Preparation and analysis of14C-lignin grass lignocellulose and DHP

(¹⁴C-lignin) grass lignocellulose was prepared from wheat seedlings injected with (¹⁴C-uniform) phenylalanine. Seedlings were injected 2 wk after germination and grown for 3–4 wk in a diurnal light cycle before harvesting. The plant material was ground in liquid N₂, extracted with hot water, benzene-ethanol, and ethanol, and treated with protease. Treatment of the lignocellulose with acid, alkali, and cellulase solubilized¹⁴C, which was analyzed by HPLC and TLC. Reverse-phase HPLC demonstrated that¹⁴C-ferulic and coumaric acid were bound primarily to carbohydrate and lignin, respectively. Gel permeation chromatography by HPLC of¹⁴C solubilized by treatment with 1M NaOH confirmed that the majority of the¹⁴C was incorporated into high molecular weight material. No¹⁴C was detected in either hexoses or pentoses obtained from the lignocellulose and only a minor amount was present as¹⁴C-phenylalanine. These studies show that (¹⁴C-lignin) grass lignocelluloses must be carefully characterized before being used as defined substrates for biodegradation studies. Coniferyl alcohol was synthesized by a route derived from those of Nakamura et al. (1974) and Nakamura and Higuchi (1976). DHP was then prepared by a modification of the method of Brunow and Wallin (1981) in which solutions of coniferyl alcohol and hydrogen peroxide were added alternately by a computer controlled HPLC system so that the coniferyl alcohol concentration was maintained below 1 mM throughout the synthesis. The DHP obtained was characterized by HPLC gel permeation chromatography and by NMR. The results of these analyses will be discussed.     

Polyamide Layer Chromatography of Alkaloids

Thirty alkaloids were separated by polyamide layer chromatography. The Rf values on seven solvent systems were tabulated and their behavior discussed.     

Conversion of 3,n-dithiabicyclo[n.3.1]alkatrienes to bicyclo[n.3.1]alkapentaenes

The application of the Ramberg-Backlund reaction in the conversion of several 3,n-dithiabicyclo[n.3.1]alkatrienes to the corresponding bicyclo[n.3.1]alkapentaenes is reported. Proton magnetic resonance and ultraviolet spectra were utilized in the overall characterization of bicyclo[8.3.1]tetradeca-2,8,10,12,1(14)-pentaene, bicyclo[9.3.1]pentadeca-2,9,11,1(15)-pentaene, and their precursors. The final step in the synthesis was a Ramberg-Backlund of bis-α,α′-chloro sulfone. The intermediate, 2-chloro-3-thiabicyclo[9.3.1]pentadeca-9,11,13,1(15)-tetraene 3,3-dioxide, was isolated and characterized. The structure and stability of the bridged α,α′-dichloro sulfide intermediates were examined.     

Micelles of imidazolium-functionalized polystyrene diblock copolymers investigated with neutron and light scattering

We synthesize a series of block copolymers comprising a polystyrene (PS) block and an imidazolium-functionalized PS (IL) block and characterize their assembly properties. We use small-angle neutron scattering and dynamic light scattering to determine the micelle size and shape in dilute solutions and to assess the micelle interactions in concentrated solutions. By studying a series of copolymers with fixed PS block length, we find that the length of the IL block governs the micelle dimensions. Our data suggest that these copolymers form elongated micelle structures where the IL block is extended in the micelle core. We find that these micelles can sequester water and that interactions between the micelles lead to structure factor peaks at elevated concentrations.     

A small cavity with reactive internal shell atoms spanned by four {As(W/V)9}-type building blocks allows host-guest chemistry under confined conditions

The reaction of [H2As(III)W18O60]7- with VO2+ and SO4(2-) ions in aqueous solution leads to a V(IV)/V(V) mixed-valence cluster anion containing the {As4M40O140}-type cryptand which has a high formation tendency. An important result is that it exhibits a new type of reactive internal cavity shell. The correspondingly obtained compound Na(NH4)20[{(V(IV)O(H2O))(V(IV)O)2(SO4)2}{(As(III)W9O33)2(As(III)W7.5V(V)1.5O31)2(WO2)4}] x 40 H2O (1), which can also be synthesized from a precursor with the preorganized cryptand, was characterized by elemental and thermogravimetric analyses (determination of crystal water content), redox titrations (determination of the number of V(IV) centers), electronic absorption as well as vibrational spectra, single-crystal X-ray structure analysis (including bond valence sum calculations), and magnetic susceptibility measurements. The relatively small central cavity--formed by the linking of four {AsM9}-type lacunary units (M = W/V) by four WO6 octahedra--allows positioning of a variety of cationic as well as anionic "guests" under confined conditions according to a new approach: replacement of some of the W by V atoms leads to high reactivity of the internal cavity shell as a result of relatively weak VO bonds compared to the WO bonds. This allows an interesting "encapsulation chemistry" with new options. In the present case the cavity contains besides an arrangement of three V(IV) centers, two sulfate groups that replace O atoms of the {AsM9} units as well as an interesting hydrogen bond situation.     

Palladium-catalyzed cross-coupling of B-benzyl-9-borabicyclo[3.3.1]nonane to furnish methylene-linked biaryls

[reaction: see text] Benzylboranes are noticeably uncommon partners within Suzuki-Miyaura coupling reactions. B-Benzyl-9-BBN was successfully coupled to a range of aryl/heteroaryl bromides, chlorides, and triflates to give pharmacologically important methylene-linked biaryl structures. Activated, deactivated, and sterically hindered substrates were successfully coupled in high yield using Pd(PPh(3))(4) or Pd(OAc)(2) with SPhos as the catalyst system.     

Rotational spectrum and carbon-13 hyperfine structure of the C3H, C5H, C6H, and C7H radicals

By means of Fourier transform microwave spectroscopy of a supersonic molecular beam, we have detected the singly substituted carbon-13 isotopic species of C(5)H, C(6)H, and C(7)H. Hyperfine structure in the rotational transitions of the lowest-energy fine structure component ((2)Pi(12) for C(5)H and C(7)H, and (2)Pi(32) for C(6)H) of each species was measured between 6 and 22 GHz, and precise rotational, centrifugal distortion, Lambda-doubling, and (13)C hyperfine coupling constants were determined. In addition, resolved hyperfine structure in the lowest rotational transition (J = 32-->12) of the three (13)C isotopic species of C(3)H was measured by the same technique. By combining the centimeter-wave measurements here with previous millimeter-wave data, a complete set of (13)C hyperfine coupling constants were derived to high precision for each isotopic species. Experimental structures (r(0)) have been determined for C(5)H and the two longer carbon-chain radicals, and these are found to be in good agreement with the predictions of high-level coupled-cluster calculations. C(3)H, C(5)H, and C(7)H exhibit a clear alternation in the magnitude and sign of the (13)C hyperfine coupling constants along the carbon-chain backbone. Because the electron spin density is nominally zero at the central carbon atom of C(3)H, C(5)H, and C(7)H, and at alternating sets of carbon atoms of C(5)H and C(7)H, owing to spin polarization, almost all of the (13)C coupling constants at these atoms are small in magnitude and negative in sign. Spin-polarization effects are known to be important for the Fermi-contact (b(F)) term, but prior to the work here they have generally been neglected for the hyperfine terms a, c, and d.     

Relating ground water and sediment chemistry to microbial characterization at a BTEX-contaminated site

The National Center for Manufacturing Science is investigating bioremediation of petroleum hydrocarbon at a site near Belleville, MI. As part of this study, we examined the microbial communities to help elucidate biodegradative processes currently active at the site. We observed high densities of aerobic hydrocarbon degraders and denitrifiers in the less-contaminated sediments. Low densities of iron and sulfate reducers were measured in the same sediments. In contrast, the highly contaminated sediments showed low densities of aerobic hydrocarbon degraders and denitrifiers, and high densities of iron and sulfate reducers. Methanogens were also found in these highly contaminated sediments. These contaminated sediments also showed a higher biomass, by the phospholipid fatty acids, and greater ratios of phospholipid fatty acids, which indicate stress within the microbial community. Aquifer chemistry analyses indicated that the highly contaminated area was more reduced and had lower sulfate than the less-contaminated area. These conditions suggest that the subsurface environment at the highly contaminated area had progressed into sulfate reduction and methanogenesis. The less-contaminated area, although less reduced, also appeared to be progressing into primarily iron- and sulfate-reducing microbial communities. The proposed treatment to stimulate bioremediation includes addition of oxygen and nitrate to the subsurface. Ground water chemistry and microbial analyses revealed significant differences that resulted from the injection of dissolved oxygen and nitrate. These differences included an increase in Eh, small decrease in pH, and large decreases in BTEX, dissolved iron, and sulfate concentrations at the injection well. Injected nitrate was rapidly utilized by the subsurface microbial communities, and significant nitrite amounts were observed in the injection well and in nearby down-gradient observation wells. Microbial and molecular analyses indicated an increase in denitrifying bacteria after nitrate injection. The activity and population of denitrifying bacteria were significantly increased at the injection well relative to a down-gradient well for as long as 2 mo after the nitrate injection ended.

     

Ground state correlations in H2 measured by the (e,2e) technique

The relative intensities for exciting the 1sσ_g, 2pσ_u, 2pπ_u, and 2sσ_g states of H₂ are measured in a 1200 eV noncoplanar symmetric (e,2e) experiment on H₂. Momentum distributions are obtained at separation energies corresponding to the various transitions. The ratio of transition probability to the excited states relative to the ground state is strongly dependent on the ion recoil momentum q, having a minimum value of approximately 2% at small q. The excited state cross sections are sensitive to electron correlation effects and the data are compared with calculated cross sections using a configuration interaction wavefunction for H₂.     

Do Valine Side Chains Have an Influence on the Folding Behavior of β‐Substituted β‐Peptides?

The influence of valine side chains on the folding/unfolding equilibrium and, in particular, on the 3₁₄‐helical propensity of β³‐peptides were investigated by means of molecular‐dynamics (MD) simulation. To that end, the valine side chains in two different β³‐peptides were substituted by leucine side chains. The resulting four peptides, of which three have never been synthesized, were simulated for 150 to 200 ns at 298 and 340 K, starting from a fully extended conformation. The simulation trajectories obtained were compared with respect to structural preferences and folding behavior. All four peptides showed a similar folding behavior and were found to predominantly adopt 3₁₄‐helical conformations, irrespective of the presence of valine side chains. No other well‐defined conformation was observed at significant population in any of the simulations. Our results imply that β³‐peptides show a structural preference for 3₁₄‐helices independent of the branching nature of the side chains, in contrast to what has been previously proposed on the basis of circular‐dichroism (CD) measurements.