Degradation of munition wastes byPhanerochaete chrysosporium

“Pink water” is a waste-water stream generated by munitions LAP (loading, assembly, and packing) operations. The major components of this waste water are trinitrotoluene (TNT) and cyclotrimethylene trinitramine (RDX) at concentrations of 120-175 mg/L and 25 mg/L, respectively. Currently, pink water is treated by activated carbon adsorption. Removal efficiencies of >99.5% have been reported. However, this treatment method suffers a serious limitation in that the carbon cannot be safely regenerated. Loaded carbon is disposed of by incineration after a single use.

We have demonstrated that TNT, RDX, simulated, and actual pink water can be effectively treated byPhanerochaete chrysosporium immobilized on the disks of a rotating biological contractor (RBC) in both batch and continuous modes. Greater than 90% removal of TNT from a simulated pink water was observed in a continuous RBC with a residence time of about 24 h. The disk area required was about 10,000 ft²/gpm (4091 m²/m³h) feed. RDX was amenable to treatment, but RDX removal rates were somewhat slower. A full-scale treatment system was designed on the basis of laboratory data, and a cost analysis was performed. This analysis has shown that biotreatment of pink water can be a cost-effective alternative to carbon adsorption.

     

Kinetics of chlorination of some Ortho-, Meta-, and Para-substituted phenols by N-chloro-3-methyl-2,6-diphenylpiperidin-4-one: A LFER study

The kinetics of chlorination of a number of ortho-, meta-, and para-substituted phenols by N-chloro-3-methyl-2,6-diphenylpiperidin-4-one (NCP) in acid medium have been investigated. The reaction is of first order with respect to oxidant and the order with respect to the substrate varies depending on the nature of the substituent present in the ring. With cresols and m-chlorophenol the order is unity, with p-methoxyphenol, zero and with the other phenols, a fraction. Isokinetic and Exner plots give straight lines with fine correlation coefficients. But the Hammett plot gives a curve that was concave downwards, instead of a straight line. The observed Hammett plot deviation has been accounted for suitably. Regression analyses of the rate data of ortho-substituted phenols by using Taft and Charton equations to separate steric effects from electronic effects have been carried out. In this reaction, the localized electronic effect plays a major role while steric and resonance effects play a minor role.     

Modeling energy landscapes of proton motion in nonaqueous, tethered proton wires

We have modeled structures and energetics of anhydrous proton-conducting wires: tethered hydrogen-bonded chains of the form ···HX···HX···HX···, with functional groups HX = imidazole, triazole, and formamidine; formic, sulfonic, and phosphonic acids. We have applied density functional theory (DFT) to model proton wires up to 19 units long, where each proton carrier is linked to an effective backbone to mimic polymer tethering. This approach allows the direct calculation of hydrogen bond strengths. The proton wires were found to be stabilized by strong hydrogen bonds (up to 50 kJ/mol) whose strength correlates with the proton affinity of HX [related to pK(b)(HX)] and not to pK(a)(HX) as is often assumed. Geometry optimizations and ab initio molecular dynamics near 400 K on imidazole-based proton wires both predict that adding a proton to the end of such wires causes the excess charge to embed into the interior segments of these wires. Proton translocation energy landscapes for imidazole-based wires are sensitive to the imidazole attachment point (head or feet) and to wire architecture (linear or interdigitated). Linear imidazole wires with head-attachment exhibit low barriers for intrawire proton motion, rivaling proton diffusion in liquid imidazole. Excess charge relaxation from the edge of wires is found to be dominated by long-range Grotthuss shuttling for distances as long as 42 ?, especially for interdigitated wires. For imidazole, we predict that proton translocation is controlled by the energetics of desorption from the proton wire, even for relatively long wires (600 imidazole units). Proton desorption energies show no correlation with functional group properties, suggesting that proton desorption is a collective process in proton wires.     

Catalytic Ni(II) in reactions of SmI2: Sm(II)- or Ni(0)-based chemistry?

The addition of catalytic amounts of Ni(II) salts provide enhanced reactivity and selectivity in numerous reactions of SmI(2), but the mechanistic basis for their effect is unknown. We report spectroscopic and kinetic studies on the mechanistic role of catalytic Ni(II) in the samarium Barbier reaction. The mechanistic studies presented herein show that the samarium Barbier reaction containing catalytic amounts of Ni(II) salts is driven solely by the reduction of Ni(II) to Ni(0) in a rate-limiting step. Once formed, Ni(0) inserts into the alkyl halide bond through oxidative addition to produce an organonickel species. During the reaction, the formation of colloidal Ni(0) occurs concomitantly with Ni(0) oxidative addition as an unproductive process. Overall, this study shows that a reaction thought to be driven by the unique features of SmI(2) is in fact a result of known Ni(0) chemistry.     

Synthesis,spectral, thermal,optical and dielectric studies on 4-dimethylaminopyridinium picrate crystals

Single crystal of 4-dimethylaminopyridinium picrate was grown by slow evaporation solution growth method. The optical properties of the crystal were studied by using UV–vis absorption and transmittance studies. The emission spectrum indicates that the crystal shows green and red fluorescence emissions. The band gap energy of the crystal was calculated and it is found to be 2.05 eV. The thermal stability of the crystal was studied using thermogravimetry-differential thermal (TG-DTA) analyses. The thermal anomalies observed in the differential scanning calorimetry (DSC) heating and cooling cycles indicate the occurrence of a first order phase transition. FTIR spectrum was used to confirm the presence of various functional groups in the crystal. The synthesized crystal shows SHG efficiency 32 times greater than that of potassium dihydrogen phosphate (KDP). The dielectric constant and dielectric loss of the crystal decreases with increases in frequency.     

Growth,thermal, spectral optical and dielectric characterization of semiorganic material: Dihydroxylammonium tetrachlorostrontium(II) dihydrate

Single crystals of dihydroxylammonium tetrachlorostrontium(II) dihydrate were grown by slow evaporation solution growth method at ambient temperature. The suitability of this material for optical application was studied by UV–visible absorption and optical transmittance spectroscopic techniques. The powder X-ray diffraction (XRD) method was used to confirm the crystalline nature of the compound and it is observed that the compound crystallized in orthorhombic system. The thermal stability of the title compound was studied by thermogravimetry and differential thermal (TG–DTA) analyses. The thermal anomalies observed in the low temperature differential scanning calorimetry (DSC) study indicate the occurrence of the first order structural phase transitions in the compound. The FTIR spectrum characterizes the various chemical bonding and water molecules in the compound. The nonlinear optical property of the material was analyzed by modified Kurtz–Perry powder technique. The dielectric constant and dielectric loss of the compound decreases with increase in frequency.     

Sustained release applications of a fluoroalkyl ester-functionalized amphiphilic cyclodextrin by inclusion complex formation with water-soluble drugs in supercritical carbon dioxide

An amphiphilic γ-cyclodextrin, selectively functionalized with perfluorobutanoyl group, octakis(6-O-perfluorobutanoyl)-γ-cyclodextrin (γ-CyD-F), was investigated as a potential sustained release carrier for hydrophilic drugs, taking molsidomine (MOL) as a model drug. Supercritical carbon dioxide, an environmentally benign solvent, was used for the preparation of MOL/γ-CyD-F inclusion complexes. The molecular encapsulation of MOL by the amphiphilic cyclodextrin was confirmed by differential scanning calorimetry (DSC) and powder X-ray diffraction (XRD) studies. Additionally, ¹H NMR spectroscopy was used to investigate the inclusion mode of drug with the γ-CyD-F. The in-vitro release of MOL from the peanut oil suspensions into aqueous phase was found to be significantly retarded by the complexation with γ-CyD-F, mainly due to the hydrophobic properties associated with the γ-CyD-F.     

A computational study of the formation and dimerization of benzothiet-2-one

A computational B3LYP/6-31G(d,p) study of the formation of benzothiet-2-one (4) from benzothiophenedione (2) and its subsequent dimerization to 5 was performed. The proposed intermediate ketene 3 has no gas-phase barrier to ring closure to 4. Three transition structures for dimerization were located. The geometry of the lowest energy one (TS8a) has a geometry corresponding to a two atom + two atom, face-to-face addition of the two thiolactone moieties. The orbital interactions suggest that the reaction is pseudopericyclic.     

Chiroptical dissymmetries in fluorescence excitation from single molecules of (M-2) helicene dimers

We report on the single-molecule chiroptical properties of "right"-handed bridged triaryl amine helicene dimers, MH2. Using an experimental setup to precisely define the circular excitation polarization at the sample plane, we investigated the circular dichroic response in luminescence from individual molecules in which induced ellipticity from microscope optics is minimized. Our results comparing circular anisotropies in fluorescence excitation from MH2 and perylene diimide (PDI), an achiral, centrosymmetric chromophore, demonstrate a significant reduction in the breadth of the distribution of circular dissymmetry parameters obtained from modulation of the circularly polarized excitation source (457 nm). For PDI, we observe a symmetric distribution of circular anisotropy parameters centered about zero, with a fwhm of 0.25. For MH2, we observe an asymmetric distribution peaked at g = -0.09, with a slightly larger width as the corresponding PDI distribution. These results indicate that the large dissymmetry parameters (|g| > 0.5) in fluorescence excitation described in our original report (Hassey, R.; et al. Chirality 2008, 20, 1039-1046 and Hassey, R.; et al. Science 2006, 314, 1437-1439) were indeed affected by (at the time, unknown) linear polarization artifacts. However, the present results on MH2 provide compelling evidence for single-molecule circular dissymmetries much larger than solution or thin-film ensemble values, defined primarily by the enhanced rotatory strength (relative to the monomer), and restricted orientation at the sample surface.     

A facile one-pot synthesis of novel amphiphilic perfluoroalkyl ester functionalized γ-cyclodextrin and complex formation with anionic surfactants

γ-Cyclodextrin (γ-CyD) was hydrophobically modified by selective functionalization at the C-6 position (primary face) with fluoroalkyl ester groups. This new amphiphilic γ-CyD was prepared in a facile one-pot synthesis by direct esterification of γ-CyD with perfluorobutanoic acid on the narrow rim of macrocylic molecule. The selective per-substituted product, octakis (6-O-perfluorobutanoyl)-γ-cyclodextrin (γ-CyD-F), was confirmed by ¹H NMR, ¹³C NMR and ¹⁹F NMR spectroscopic methods. The complexing ability of the γ-CyD-F was investigated with different types of anionic surfactant having single or double hydrophobic tail groups. Predominant complex formation was observed in all cases with an equimolar mixture of surfactant and γ-CyD-F in methanol irrespective of the type of the surfactant.