outcomes with persistently reduced height‐for‐age Z scores, and elevated weight and body mass index (BMI) Z scores. Energy intakes for all subjects were within 80% to 120% of the dietary reference intakes for age. All children had low intakes of intact protein compared with current guidelines and were supplemented with medical formula and single l‐amino acids (valine and/or isoleucine), which led to the excess consumption of total protein. Conclusion Despite adequate total protein and energy intakes, all children had persistently low height Z scores. Restricted intact protein consumption together with the abundant use of medical formula could have affected overall growth. To optimize dietary management in patients with PROP, further research is needed to determine the optimal intake of medical formula relative to intact protein.

The interaction between antihistaminic drug oxatomide (OXT) and calf-thymus DNA (CT-DNA) has been investigated in a physiological buffer (pH 7.4) using UV–Vis, fluorescence, 1H NMR and circular dichroism spectral techniques coupled with viscosity measurements, KI quenching, voltammetry and in silico molecular modeling studies. OXT binds with CT-DNA in a concentration-dependent manner. At a lower [Drug]/[CT-DNA] molar ratio (0.6–0.1), OXT intercalates into the base pairs of CT-DNA, while at a higher [Drug]/[CT-DNA] molar ratio (13–6), the drug binds in the minor grooves of CT-DNA. The binding constants for the interaction are found to be in the order of 103–105 M−1, and the groove binding mode of interaction exhibits a slightly higher binding constant than that of intercalative mode. Thermodynamic analysis of binding constants at three different temperatures suggests that both these modes of binding are mainly driven by hydrophobic interactions (ΔHo > 0 and ΔSo > 0). Voltammetric investigations indicate that the electro-reduction of OXT is an adsorption controlled process and shifts in reduction peak potentials reiterate the concentration-dependent mode of binding of the drug with CT-DNA. The free energy landscape obtained at the all-atom level, using metadynamics simulation studies, revealed two major binding forces: partial intercalation and minor groove binding, which corroborate well with the experimental results. Communicated by Ramaswamy H. Sarma

Triple-negative breast cancer (TNBC) patients exhibit variable responses to chemotherapy, suggesting an underlying molecular heterogeneity. In the current study, we analyzed publicly available transcriptome data from 360 TNBC and 88 normal breast tissues, which revealed activation of nucleosome and cell cycle as the hallmarks of TNBC. Mechanistic network analysis identified activation of FOXM1 and ERBB2, and suppression of TP53 and NURP1 networks in TNBC. Employing Iterative Clustering and Guide-gene Selection (ICGS), Uniform Manifold Approximation and Projection (UMAP), and dimensionality reduction analyses, we classified TNBC into seven molecular subtypes, each exhibiting a unique molecular signature, including immune infiltration (CD19, CD8, and macrophages) and mesenchymal signature, which correlated with variable disease outcomes in a larger cohort (1,070) of BC. Mechanistically, depletion of TTK, TPX2, UBE2C, CDCA7, MELK, NFE2L3, DDX39A, and LRP8 led to substantial inhibition of colony formation of TNBC models, which was further enhanced in the presence of paclitaxel. Our data provide novel insights into the molecular heterogeneity of TNBC and identified TTK, TPX2, UBE2C, and LRP8 as main drivers of TNBC tumorigenesis., Graphical Abstract, TNBC patients exhibit variable responses to therapy, suggesting an underlying molecular heterogeneity. Herein, we classified TNBC into seven molecular subtypes with distinct molecular signatures. Our data highlight pivotal roles for TTK, TPX2, and LRP8 in TNBC biology and their sensitivity to paclitaxel, suggesting their potential utilization as therapeutic targets.

Rivers engage in carbon cycle by transporting the dissolved products of weathering of rocks to the oceans, and this process is sensitive to the global climatic changes. The present study was carried out with an objective of estimating the spatial and temporal variation in carbon consumption due to rock weathering in Cauvery, which is a major non-perennial tropical river in the peninsular India. The samples of all the rock types of this river basin were collected and subjected to mineralogical analysis. The water samples from this river were collected three times a year from 2013 to 2017 at 28 locations and were analysed for pH, EC and major ions. The spatiotemporal variations in the chemistry of river water were used to understand the amount of carbon dioxide consumed by rock weathering. The contribution of weathering to dissolved load of the river was higher followed by the contribution of anthropogenic activities and rainfall. The contribution of silicate weathering is dominant during the high river flow, whereas during low flow time periods, the contribution of carbonate weathering is on par with silicate weathering. The carbon consumption due to weathering in the Cauvery river was higher when the flow was significant, and it was lower during summer months. It is also evident that the carbon consumption is high in the upper and middle regions of the basin due to the weathering of gneissic and granodiorite rocks. Thus, the carbon consumption and flux in this basin are dynamic, both spatially and temporally. The east flowing rivers draining through the peninsular India, which is mostly composed of massive rocks, also functions as carbon sink, thus benefitting the environment by reducing the excess CO2 in the atmosphere.

Four new naphthyridine derivatives (R1-R4) possessing amino acid or boronic acid moieties have been synthesized and characterized using 1H and 13C NMR, FT-IR, and mass spectral techniques. The mechanism of binding of these probes with calf thymus DNA (CT-DNA) has been delineated through UV-Vis, fluorescence, and circular dichroism (CD) spectral techniques along with thermodynamic and molecular docking studies. Small hypochromicity in absorption maximum of the probes without any shift in wavelength of absorption suggests groove binding mode of interaction of these probes with CT-DNA, confirmed by CD and 1H NMR spectral data competitive binding assay with ethidium bromide (EB). CT-DNA quenches the fluorescence of these probes via a static quenching mechanism. In the case of R1 and R4, the observed ΔHo 0suggest that these probes interact with CT-DNA through H-bonding and hydrophobic interactions, while in the interaction of R2 and R3, van der Walls and H-boding forces are found to be dominant (ΔHo

In recent days, to increase the weld strength of the hard material was difficult. At the same time, more amounts of heats were generated and insufficient of welding joint was also occurred. The excess flow of heat may leads to damage the welded joints. Friction Stir Welding (FSW) with cooling arrangement was used to avoid the welding defects. The cooling system has been attached to the tool holder. It was used to manage or control the heat produced during welding process and its weld efficiency was also improved. Cubic Boron Nitride (CBN) tip was used to improve the welding strength and it was protects the tool life. The experimental investigation was conducted on High Yield Strength Deformed (HYSD) steel. FSW parametric effect and optimization was carried out by Taguchi method. The role of factors and their effects were studied through variance test and interaction plots. The comparison of weld strength was discussed with and without coating of CBN and cooling system.

In present study, a novel random copolyester i.e. poly(3-oxy-5-methylphenyl-4-oxynaphthal-1- yl)isophthalate (PONI) was synthesized through solution polycondensation methodology involving orcinol, 1,4-naphthalene diol and isophthaloyl chloride and its solubility in common solvents along with viscosity measurements were performed. The structure of the repeat units in the polyester chain were ascertained based on the spectral characterization of UV-visible, FTIR, 1H & 13C NMR techniques. Thermal analysis of the copolyester were performed by TGA and DSC studies. The activation energy for thermal decomposition of polyester was estimated by well-known kinetic methods. The surface morphology and crystalline nature of the polymer were explored by employing SEM and WAXD methods. The antimicrobial efficacy of copolyester was assessed through well-diffusion method using a Gram-positive and a Gram-negative bacteria. The in vitro cytotoxicity of the polyester prepared was verified against HeLa cell line using MTT assay.

A quinoline-based Schiff base sensor, 6-methyl-2-oxo-1,2-dihydro-quinoline-3-carboxaldehyde-4(N)-phenylsemicarbazone (6MPS), has been developed for selective sensing of methionine and aspartic acid in aqueous medium through "on-off-on" type selective detection of copper ion. Fluorescence imaging of 6MPS, 6MPSC, 6MPSCN, 6MPSC-met, 6MPSCN-met, 6MPSC-asp and 6MPSCN-asp has been successfully demonstrated, in which the sensing probes 6MPSC-met, 6MPSCN-met, 6MPSC-asp and 6MPSCN-asp displayed bright green fluorescence in both in vitro and in vivo live cells.

Biotic stresses, including fungal infections, result in increased production of flavonoid compounds, including 3-deoxyanthocyanidins (3-DAs), in the leaf tissues of Sorghum bicolor. Our objectives were to determine whether sorghum genotypic variation influenced root flavonoid and 3-DA concentrations and rhizosphere microbial communities and to identify how these relationships were affected by abiotic stress. We evaluated root chemicals and rhizosphere microbiomes of five near-isogenic lines of sorghum before and after a late-season frost. Roots were analyzed for total flavonoids, total phenolics, 3-DA concentrations, and antioxidant activity. Amplicon sequencing of 16S ribosomal RNA genes and internal transcribed spacer regions was performed on rhizosphere soils. Concentrations of luteolinidin (a 3-DA) and total flavonoids differed between several lines before frost; however, these relationships changed after frost. Luteolinidin increased in three lines after frost, whereas total flavonoids decreased in all the lines after frost. Lines that differed in luteolinidin and total flavonoid concentrations before frost were different from those after frost. Rhizosphere community compositions also differed before and after frost but only fungal community compositions differed among sorghum lines. Bacterial community compositions were highly correlated with total flavonoid and luteolinidin concentrations. Furthermore, a greater number of bacterial taxa were correlated with total flavonoids and luteolinidin compared with fungal taxa. Collectively, this study provides evidence that plant genotypic variation influences root flavonoids and rhizosphere community composition and that these relationships are affected by frost. Plant–microbe interactions and secondary metabolite production may be important components to include for selective breeding of sorghum for frost stress tolerance.

Hybrid aluminum metal matrix composites have prominence than conventional metals. Aluminum is used as base metal in many metal matrix composites, as it is widely used in industries and researches. The low density that is obtained after alloying is the major advantages of hybrid composite. The present study involves synthesis of Al6061/B4C/Mica hybrid metal matrix composite using stir casting method by mica particles as 3, 4, 5, 6wt.%, while maintaining 10wt.% of boron carbide. The best mechanical properties are reported by inclusion of 3wt.% of mica, while further addition of mica more than 3wt.% pulls down the mechanical properties and hence not sensible. The early-stage of strain hardening, and high tensile strength-yield strength ratio is observed, which concludes the fabricated hybrid aluminum composite is well suitable for automotive-related sheet forming operations.

Zn-doped TiO2 films were deposited on ultrasonically treated alumina substrates via the automatic nebulizer spray pyrolysis method. In this study, the thickness of the as-prepared films was gradually reduced, and their Brunauer–Emmett–Teller (BET) surface area and pore volume results were notably improved; in addition, values for the blue-shifted sharp edge absorption with an enlarged bandgap (Eg) were revealed in the deposited films. The agglomerated granular form has evolved into tiny grains with porous brighter particles scattered over the surface of the coated films. The sensing performance to reducing gases for combustible gas of ammonia (NH3) and volatile organic compounds of methanol (CH4O) and formaldehyde (HCHO) with the function of operating temperature and gas concentration were studied, and the highest sensing response of the hazardous formaldehyde (HCHO) reducing gas was noticed.

BACKGROUND Rice is one of the most commonly consumed cereal grains and is part of staple diets in the majority of the world. However, it is regarded as an incomplete protein, with lysine being a limiting amino acid. OBJECTIVES Our objectives were to determine the bioavailability of lysine in school-age children consuming cooked white rice and to assess the effect of rice starch retrogradation. METHODS Bioavailability or metabolic availability (MA) of lysine was determined using the indicator amino acid oxidation (IAAO) method in a repeated-measures design. Six healthy school-age children (3 boys, 3 girls) with a mean ± SD age of 6.8 ± 0.98 y randomly received 4 crystalline l-lysine intakes (2, 6, 10, 14 mg · kg-1 · d-1), and 5 rice intakes to provide lysine at 8, 11, or 14 mg · kg-1 · d-1. The 14 mg · kg-1 · d-1 intakes were measured twice as warm rice and once as cold rice (to assess the impact of starch retrogradation on MA). Diets provided protein at 1.5 g · kg-1 · d-1 and calories at 1.7 times the participant's measured resting energy requirement, and were isonitrogenous. Breath samples were collected at baseline and during an isotopic steady state for 13C enrichment measurement. The MA of lysine from rice was determined by comparing the IAAO response of rice with l-lysine using the slope-ratio and single intake methods. Starch retrogradation was characterized using differential scanning calorimetry. RESULTS MA of lysine in warm rice measured in school-age children was 97.5% and was similar to a repeated rice study (97.1%) within the same study population. MA of lysine was reduced significantly (P

A major benefit of intramolecular singlet fission (iSF) materials, in which through-bond interactions mediate triplet pair formation, is the ability to control the triplet formation dynamics through molecular engineering. One common design strategy is the use of molecular bridges to mediate interchromophore interactions, decreasing electronic coupling by increasing chromophore-chromophore separation. Here, we report how the judicious choice of aromatic bridges can enhance chromophore-chromophore electronic coupling. This molecular engineering strategy takes advantage of "bridge resonance", in which the frontier orbital energies are nearly degenerate with those of the covalently linked singlet fission chromophores, resulting in fast iSF even at large interchromophore separations. Using transient absorption spectroscopy, we investigate this bridge resonance effect in a series of pentacene and tetracene-bridged dimers, and we find that the rate of triplet formation is enhanced as the bridge orbitals approach resonance. This work highlights the important role of molecular connectivity in controlling the rate of iSF through chemical bonds and establishes critical design principles for future use of iSF materials in optoelectronic devices.

Swept friction stir spot welding (SFSSW) is one of the preferred welding methods used in joining metals. The application of this joining process is limited by path deviation, insufficient tool plunging and vibrations caused by high torque and force during the welding. In order to improve the weld strength and weld repeatability, the optimum process parameters of SFSSW of aluminium 6061-T6 alloy were investigated through Grey rational analysis. Initially, Taguchi L16 array consisting of diameter of guide hole, tool rotational and traverse speeds was developed and experiments were conducted by filling guide hole with Silicon Carbide nanoparticles. Grey relational analysis of the experiments reports that guide hole diameter = 3 mm, rotational speed = 1600 rpm and traverse speed = 20 mm/min are found to be optimal parameters for attaining the maximum lap shear strength and hardness. The cause-and-effect analysis of data reports that the amount of SiC added to the guide hole is the most significant factor influencing the weld strength. Furthermore, mechanical and metallurgical characterisation of weld samples prepared at optimum condition were compared with neat samples. The microstructural analysis of stir zone and the fractured area were also presented. The addition of nanoparticles and use of predicted optimum weld condition results homogeneous distribution, refined grains in the stir zone that causes a noteworthy increase in the weld strength.

Introduction: The N-heterocyclic compounds have been extensively studied in pharmaceutical industries. Furthermore, syntheses of such compounds employing organo-catalyst have been associated with sustainable technology. Methods: The synthesis of new, stable ionic liquids and their catalytic applications in one-pot multicomponent Biginelli reaction is presented. The method provides broad substrate scope, yielding the corresponding 3,4-dihydropyrimidin-2(1H)-ones and 3,4-dihydropyrimidin-2(1H)-thiones, in good to excellent yields, respectively. Results and Conclusion: The developed reactions are associated with certain advantages, short reaction time and sustainable conditions. The protocol has advantages eco-friendly procedure, recovery and reusability of catalyst, which showed consistent activity.

BACKGROUND In general, pulse protein is limiting in the indispensable amino acid methionine, and antinutritional factors in pulses can affect methionine bioavailability. Complementation with grains such as rice can improve pulse protein quality, but knowledge of methionine bioavailability in pulses and grains is necessary to correct for available methionine when planning and assessing dietary protein intake. OBJECTIVES The study objectives were to determine the bioavailability of methionine in rice and chickpeas separately and to assess the effect of complementation of chickpeas and rice. METHODS Eleven healthy young men (

A study was carried out to prepare low fat probiotic ice cream by incorporating starches and Lactobacillus reuteri. Ice cream having 10 per cent milk fat was kept as control (FFIM). Different treatments of ice cream having 1, 2 and 3 per cent fat were prepared by incorporating either tapioca starch or maltodextrin at 3, 4 and 5 per cent levels with 10% fruit pulp respectively. The calorific value and organoleptic evaluation were studied during different storage periods up to 6 weeks in different treatments of ice cream at -23 °C. The organoleptic evaluation revealed a highly significant (P

Objectives: Epidemiological data suggests the highest density of histamine H3-receptors (H3R) in basal ganglia of central nervous system (CNS) wherein they function as inhibitory auto-receptors and control the release of many neurotransmitters. Inhibition of H3R increases the turnover of neurotransmitters, especially dopamine in basal ganglia and could be beneficial to treat Parkinson’s disease. Methods: In this study, we formulated the brain targeting liposomes of conessine, a selective antagonist for H3R to increase bioavailability and developed and validated a rapid and sensitive reverse phase ultra-force liquid chromatographic (RP-UFLC) method and to quantitate conessine in Wistar rat plasma and tissue. Plasma and tissue samples were extracted by protein precipitation technique using acetonitrile (ACN) and aripiprazole as the internal standard. Chromatographic separation was performed on the Hibar C18 column with a mobile phase of Hexane Sulphonic acid (10 mM, pH 10.0 adjusted with ammonia) and methanol at a flow rate of 0.9 ml/min. Results: The lower limit of quantification of the developed method was 4.0 ng/ml and 6.0 ng/g in plasma and tissue samples, respectively. Liposomes of conessine (equivalent to 20 mg/kg) administered orally to animals, demonstrated remarkable absorption into the systemic circulation with maximum concentration (~8700 ng/ ml) within 2.0 h. The order of area under curve was found to be kidney> brain> liver> lungs> spleen> heart. Conclusion: The liposomes of conessine were rapidly taken up into the brain and showed a good brain concentration after 2.0 h; sustenance up to 4.0 h was achieved which is better than conessine solution. Key words: Conessine, RP-UFLC method, Pharmacokinetic, Tissue distribution, Validation.

Soft actuators are generally built to achieve extension, contraction, curling, or bending motions needed for robotic or medical applications. It is prepared with a cylindrical tube, braided with fibers that restrict the radial motion and produce the extension, contraction, or bending. The actuation is achieved through the input of compressed air with a different pressure. The stiffness of the materials controls the magnitude of the actuation. In the present study, Silastic-P1 silicone RTV and multi-wall carbon nanotubes (MWCNT) with reinforced silicone are considered for the evaluation. The dumbbell samples are prepared from both materials as per ASTM D412-06a (ISO 37) standard and their corresponding tensile strength, elongation at break, and tensile modulus are measured. The Ogden nonlinear material constants of respective materials are estimated and used further in the finite element analysis of extension, contraction, and bending soft actuators. It is observed that silicone RTV is better in high strain and fast response, whereas, silicone/MWCNT is better at achieving high actuation.

Background: Chitosan, chitosan nanoparticle, ethanolic extracts of Anacyclus pyrethrum root and Cyperus rotundus rhizome were evaluated against plasmid mediated multidrug resistance of Enterococcus faecalis, Staphylococcus aureus and Bacillus sp. isolated from unstimulated saliva of chronic periodontitis. The main aim of the current study centres the reduction of antibiotic consumption and the development of natural compounds to combat multidrug resistance. Methods: Identification of bacteria, antimicrobial susceptibility, plasmid stability and plasmid curing was carried out for the characterization of resistance plasmids. Results: E. faecalis showed 89% of sensitivity to chitosan nanoparticle, chitosan 81%, C. Rotundus 69% and A. pyrethrum 62% for S. aureus, with the MIC >100 µg/ml. In comparison with the antimicrobials tested, maximum resistance to tetracycline (89%) for E. faecalis, is followed by ampicillin (87%) and tetracycline (81%) for S. aureus. Meanwhile, chloramphenicol and tetracycline (80%) for Bacillus sp. The plasmid stability for E. faecalis (20%), S. aureus (C. rotundus>chitosan>A. pyrethrum. Conclusion: Chitosan, Chitosan nanoparticle, C. rotundus, and A. pyrethrum offered a greater potential in eliminating plasmid mediated resistance acquired by periodontal pathogens, thus addressing this crisis in dentistry.

Molecular chirality can be exploited as a sensitive reporter of the nature of intra- and interchromophore interactions in π-conjugated systems. In this report, we designed an intramolecular singlet fission (iSF)-based pentacene dimer with an axially chiral binaphthyl bridge (2,2'-(2,2'-dimethoxy-[1,1'-binaphthalene]-3,3'-diyl) n-octyl-di-isopropyl silylethynyl dipentacene, BNBP) to utilize its chiroptical response as a marker of iSF chromophore-bridge-chromophore (SFC-β-SFC) interactions. The axial chirality of the bridge enforces significant one-handed excitonic coupling of the pentacene monomer units; as such, BNBP exhibits significant chiroptical response in the ground and excited states. We analyzed the chiroptical response of BNBP using the exciton coupling method and quadratic response density functional theory calculations to reveal that higher energy singlet transitions in BNBP involve significant delocalization of the electronic density on the bridging binaphthyl group. Our results highlight the promising application of chiroptical techniques to investigate the nature of SFC-β-SFC interactions that impact singlet fission dynamics.

The required acidity of 0.175±0.54 per cent lactic acid and a pH of 5.65±0.15, suitable for spray drying were reached in three hours by synbiotic milk prepared by substitution of enzymatically modified soymilk to bifidogenic milk at 15 per cent level (SyM15). There was significant difference in acidity between control and synbiotic milk prepared by substitution of enzymatically modified soymilk to bifidogenic milk (SyM) at 10, 15 and 20 per cent level. The pH development at 0h, 1h, 2h, 3h after inoculation of Bifidobacterium longum at in modified milk incubated at 37C anaerobically were estimated and statistical analysis revealed that there exists no significant differences in pH between SyM15, SyM20.

The common phenomenon that the nonviral vectors have much lower transfection efficiency in vivo than in vitro greatly restricts their further developments and applications. Possible reasons are lacking targeting ability, elimination by the reticuloendothelial system (RES), and insufficient nuclear transport. Here, a novel, flexible, and deformable polymer Fe@PEI-R12 (tLyp-1-NLS) is reported for shortening the gap between in vitro and in vivo gene transfection efficiency. The amorphous network structure Fe@PEI with deformation ability acquired by coordination cross-linking of Fe3+ and low-molecular-weight polyethylenimine (LMW-PEI) constructs the core and serves as the gene reservoir, and it can squeeze out through RES filter holes when trapped in the spleen. The bifunctional peptide R12 provided tumor targeting and enhanced nuclear delivery ability. Additionally, the Fe3+ from Fe@PEI-R12 could trigger endogenous hydrogen peroxide (H2O2) decomposition to produce O2, thereby reducing the adverse effects of tumor hypoxia. It is demonstrated that the Fe@PEI-R12/pDNA complexes could pass through membrane filters, subsequently achieving long circulation time, and Fe@PEI-R12 had a tendency to accumulate in tumor tissue and mediate pGL3-control expression. Therefore, the multifunctional nanoplatform has the potential for effective in vivo gene delivery.

We have synthesized two ionic liquids namely 1-hexyl-1,2,4-triazolium methanesulfonate and 1-hexyl-1,2,4-triazolium trifluoroacetate. We have carried out the reduction of various aldehydes and ketones by NaBH4 in the presence of the synthesized ionic liquids. Cinnamaldehyde and acetophenone are used for the optimization of the reaction condition. Reduction of different aldehydes and ketones were carried out and a good yield of product is obtained where the ionic liquid with anion methanesulfonate is used. In the case of ketones, ionic liquid 1-hexyl-1,2,4-triazolium trifluoroactetate gives a good yield.

It is well known that applying green chemistry aspects for organic reactions would reduce the toxicity of chemicals and it reduces the amount of volatile organic solvents too. Thus we have developed a Bronsted acidic 1-pentyl-1,2–4-triazolium methanesulfonate as a room temperature ionic liquid for organic reactions as reaction medium. The same has been employed as organocatalyst for the synthesis of β-Carbonyl Compounds. The present papers reveal the significance of ionic liquids in optimization of reaction condition in terms of equivalence of reagents, impact of solvents and amount of catalyst, synthesis of library of halogen rich β-carbonyl compounds.

Green Lacewing, Chrysoperla zastrowi sillemi (Esben - Petersen) (Neuroptera: Chrysopidae) is one of the most important natural enemy and has a great role in reducing population of phytophagus insects in field crops and vegetables. Laboratory study was conducted during 2019–20 to record foraging potential of different larval stages of C. z. sillemi against two tailed mealybug Ferrisia virgata nymphs. Predator was found feeding on all the nymphal instars of F. virgata. Feeding potential of C. z. sillemi on the nymphs F. virgata revealed that maximum number of F. virgata nymphs (37.30) was consumed by third instar grub during its developmental period of 3.30 days. A total of 66.87 nymphs were consumed by C. z. sillemi during its total larval period of 9.16 days. The insecticide-tolerance and hatchability of eggs of C. z. sillemi was tested against six different insecticides viz, imidacloprid 17.8 SL (0.00712%), thiamethoxam 25% WG (0.005%), chlorantraniliprole 18.5 SC (0.0037%), fipronil 5% SC (0.01%), spinosad 45% SC (0.0125%) and azadiractin 1% EC (0.02%) having varied formulation used in guava ecosystem to control the pests. Interestingly, the hatchability of the eggs varied from 78.5% recorded in untreated check to 41.0% in imidacloprid 17.8 SL (0.00712%). Treatments were evaluated for their toxicity to C. z. sillemi third instar grubs. After 24 hrs of treatment, maximum grub mortality of 80.0% was encountered in thiamethoxam 25 WG (0.005%) treatment.

Singlet fission (SF) is an exciton multiplication process with the potential to raise the efficiency limit of single junction solar cells from 33% to up to 45%. Most chromophores generally undergo SF as solid-state crystals. However, when such molecules are covalently coupled, the dimers can be used as model systems to study fundamental photophysical dynamics where a singlet exciton splits into two triplet excitons within individual molecules. Here we report the synthesis and photophysical characterization of singlet fission of a hexacene dimer. Comparing the hexacene dimer to analogous tetracene and pentacene dimers reveals that excess exoergicity slows down singlet fission, similar to what is observed in molecular crystals. Conversely, the lower triplet energy of hexacene results in an increase in the rate of triplet pair recombination, following the energy gap law for radiationless transitions. These results point to design rules for singlet fission chromophores: the energy gap between singlet and triplet pair should be minimal, and the gap between triplet pair and ground state should be large., We report the synthesis and photophysical characterization of highly exoergic singlet fission in a hexacene dimer revealing exciton dynamics that follow the energy gap law.

The dispersion of magnetic nanoparticles in matrix is crucial to ensure optimum performance of the composite. The difficulty level of achieving good dispersion is further increase when a multi-phases of matrix is present. A pre-coating technique of magnetic nanoparticles with polypropylene using ball-mill prior to melt-blending process was employed to prepare a multi-phases thermoplastic natural rubber composite. The effect of filler loading (2 wt%-10 wt%) on morphology, structure, magnetic properties, thermal stability and dynamic mechanical properties of the composites were investigated. It was found that the NiZn ferrite nanoparticles act as nucleating agent to form beta isostatic polypropylene thermoplastic composites. The composites' magnetic properties are directly dependent on the filler concentration. The dispersion of magnetic fillers in polymer matrix plays role in affecting the magnetic properties and thermal stability. The preference of filler to locate at amorphous phase has distorted the chain orientation of natural rubber and polypropylene. Hence, the polymorphism and crystallinity of the matrix varied as the filler loading increased, affecting the dynamic mechanical properties. It was found that 8 wt% NiZn nanocomposite exhibits highest E’ and tanδ, indicating the dynamic mechanical properties of NiZn nanocomposite are affected by β-phase degree. Keywords: Magnetic, Thermoplastic natural rubber, Nanoparticles, Composites

Nontypeable Haemophilus influenzae (NTHi) is a leading cause of respiratory tract infections worldwide and continues to be a global health burden. Adhesion and colonization of host cells are crucial steps in bacterial pathogenesis, and in many strains of NTHi, the interaction with the host is mediated by the high molecular weight adhesins HMW1A and HMW2A. These adhesins are N-glycoproteins that are modified by cytoplasmic glycosyltransferases HMW1C and HMW2C. Phase variation in the number of short sequence repeats in the promoters of hmw1A and hmw2A directly affects their expression. Here, we report the presence of similar variable repeat elements in the promoters of hmw1C and hmw2C in diverse NTHi isolates. In an ex vivo assay, we systematically altered the substrate and glycosyltransferase expression and showed that both of these factors quantitatively affected the site-specific efficiency of glycosylation on HMW-A. This represents a novel mechanism through which phase variation can generate diversity in the quantitative extent of site-specific post-translational modifications on antigenic surface proteins. Glycosylation occupancy was incomplete at many sites, variable between sites, and generally lower close to the C-terminus of HMW-A. We investigated the causes of this variability. As HMW-C glycosylates HMW-A in the cytoplasm, we tested how secretion affected glycosylation on HMW-A and showed that retaining HMW-A in the cytoplasm indeed increased glycosylation occupancy across the full length of the protein. Site-directed mutagenesis showed that HMW-C had no inherent preference for glycosylating asparagines in NxS or NxT sequons. This work provides key insights into factors contributing to the heterogenous modifications of NTHi HMW-A adhesins, expands knowledge of NTHi population diversity and pathogenic capability, and is relevant to vaccine design for NTHi and related pathogens.

Five new chemo-receptors, based on arylamino-naphthoquinone, possessing electron donating and electron withdrawing substituents have been prepared by single step green method. These receptors are found to be highly selective and sensitive towards cyanide ions in aqueous HEPES buffer solution (pH 7.2). The mechanism, as evidenced by 1H NMR, electrochemical and theoretical studies, is based on instantaneous deprotonation of –NH moiety by cyanide, which is enabled by substituent dependent resonance effect of the phenyl ring. This is confirmed by single crystal XRD data. The detection limit is calculated to be in the order of 10−8 M, which is much lower than the permissible limit of cyanide in drinking water set by WHO (1.9 × 10−6 M).

The role of piperine, a water insoluble alkaloid compound on the nucleation, crystallinity, size, shape and dispersion of hydroxyapatite (HAp) nanoparticles was investigated. Two different concentrations of piperine were used as an organic modifier. FTIR spectra support the transformation of functional groups. The XRD pattern reveals the crystalline nature of the materials. The TEM images disclose the mechanism of nucleation, formation, shape, size and morphology of HAp nanorods. The addition of the piperine during the synthesis altered the morphology of HAp nanorods. Piperine, as water insoluble alkaloid could affect the morphology of the HAp nanoparticles with agglomeration. These types of well defined and shaped HAp nanorods can be used as a delivery service for drug release and in the field of biomaterial research.

The reaction of (NHC)ZnEt2 (1) with 2,6-dimethylphenol in the molar ratio 1:2 at room temperature resulted in a monomeric zinc dimethylphenoxide [(NHC)Zn(OC6H3-2,6-Me2)2] (NHC = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) (2). Whereas, the reaction of 1 with 2,6-dimethylphenol in the presence of water in the molar ratios 1:2:0.5 or 1:2:1 afforded [(NHC)2Zn2(μ-OH)(μ-OC6H3-2,6-Me2)(OC6H3-2,6-Me2)2] (3) and [(NHC)Zn(μ-OH)(OC6H3-2,6-Me2)]2 (4) respectively. Moreover, reaction of 1 with 2,6-diisopropylphenol in the presence of a base led to the isolation of [(NHC)Zn(μ-OH)(OC6H3-2,6-iPr2)]2 (5). Compounds 2–5 have been fully characterized by spectroscopic and single crystal X-ray diffraction studies. In this paper, we have discussed the synthesis, structural characterizations of 2–5 and the mechanism for the formation of compounds 3–5 from 2.

The present study aimed at evaluating the effects of lycopene on CMS-induced depressive-like behavioral changes in Wistar rats. In present study, rodents were selected randomly and grouped in to seven groups. Each group consists of six animals. All the groups are subjected to chronic mild stress in an unpredictable manner except the control group, which is free from stress. Behavioral changes induced during chronic mild stress were assessed by conducting the behavioral tests like forced swim test, sucrose preferences test, elevated plus maze test and open field tests in screening depressant and anxiety activity. The data analysis showed chronic mild stress produced depressive and anxiogenic behavior in the experimental rats. A significant increase in the immobility time and decrease in sucrose consumption in sucrose preference test are noted in CMS and vehicle groups. Similarly, in an elevated plus maze a significant decrease in the entries in the open arm and decrease in central square entries, and rearing behavior and increase in the duration of immobility were observed in open field test.Lycopene treatment for 6-weeks significantly decreased immobility time and increased in sucrose consumption observed in the forced swim test and sucrose preference test respectively. Lycopene significantly increased number of entries in the open arm of elevated plus maze and decreased grooming and freezing behavior in open field method. lycopene supplemented dose of 5mg/kg showed an insignificant results in all the behavioral models (p>0.05).The data were expressed as Mean±SD.Data were analyzed and differences between the means were determined by one-way analysis of variance (ANOVA) Using graph pad prism version 5.03 statistical software. In all the tests, differences were considered significant if p

The objective of this work is eco-friendly synthesis of Carbon/Copper oxide nano composites (C/CuO nano composites) from the aqueous extract of Aristolochia bracteolata (ABLPAE) via response surface methodology (RSM). Here we optimized various parameters to find out the absorption maximum value using RSM technique. Then the synthesized C/CuO nano composites were processed using different analytical tools. The crystanality of C/CuO was investigated using XRD analysis which exhibited crystalline size of 43 ± 2 nm. Additionally, synthesized C/CuO nano composites were used to study larvicidal activity using MANOVA; LSD-DMRT test. We found that results showed LC50 value at 26.42 ppm and 86.13 ppm for LC90. Ovicidal activity by anti-feedant method resulted in a dose dependent manner with a high mortality rate at higher concentrations.

Nanoceria green synthesis using Pisonia alba leaf extract was reported in this study. UV–Vis spectroscopy, TEM, EDX, XRD and FTIR were employed to characterize the synthesized nanoceria (CeO2 nanoparticles). The nanoceria synthesis and size were confirmed by UV–Vis and TEM analysis. The cerium signals observed in the EDX spectrum revealed that the synthesized nanoceria was pure in nature. The cubic fluorite crystal structure of the nanoceria was confirmed from XRD analysis. The chemical bonds pertaining to the bioreducing phytochemicals in P. alba leaf extract were identified by FTIR analysis. Nanoceria showed good antioxidant activity which was assessed by DPPH and FRAP assay. P. alba leaf extract derived nanoceria was highly inhibited the growth of Aspergillus flavus and Fusarium solani fungal strains. The antioxidant and antifungal properties of P. alba leaf extract derived nanoceria can make it as a suitable candidate for biological applications.

A series of 2-chloro N-substituted amino quinolines (2a–2j) were prepared and characterized by analytical and spectroscopic methods. As quinoline is an important pharmacophoric moiety, the prepared compounds were screened against a non-small cell lung cancer cell line, A549. One of the compounds, 2-chloro-8-methyl-N-(quinolin-5-yl)quinolin-4-amine (2b) is found to be active with inhibition concentration value of (IC50) 29.4 μM. The molecular docking studies with the predominant PI3K/AKT/mTOR pathway proteins also revealed the lesser binding energy with 2b. All the compounds are predicted to satisfy the ADME profile and the results let us to consider 2b as a lead compound for new generation of A549 cell line inhibitors and for further studies in this way.

Singlet fission has emerged as a key mechanism of exciton multiplication in organic chromophores, generating two triplet excitons from a single photon. Singlet fission is typically studied in crystalline films or in isolated dimers. Here, we investigate an intermediate regime where through-space interactions mediate singlet fission and triplet pair recombination within isolated polymer chains. Specifically, we investigate how appending pentacenes to a polynorbornene backbone can lead to macromolecules that take advantage of through-space π-π interactions for fast singlet fission and rapid triplet pair dissociation. Singlet fission in these systems is affected by molecular dynamics, and triplet-triplet recombination is a geminate process where the rate of recombination scales with molecular-weight. We find that these pendent pentacene polymers yield free triplets with lifetimes that surpass those of crystalline chromophores in both solution as isolated polymers and in thin films.

A novel synthetic strategy for the construction of substituted imidazoles from acetophenones and benzylamines via N-heterocyclic carbene (NHC) - catalysis was reported. This reaction can be performed under solvent-free condition without pre-functionalization of substrates. Various substituted acetophenones and benzylamines were converted to its corresponding imidazoles with good to excellent yields.

A bisimidazole ensemble (R) possessing naphthoquinone as signaling unit is synthesized and characterized using 1H and 13C NMR and LC-MS spectral techniques. Anion sensing behaviour of the receptor has been investigated using electronic and fluorescence spectral techniques. The receptor exhibits a striking colour change from yellow to brown selectively with cyanide in aqueous HEPES buffer-DMSO (1:1 v/v) medium with a detection limit of 1 μM. Job's continuous variation method suggests that the stoichiometry of the interaction is 1:2 (R:CN−). The binding constant for receptor-cyanide complex was found to be 8.7 × 102 M−1. The mechanism of detection of cyanide occurs via deprotonation of imidazole N-H protons, which is well supported by electrochemical study. DFT based theoretical calculations shows that the energy gap between HOMO and LUMO decreases from 3.3086 (in R) to 1.7799 eV (in R + CN−), which is responsible for the red-shift observed in the UV–Vis spectrum of R upon addition of cyanide ions. The present quinone-bisimidazole based receptor shows few advantages over similar bisimidazoles reported elsewhere.

This study investigates the contamination of groundwater by chromium and fluoride around leather tanning industries. Major ions, chromium, δ53Cr/δ52Cr and fluoride were analyzed by advanced analytical methods. High degree of variation was observed in the concentration of chloride in groundwater, which ranged between 205 and 3310 mg/L, around 56% of the samples were recorded above the acceptable limit indicating the quality of groundwater is fresh to saline and it could be due to mixing of tannery effluents with freshwater aquifers. The chromium in the groundwater around 40% of the sampling wells exceeds the permissible limit whereas, 37% of wells were with fluoride above the accepted limit. Geochemical modelling using Phreeqc suggest that the saturation index of minerals such as calcite, dolomite, fluoride, gypsum and anorthite is affected by precipitation, dissolution and ion exchange processes. Concentration of chromium isotopes δ53Cr and δ52Cr reveals the source of Cr in the groundwater is more likely from tannery effluents. Accumulation of fluoride in groundwater is contributed by bedrock, charnockite, granite, epidote hornblende gneiss, fissile hornblende biotite gneiss in the study area. Groundwater contamination in this area is caused by both natural as well as anthropogenic sources. Around 37% of the samples exceeds HQI limit (HQI>1), which indicates possible health problems to the public upon prolonged use of untreated groundwater for drinking. To overcome this situation, it's essential to improve the performance of the effluent treatment plants and recharge structure to recover the quality of groundwater.

A Novel chemosensor R possessing napthoquinone substituted benzaldehyde has been successfully designed, synthesized and characterized using NMR and mass spectral techniques. The receptor exhibits striking colour change from pale yellow to intense green with sodium cyanide in DMF-H2O (80–20% v/v) in a wide range of pH (3−12). Based on the results of spectral (UV–Vis, fluorescence and NMR), electrochemical and kinetic studies a plausible mechanism has been proposed for the cyanide detection process. The mechanism of sensing of cyanide by R is through the formation of cyanohydrin in acidic, neutral and basic solutions, which is the novelty of the receptor. The pseudo-first-order rate constants for the formation of cyanohydrin are found to be 2.9 × 10−3, 3.9 × 10−3 and 4.6 × 10−3 min−1 at pH values 5, 7 and 10, respectively in DMF-H2O (80–20% v/v) medium, supporting the ability of R to form cyanohydrin with equal ease in different pH values. The results of Job's continuous variation method indicates a 1:2 (R:CN−) stoichiometry for the interaction. The only minor drawback with the receptor is the time taken to impart visible colour change with cyanide ion, which is not instantaneous.

The objective of this study is to develop a Fluoride Index for mitigation of geogenic contamination by Managed Aquifer Recharge (FIMAR). This index was tested by applying to the Pambar river basin in southern India. About 40% of the study area had fluoride >1.5 mg/L, contributed from the dissolution of fluorite, fluorapatite, biotite and hornblende. The relationship between groundwater level and fluoride concentration exhibited two types of relationship. In shallow wells, groundwater recharge during monsoon increases the groundwater level and dilutes the fluoride concentration. During summer, evaporation decreases the groundwater levels and increases the fluoride content. In deep wells, the fluoride-rich salts that is deposited in the unsaturated zone due to evaporation in the pre-monsoon season is flushed during groundwater recharge and thus, the fluoride concentration increases with increase in groundwater level. This relationship was used as a key layer in FIMAR. Overlay analysis including the well type derived from the groundwater level and fluoride fluctuation, average fluoride concentration, geology, geomorphology, soil, drainage density, land use, lineament density and thickness of the weathered zone indicated 30% of the area was suitable for MAR to mitigate fluoride contamination. Since the construction of new MAR structures is cost-intensive, it is proposed to rejuvenate the existing ponds in the areas identified by FIMAR to induce recharge and dilute fluoride concentration. The positive impact was confirmed using numerical and geochemical modelling. This proves that FIMAR can be used as a planning tool in fluoride endemic areas and that the future MAR methods will be beneficial to mitigate geogenic fluoride contamination.

In the present study, batch scale biodiesel production was carried out using castor oil by alkali-catalyzed transesterification process was reported. Initially, the transesterification parameters like reaction time, catalyst concentration, reaction temperature and oil: methanol molar ratio on biodiesel production was optimized by conventional method followed by statistical based central composite design method. According to the optimized experimental results, the maximum of 94.9% FAME yield was obtained at 60 °C with 1.25% (w/v) KOH catalyst and 1:12 oil: methanol molar ratio for 60 min of reaction, which was in agreement with the predicted yield (93.7%). The purification of crude biodiesel was performed by simple evaporation and silica gel adsorption. The quality of fatty acid methyl ester was examined by Fourier Transform Infrared spectroscopy (FT-IR), Thin layer chromatography (TLC) and Gas Chromatography–Mass Spectrometry (GC–MS). The analytical results showed that significant quantity of methyl ester groups like ricinoleic, linolenic, palmitic acid and oleic acid were present in the biodiesel.

Recent synthetic studies on the organic molecules tetracene and pentacene have found certain dimers and oligomers to exhibit an intense absorption in the visible region of the spectrum which is not present in the monomer or many previously-studied dimers. In this article we combine experimental synthesis with electronic structure theory and spectral computation to show that this absorption arises from an otherwise dark charge-transfer excitation 'borrowing intensity' from an intense UV excitation. Further, by characterizing the role of relevant monomer molecular orbitals, we arrive at a design principle that allows us to predict the presence or absence of an additional absorption based on the bonding geometry of the dimer. We find this rule correctly explains the spectra of a wide range of acene derivatives and solves an unexplained structure-spectrum phenomenon first observed seventy years ago. These results pave the way for the design of highly absorbent chromophores with applications ranging from photovoltaics to liquid crystals., 29 pages, 63 pages with SI, 5 figures

This research investigates biodiesel mixtures’ performance and emission characteristics with fuel additives (Lanthanum oxide) at different proportions such as B20, B20 + 50 ppm, and B20 + 100 ppm. The study of the Scanning Electron Microscope and Energy Dispersive X-ray has synthesized and characterized these nanoparticles. At 50 ppm and 100 ppm, nano-additives were prepared for 30 min combined with B20 in a magnetic stirring process, followed by 10 min of ultrasound. However, the use of such mixtures is influence due to improved combustion properties of biodiesel blends resulting in high NOx release from engine exhaust. Usually, all unhealthy exhaust pollutants, including Hydrocarbon, and Carbon Monoxide, decrease marginally, except for nitrogen oxides in higher biodiesel blended with fuel additives. The brake thermal efficiency in the distributed biodiesel mixture of nanoparticles increased compared to B20. Incomplete combustion products have decreased, such as carbon monoxide and unburnt Hydrocarbon compared to B20.

Multi-layered coastal aquifers are complex aquifer systems with two or more aquifers divided by the impermeable or semi permeable layers. The objective is to assess the interaction between the aquifers using geochemical indicators in the urbanised multi-layered coastal aquifer of Sankaraparani river basin, India. Hydrogeologically, the coastal part of this region comprises of alluvium formation as upper aquifer and sandstone formation as lower aquifer. Groundwater samples were collected from 33 representative wells during June 2017 and January 2018. Electrical conductivity, pH, and alkalinity were measured in the field while the concentration of major ions was analysed in the laboratory. The groundwater level in the upper aquifer varies from 7.4 to 18 m msl. Na-Cl type groundwater is dominant in the upper aquifer whereas Ca-HCO3 and mixed Ca-Na-HCO3 type groundwater is dominant in lower aquifer. The processes that controls the groundwater chemistry are sulphate reduction, freshening ion exchange, calcite dissolution and conservative mixing of seawater and freshwater. Significantly different values of electrical conductivity, sodium and chloride ratio, base exchange index as well as the different geochemical facies between the upper and lower aquifer indicates the absence of interaction between the aquifers near to the coast. Whereas in the west, the similarity in these confirms the interaction and both the formation function as single aquifer. The groundwater in the upper aquifer is affected by seawater intrusion upto 2 km whereas the lower aquifer is not affected.