Particle and heavy metal accumulation by two plant species in a coal mining area of Odisha, India.

Mining activities lead to severe particulate matter (PM) pollution that consequently has a detrimental effect on ecosystem. A study was therefore conducted in a coal mining area of Odisha, India with an objective to assess the particulate matter pollution on the basis of differential aerodynamic size (PM10 and PM2.5) of the particles, the metallic (Zn and Fe) composition, and also to evaluate their nature of deposition on two identified plant species. The results suggest a significant variation in particle and heavy metal fractions in the ambient air of different sites (p < 0.05). Fe dominated the finer particle (PM2.5) fraction while Zn dominated the coarser counterpart (PM10) in the ambient air. When evaluated for the particle and heavy metal deposition on leaf surface, Shorea robusta performed better in trapping the coarser particles (PM10) while Holarrhena floribunda was found to be an efficient scrubber of the finer particles (PM2.5). Fe deposition on surface of leaves was comparatively higher than Zn irrespective of plant species or size fractions. Therefore, it is concluded that both S. robusta and H. floribunda should be planted in a schematic manner to tackle the particulate pollution in coal mining areas.

Altitude governs the air pollution tolerance and heavy metal accumulation in plants.

Plant response to changing air pollution is a function of various factors including meteorology, type of pollutants, plant species, soil chemistry, and geography. However, the impact of altitude on plant behavior has received little attention to date. A study was therefore conducted to evaluate the impact of altitude on the air pollution tolerance index (APTI), heavy metal accumulation, and deposition in plant species. The results favor the hypothesis of a definite impact of altitude on biochemical and heavy metal accumulation in plants. While a significant decline (p < 0.05) in the relative water content (RWC), APTI, and heavy metal accumulation with increasing altitude was evident in the studied plant species, the behavior of ascorbic acid, leaf extract pH, chlorophyll content, and the particle heavy metal deposition was erratic and did not display any statistically significant differences. The metal accumulation index was in the following order: Ni > Zn > Cu > Pb > Cd > Co. Similarly, the particle heavy metal deposition on the leaf surface (µg/cm2) displayed significant species variability (p < 0.05) and was in the order: Cu (0.303) > Pb (0.301) > Ni (0.269) > Zn (0.241) > Cd (0.044) > Co (0.025). The accumulated heavy metal and RWC showcased a significant positive correlation with the APTI, suggesting the dominant role of RWC in the plant's tolerance against air pollution in an altitudinal gradient. Future studies on the role of micrometeorological conditions in altering APTI may be fruitful in ascertaining these postulations.

Soil organic carbon fractionation of spoiled and unspoiled soils under different land use and land cover systems.

Alteration in land use and land cover is the key factor affecting the soil carbon fractions and its distribution. A study was carried out to estimate the carbon fractions in soils of agricultural, forest and pasture lands in two different areas separated on the basis of industrial activities (spoiled and unspoiled) to get an insight on the long-term soil carbon storage potential. The results showed that the mean values of the total organic carbon (TOC) and various fractions are significantly different between the land use types (p < 0.05). Irrespective of the land uses, the forest land showed significantly higher TOC (7.97) than agricultural land (6.98) and pasture lands (6.68). Further, evaluation of carbon management index (CMI) indicated that forest lands had highest CMI value compared to the other land uses. The spoiled area had significantly higher TOC and carbon fractions than their respective counterparts in the unspoiled area (p < 0.05) due to the negative industrial impact on soil biological processes. The PCA separates the sources of different carbon fractions and revealed an association of N (nitrogen) and K (potassium) with VL (very labile) and L (labile) fractions and the association of P (phosphorous) with stable R (recalcitrant) form. Therefore, it can be inferred from the present study that alterations in land use not only result in soil quality degradation but also trigger a reduction in potential for long term soil C sequestration.

Stimulus Responsive Remotely Rupturable Adhesive Marbles Realized through a Hybrid Nanoparticle Concept.

Adhesive marbles, an innovative concept derived from liquid marble technology that is "remotely breakable on demand" by external stimuli, offer diverse application prospects. Therefore, a chemically linked superomniphobic hybrid perfluorinated carbon black-silica nanoparticle (PCBSN) was realized by functionalizing surface groups and used for encapsulating adhesives. PCBSN successfully encapsulated liquids and adhesives to form water (WM, contact angle 158°), epoxy (EM, contact angle 145°), and silicone (SM, contact angle 135°) marbles, regardless of the surface tension and polarity. Studies on the interface characteristics revealed that the work performed for marble formation maintained an inverse relationship with the surface energy of particles and the surface tension of encapsulated liquids. The marble formation energy was determined to be higher for EM (1.071 × 10-17 J) and lower for SM (0.946 × 10-17 J). Upon exposure to laser, marbles showed a rapid photothermal response, and the heat transferability on the surface of marbles followed the order SM > EM > WM. The marbles were remotely rupturable by regulating the applied laser power, with breaking time being tunable from <10 to 500 s. The photothermal efficiency (%) of marbles can be graded as good and falls in the range of 88.6 × 10-3 (EM) and 162.9 × 10-3 (SM) at 1.5 W laser power. The marbles possessed high mechanical integrity and repeated cyclability before breaking on the rolling impact test. These adhesive marbles formed from PCBSNs may represent attractive candidates for such applications as "bonding from a distance" through remote means.

The 46 kDa dimeric protein from Variovorax paradoxus shows faster methotrexate degrading activity in its nanoform compare to the native enzyme.

Methotrexate degrading enzymes are required to overcome the toxicity of the methotrexate while treating the cancer. The enzyme from Variovorax paradoxus converts the methotrexate in to non toxic products. Methotrexate degrading enzyme from V. paradoxus is a dimeric protein with a molecular mass of 46 kDa and it acts on casein and gelatin. This enzyme is optimally active at pH 7.5 and 40°C and nanoparticles of this enzyme were prepared by desolvation-crosslinking method. Enzyme nanoparticles could degrade methotrexate faster than the native enzyme and they show lower Km compare to the native enzyme. Enzyme nanoparticles show better thermostability and they were stable for much longer time in the serum compare to the native enzyme. Enzyme nanoparticles show better functionality than the native enzyme while clearing the methotrexate added to the serum suggesting their advantage over the native enzyme for the therapeutic and biotechnological applications.

Decomposition of O,S-dimethyl methylphosphonothiolate by ammonia on magnesium oxide: a theoretical study of catalytic detoxification of a chemical warfare agent.

The adsorption of a model nerve agent, O,S-dimethyl methylphosphonothiolate (DMPT), on the hydroxylated and unhydroxylated nano-crystalline magnesium oxide surface followed by the nucleophilic attack of ammonia (NH3) is investigated at the M06-2X/6-311++G(d,p) level of theory using the representative cluster models. The geometries of DMPT and NH3 are fully optimized, while the geometry of the oxide fragment is kept frozen. The main insight of this study is the incorporation of the Eley-Rideal mechanism for the first time in the detoxification process, where one of the reactant molecules (DMPT) is adsorbed and the other one (NH3) reacts with it directly impinging from the gas phase. There are two possible pathways of nucleophilic detoxification, either concerted or stepwise. The nature of the first transition state of nucleophilic attack in both pathways is the vital step for degradation. Our calculated results predict that the reaction of DMPT with NH3 gives rise to both P-S and P-O bond cleavage completely. Also, the P-S cleavage is found to be the favorable one over P-O bond breaking. The exploration of the overall reaction mechanism has established the catalytic activity of nano-crystalline MgO in nucleophilic DMPT degradation, as in all cases the activation barriers have reduced compared to the previously reported aminolysis of DMPT in the gas phase. Interestingly, the hydroxylated model has better catalytic performance than the unhydroxylated one.

Size dependent structural, electronic, and magnetic properties of Sc(N) (N=2-14) clusters investigated by density functional theory.

Structural, electronic, and magnetic properties of ScN (N=2-14) clusters have been investigated using density functional theory (DFT) calculations. Different spin states isomer for each cluster size has been optimized with symmetry relaxation. The structural stability, dissociation energy, binding energy, spin stability, vertical ionization energy, electron affinity, chemical hardness, and size dependent magnetic moment per atom are calculated for the energetically most stable spin isomer for each size. The structural stability for a specific size cluster has been explained in terms of atomic shell closing effect, close packed symmetric structure, and chemical bonding. Spin stability of each cluster size is determined by calculating the value of spin gaps. The maximum value for second-order energy difference is observed for the clusters of size N = 2, 6, 11, and 13, which implies that these clusters are relatively more stable. The magnetic moment per atom corresponding to lowest energy structure has also been calculated. The magnetic moment per atom corresponding to lowest energy structures has been calculated. The calculated values of magnetic moment per atom vary in an oscillatory fashion with cluster size. The calculated results are compared with the available experimental data.

Bhasma : The ancient Indian nanomedicine.

Ayurveda and other Indian system of medicine use metals, but their use is also amply described in Chinese and Egyptian civilization in 2500 B.C. Bhasma are unique ayurvedic metallic/minerals preparation, treated with herbal juice or decoction and exposed for Ayurveda, which are known in Indian subcontinent since 7(th) century A.D. and widely recommended for treatment of a variety of chronic ailments. Animal's derivative such as horns, shells, feathers, metallic, nonmetallic and herbals are normally administered as Bhasma. A Bhasma means an ash obtained through incineration; the starter material undergoes an elaborate process of purification and this process is followed by the reaction phase, which involves incorporation of some other minerals and/or herbal extract. There are various importance of Bhasma like maintaining optimum alkalinity for optimum health, neutralizing harmful acids that lead to illness; because Bhasma do not get metabolized so they don't produce any harmful metabolite, rather it breakdowns heavy metals in the body. Methods including for Bhasma preparation are parpati, rasayoga, sindora, etc., Bhasma which contain Fe, Cu, S or other manufacturing process plays a specific role in the final product(s). Particle size (1-2 µ) reduced significantly, which may facilitate absorption and assimilation of the drug into the body system. Standardization of Bhasma is utmost necessary to confirm its identity and to determine its quality, purity safety, effectiveness and acceptability of the product. But the most important challenges faced by these formulations are the lack of complete standardization by physiochemical parameters.

Fluorene-based chemodosimeter for "turn-on" sensing of cyanide by hampering ESIPT and live cell imaging.

A new salicylaldehyde appended fluorene-based chemodosimeter (FSal) has been designed by taking consideration of the special nucleophilicity of cyanide ion. FSal shows selective affinity towards CN- over other anions (namely F-, Br-, NO3 -, ClO4 -, N3 -, H2PO4 -, AcO-, I-, Cl-, and NO2 -) through turn-on fluorescence with a minimum detection limit of 0.06 ppm. The turn-on fluorescence of the FSal-CN complex resulting from hampering ESIPT is also supported by DFT and TDDFT calculations. Biological compatibility and live cell imaging of this unique probe have also been explored.

Performance of dispersion-corrected double hybrid density functional theory: a computational study of OCS-hydrocarbon van der Waals complexes.

The performance of double hybrid density functionals (DHDFs) has been assessed by studying the spectroscopic properties and potential energy curves of OCS-C2H4 (carbonyl sulfide-ethylene) and OCS-C4H6 (carbonyl sulfide-dimethylacetylene) van der Waals complexes. Both dispersion corrected and uncorrected DHDF theories have been applied to study the intermolecular interaction energies, stability, spectroscopic parameters, rigidity, and binding energies or depths of the potential well of the weakly bound complexes and also to explore the possibility of formation of three isomers of each complex. The correlation consistent valence triple zeta quality basis set is used to investigate the complexes. The calculated results provide insight into the computational methods applied to the weakly bound complexes. The double hybrid density functional B2PLYP and mPW2PLYP methods with dispersion corrections (B2PLYP-D2, B2PLYP-D3 and mPW2PLYP-D2, mPW2PLYP-D3) performed better over the B2PLYP and mPW2PLYP density functional methods without dispersion correction to deal with the weak dispersion interaction that prevails in these complexes. The results obtained by the dispersion-corrected density functional mPW2PLYP-D2 and mPW2PLYP-D3 methods agree very well with the earlier experimental values wherever available. The contributing components of the interaction energy have been analyzed by the symmetry-adapted perturbation theory (SAPT, here, SAPT0) to get insight into the interaction energy.

Binding affinity of substituted ureido-benzenesulfonamide ligands to the carbonic anhydrase receptor: a theoretical study of enzyme inhibition.

The binding properties of a series of benzenesulfonamide inhibitors (4-substituted-ureido-benzenesulfonamides, UBSAs) of human carbonic anhydrase II (hCA II) enzyme with active site residues have been studied using a hybrid quantum mechanical/molecular mechanical (QM/MM) model. To account for the important docking interactions between the UBSAs ligand and hCA II enzyme, a molecular docking program AutoDock Vina is used. The molecular docking results obtained by AutoDock Vina revealed that the docked conformer has root mean square deviation value less than 1.50 Å compared to X-ray crystal structures. The inhibitory activity of UBSA ligands against hCA II is found to be in good agreement with the experimental results. The thermodynamic parameters for inhibitor binding show that hydrogen bonding, hydrophilic, and hydrophobic interactions play a major role in explaining the diverse inhibitory range of these derivatives. Additionally, natural bond orbital analysis is performed to characterize the ligand-metal charge transfer stability. The insights gained from this study have great potential to design new hCA-II inhibitor, 4-[3-(1-p-Tolyl-4-trifluoromethyl-1H-pyrazol-3-yl)-ureido]-benzenesulfonamide, which belongs to the family of UBSA inhibitors and shows similar type of inhibitor potency with hCA II. This work also reveals that a QM/MM model and molecular docking method are computationally feasible and accurate for studying substrate-protein inhibition.

Kinetics and mechanism of the tropospheric oxidation of vinyl acetate initiated by OH radical: a theoretical study.

Vinyl acetate [VA (CH3COOC2H3)] is an important unsaturated and oxygenated volatile organic compound responsible for atmospheric pollution. In this work, possible reaction mechanisms for the degradation of OH-initiated atmospheric oxidation of VA are investigated. The potential energy surfaces (PESs) for the reaction of OH radical with VA in the presence of O2 and NO have been studied using the M06-2X/6-311++G(d,p) method. The initial addition reactions of more and less substituted ethylenic C-atoms of VA are treated separately, followed by a conventional transition state theory (TST) calculation for reaction rates. The direct H-abstraction mechanism and kinetics have also been studied. The initial OH addition occurs through a prereactive complex, and the calculated rate constants in the temperature range 250-350 K for both the addition reactions are found to have negative temperature dependence. The calculation indicates that the reaction proceeds predominantly via the addition of OH radical to the double bond rather than the direct abstraction of H-atoms in VA. IM1 [CH3C(O)O(•)CHCH2OH] and IM2 [CH3C(O)OCH(OH)(•)CH2], the OH adduct complexes formed initially, react with ubiquitous O2 followed by NO before their rearrangement. The formation of the prereactive complex plays an important role in reaction mechanism and kinetics. The calculated rate constant, k298K = 1.61 × 10(-11) cm(3) molecule(-1) s(-1), is well harmonized with the previous experimental data, k298K = (2.48 ± 0.61) × 10(-11) cm(3) molecule(-1) s(-1) (Blanco et al.) and k298K = (2.3 ± 0.3) × 10(-11) cm(3) molecule(-1) s(-1) (Picquet-Varrult et al.). Additionally, consistent and reliable enthalpies of formation at 298.15 K (ΔfH°298.15) have been computed for all the species involved in the title reaction using the composite CBS-QB3 method. The theoretical results confirm that the major products are formic acetic anhydride, acetic acid, and formaldehyde in the OH-initiated oxidation of VA in the presence of O2 and NO, which are in excellent agreement with the experimental findings.

A computational study of detoxification of lewisite warfare agents by British anti-lewisite: catalytic effects of water and ammonia on reaction mechanism and kinetics.

trans-2-Chlorovinyldichloroarsine (lewisite, L agent, Lew-I) acts as a blistering agents. British anti-lewisite (BAL, 2,3-dimercaptopropanol) has long been used as an L-agent antidote. The main reaction channels for the detoxification proceed via breaking of As-Cl bonds and formation of As-S bonds, producing stable, nontoxic ring product [(2-methyl-1,3,2-dithiarsolan-4-yl)methanol]. M06-2X/GENECP calculations have been carried out to establish the enhanced rate of detoxification mechanism in the presence of NH3 and H2O catalysts in both gas and solvent phases, which has been modeled by use of the polarized continuum model (PCM). In addition, natural bond orbital (NBO) and atoms in molecules (AIM) analysis have been performed to characterize the intermolecular hydrogen bonding in the transition states. Transition-state theory (TST) calculation establishes that the rates of NH3-catalyzed (2.88 × 10(-11) s(-1)) and H2O-catalyzed (2.42 × 10(-11) s(-1)) reactions are reasonably faster than the uncatalyzed detoxification (5.44 × 10(-13) s(-1)). The results obtained by these techniques give new insight into the mechanism of the detoxification process, identification and thermodynamic characterization of the relevant stationary species, the proposal of alternative paths on modeled potential energy surfaces for uncatalyzed reaction, and the rationalization of the mechanistic role played by catalysts and solvents.