Extraction and separation of cationic surfactants from river sediments: application to a spectrophotometric determination of cationic surfactant in an aquatic environment using membrane filters.

The quantitative extraction of cationic surfactant (CS+) in river sediments was studied. Further, the developed method was applied to the spectrophotometric determination of CS+ in urban river sediment samples by solid-phase extraction with membranes. A mixture of methanol and hydrochloric acid was proposed as an eluent. Dried sediment was digested in the eluent under ultrasonic irradiation. After elution, the eluent was evaporated to almost dryness. The residue was dissolved in a small volume of methanol and diluted to a certain volume with water. The pH of the solution was adjusted to 4-5 to separate iron and some other metals as precipitates of hydroxides. The solution was passed through two-piled membranes: first glass-fiber and then polytetrafluoroethylene (PTFE) membranes. A small volume of methanol was passed through the membranes to elute any CS+ retaining on the membranes. After passing the methanol solution through a cationic exchange resin column, the retained CS+ was eluted with methanol containing a high concentration of sodium chloride. Water, Bromophenol Blue (BPB) and hydrochloric acid were added to the solution. The solution was passed through a mixed cellulose ester membrane filter to retain an ion associate of CS+.BPB-. The retained ion associate was dissolved in a small volume of N,N-dimethylformamide together with the membrane filter, followed by the addition of triethanolamine to make the solution alkaline. The absorbance due to BPB2- was measured at 603 nm against a reagent blank. This method was applied to the determination of CS+ in river water and sediment. A cationic surfactant in sediments at 10(-5) mol kg-1 levels was detected with satisfactory precision. It was found that CS+ was about 500-fold enriched in the sediment from water at the place where domestic wastewater was discharged.     

Oxidation of Cyclic Hemiacetals into Diketones: Final Steps in the Conversion of a Triterpenoid Ring a into a Steroidal Enone by a New Short Route

As a part of our studies in the conversion of triterpenoids into steroids we have reported¹ that the Jones oxidation of some triterpenoid hemiacetals (1) gives acyloxy acids (2) instead of the desired 1,5-diketones (3). We now report² the shortest route yet for the reconstruction of a triterpenoid ring A ketone (4) into a steroidal enone (7) involving as key steps the exhaustive Baeyer-Villiger oxidation³ of triterpenoid ketones (4) into δ-lactones (5) and mild chromium(VI) oxidation of cyclic hemiacetals (1) into diketones (3).     

Higher order corrections in perturbative quantum chromodynamics

We present some techniques which have been developed recently or in the recent past to compute Feynman graphs beyond one-loop order. These techniques are useful to compute the three-loop splitting functions in QCD and to obtain the complete second order QED corrections to Bhabha scattering.     

Photocontrol and processing of LHCP II apoprotein in Euglena: possible role of Golgi and other cytoplasmic sites.

Like other green photosynthetic eukaryotes, cells of Euglena gracilis var. bacillaris and strain Z contain a light-harvesting chlorophyll a/b complex associated with photosystem II. In Euglena, the formation of the 26.5 kDa principal light-harvesting chlorophyll a/b binding protein of photosystem II (LHCP II) has a number of unusual features. The precursors to LHCP II are large polyproteins containing multiple copies of LHCP II, and photocontrol of their formation is largely translational. Under conditions favoring LHCP II accumulation in the thylakoids, a reaction with anti-LHCP II antibody can be observed in the Golgi by immunogold electron microscopy. The timing of the immunoreaction in the Golgi in synchronous cells and in cells undergoing normal light-induced chloroplast development suggests that the nascent LHCP II passes through the Golgi on the way to the thylakoids. The compartmentalized osmiophilic structure (COS) also shows an immunoreaction. These observations, and other discussed in this paper, suggest that light permits translation of polyprotein LHCP II precursors on cytoplasmic ribosomes of the rough endoplasmic reticulum (ER) and that these pass through the ER to the Golgi where, presumably, further modifications take place. Since an LHCP II immunoreaction is found in Golgi vesicles, these may transport the nascent LHCP II to the plastid and facilitate its uptake.     

Crystal structure of YBa2Cu3O7−x thin films prepared by pulsed laser deposition with substrate bias voltage

The crystal structure of YBa₂Cu₃O_7−x thin films has been investigated by cross-section transmission electron microscopy. The samples were deposited on MgO (100) substrates at 670°C with substrate bias voltages of ±300 V. For the unbiased case, c-axis, a-axis and (103) oriented domains normal to the substrate surface were observed. In this film, the c-axis oriented domains are dominant, but the crystal often exhibits a longer c-lattice constant than that of the YBa₂Cu₃O_7−x system, so extra cationic layers are inserted in the YBa₂Cu₃O_7−x intrinsic stacking sequence. For the case of −300 V, rotated domains were dominant in the entire film; however, c-axis oriented domains also grow from the substrate surface. Small-angle semicoherent grain boundaries between them were observed. In the case of +300 V, all the grains show c-axis oriented YBa₂Cu₃O_7−x. The degree of preferential orientation of the grains is reduced at negative bias voltage of −300 V and the structure defects are reduced by applying a positive bias of +300 V.     

Numerical optimization of bolometric infrared detectors including optical loading, amplifier noise, and electrical nonlinearities

We present numerical methods for the optimization of bolometric infrared detectors which use current-biased semiconducting thermistors. We extend the analysis of Griffin and Holland to explicitly include both the electric field dependence of the thermistor resistance and amplifier noise. These methods allow the user to design and evaluate an optimized bolometer once such parameters as the optical loading, the heat sink temperature, and the materials for the thermal link and the thermistor have been chosen. Measured parameters which describe the electrical nonlinearities in neutron transmutation doped germanium are presented. The consequences for bolometer optimization of including these effects are illustrated. This program will be made available at the web site http://physics7.berkeley.edu/bolometer.html. This work was supported in part by the Director, Office of Energy Research, Office of Basic Energy Sciences, Materials Sciences Division of the U. S. Department of Energy under contract DE-AC03-76SF00098.     

Homoleptic tris(methoxydimethylsilyl)silanides of the alkaline earth metals: first zwitterionic silanides with two naked silyl anions

The first zwitterionic alkaline earth metal silanides featuring two naked silyl anions were synthesized and a combined structural and computational study on these zwitterions revealed a correlation between the energy of the HOMO and the degree of negative charge of the naked silyl anions.     

Fragmentation and reactivity in collisions of protonated diglycine with chemically modified perfluorinated alkylthiolate-self-assembled monolayer surfaces

Direct dynamics simulations are reported for quantum mechanical (QM)/molecular mechanical (MM) trajectories of N-protonated diglycine (gly(2)-H(+)) colliding with chemically modified perfluorinated octanethiolate self-assembled monolayer (SAM) surfaces. The RM1 semiempirical theory is used for the QM component of the trajectories. RM1 activation and reaction energies were compared with those determined from higher-level ab initio theories. Two chemical modifications are considered in which a head group (-COCl or -CHO) is substituted on the terminal carbon of a single chain of the SAM. These surfaces are designated as the COCl-SAM and CHO-SAM, respectively. Fragmentation, peptide reaction with the SAM, and covalent linkage of the peptide or its fragments with the SAM surface are observed. Peptide fragmentation via concerted CH(2)-CO bond breakage is the dominant pathway for both surfaces. HCl formation is the dominant species produced by reaction with the COCl-SAM, while for the CHO-SAM a concerted H-atom transfer from the CHO-SAM to the peptide combined with either a H-atom or radical transfer from the peptide to the surface to form singlet reaction products is the dominant pathway. A strong collision energy dependence is found for the probability of peptide fragmentation, its reactivity, and linkage with the SAM. Surface deposition, i.e., covalent linkage between the surface and the peptide, is compared to recent experimental observations of such bonding by Laskin and co-workers [Phys. Chem. Chem. Phys. 10, 1512 (2008)]. Qualitative differences in reactivity are seen between the COCl-SAM and CHO-SAM showing that chemical identity is important for surface reactivity. The probability of reactive surface deposition, which is most closely analogous to experimental observables, peaks at a value of around 20% for a collision energy of 50 eV.     

Subsurface damage in alumina and alumina–silicon carbide nanocomposites

The subsurface plastic deformation below alumina (Al₂O₃) and Al₂O₃–silicon carbide (SiC) nanocomposite surfaces subjected to grinding, polishing and annealing has been measured by high-resolution grazing-incidence parallel-beam X-ray powder diffraction and transmission electron microscopy. The variation with angle in the full width at half-height maximum (FWHM) of the X-ray Bragg peaks was successfully modelled by a FWHM distribution that fell exponentially with increasing depth. Consistent parameters were extracted from data taken using both prism and pyramidal reflecting planes. Correlation was found between the depth at which the FWHM fell to 1/e of the surface value and the depth of damage observed by transmission electron microscopy. The associated surface strain in the nanocomposite was found to increase linearly with increasing diameter of the diamond polishing particles. In ground 5?vol.%?SiC nanocomposite, these random surface strains fell by a factor of 7 and the depth of damage increased by a factor of 3 after annealing at 1250°C for 2?h. No differences were observed in the Bragg peak FWHM as a function of angle for material polished with 1?µm diamond grit before and after annealing.     

Infrared Spectrum of Pyromellitic Diimide HN(CO)2C6H2(CO)2NH

The IR spectrum of pyromellitic diimide, HN(CO)₂C₆H₂(CO)₂NH, has been measured for polycrystalline sample. The observed bands have been assigned to the IR active fundamentals and combinations on the basis of a D_2h molecular symmetry by comparison with those of pyromellitic dianhydride. Band shifts from dianhydride to diimide were observed for the 0[dbnd]C-X-C[dbnd]O fundamentals and the N-H modes have been assigned by comparison with those reported for phthalimides.