A computational analysis of electronic effects of borazine and its monosubstituted derivatives

The effect of several subtituent groups on the borazine ring has been investigated by an ab initio molecular orbital (SCF) method at the 6-31G level. The optimized geometry was used to calculate the molecular electrostatic potential of these structures at the 6-31G level. The negative potentials generated near the B-H protons suggest that these protons are more easily substituted than the N-H protons in borazine. The magnitude of the negative potential near the B-H protons decreases in the order OH> F> NO₂, reflecting their varying electron-withdrawing ability. Both the methyl and amino groups tend to increase this negative potential indicating their electron-donating ability.     

Discovery of structurally diverse natural product antagonists of chemokine receptor CXCR3

The chemokines (CXCL9, CXCL10 and CXCL11) and associated CXCR3 receptor are expressed during the inflammatory process from multiple sclerosis, atherosclerosis or organ transplantation resulting in the recruitment of lymphocytes leading to tissue damage. It is hypothesized that blocking of the ligand/CXCR3 receptor interaction has potential to provide opportunity for development of agents that would block tissue rejection. In this paper, four classes of natural product inhibitors (IC₅₀ ranging 0.1–41 M) have been described that block the CXCR3 receptor interaction of IP-10 ligand. These include a cyclic thiopeptide (duramycin), polyketide glycosides (roselipins), steroidal glycosides (hypoglausin A and dioscin) and a novel alkyl pyridinium alkaloid that were isolated by bioassay-guided fractionation of the organic extracts derived from actinomycete, fungal, plant and marine sources and discovered using ¹²⁵ I IP-10/CXCR3 binding assay. Duramycin was the most potent with an IC₅₀ of 0.1 M. Roselipins 2A, 2B and 1A showed IC₅₀ values of 14.6, 23.5, and 41 M, respectively. Diosgenin glycosides dioscin, hypoglaucin A and kallstroemin D exhibited IC₅₀ values of 2.1, 0.47 and 3 M, respectively. A novel cyclic 3-alkyl pyridinium salt isolated from a sponge displayed a binding IC₅₀ of 0.67 M.     

Potential of Biocellulose Nanofibers Production from Agricultural Renewable Resources: Preliminary Study

In the present preliminary study, we report results for the biocellulose nanofibres production by Gluconacetobacter xylinus. Production was examined by utilizing different feedstocks of single sugars and sugar mixtures with compositions similar to the acid hydrolyzates of different agriculture residues. Profiles for cell proliferation, sugar consumption, and the subsequent pH changes were thoroughly analyzed. Highest biocellulose production of 5.65 g/L was achieved in fructose medium with total sugar consumption of 95.57%. Moreover, the highest production using sugar mixtures was 5.2 g/L, which was achieved in feedstock with composition identical to the acid hydrolyzate of wheat straws. This represented the highest biocellulose yield of 17.72 g/g sugars compared with 14.77 g/g fructose. The lowest production of 1.1 and 1.75 g/L were obtained in xylose and glucose media, respectively, while sucrose and arabinose media achieved relatively higher production of 4.7 and 4.1 g/L, respectively. Deviation in pH of the fermentation broths from the optimum value of 4–5 generally had marked effect on biocellulose production with single sugars in feedstock. However, the final pH values recorded in the different sugar mixtures were ～3.3–3.4, which had lower effect on production hindrance. Analyzing profiles for sugars' concentrations and cell growth showed that large amount of the metabolized sugars were mainly utilized for bacterial cell growth and maintenance, rather than biocellulose production. This was clearly observed with single sugars of low production, while sugar consumption was rather utilized for biocellulose production with sugar mixtures. Results reported in this study demonstrate that agriculture residues might be used as potential feedstocks for the biocellulose nanofibres production. Not only this represents a renewable source of feedstock, but also might lead to major improvements in production if proper supplements and control were utilized in the fermentation process.     

Crystal‐structure dependence of electroactive properties in differently prepared poly(vinylidene fluoride/hexafluoropropylene) copolymer films

The electroactive properties of two random copolymers of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) were studied. The compositions were 95/5 and 85/15 mol % P(VDF/HFP). For each composition, three different film‐preparation methods were used—solvent casting, melt‐pressed quenched, and melt‐pressed slow‐cooled. The ferroelectric properties observed were strongly dependent on the preparation methods of the films as well as the HFP molar content of the samples. The highest remanent polarizations (P_r) obtained from electric displacement versus electric field (D‐E) hysteresis data are 80 and 50 mC/m² for the 5 and 15% HFP solvent‐cast samples, respectively. The slow‐cooled samples do not exhibit any ferroelectric behavior for either the 5 or 15% HFP copolymers. It was also observed that both the 5 and 15% HFP slow‐cooled samples have a smaller electrostrictive response relative to the other two types of samples. Wide‐angle X‐ray diffraction and DSC results suggest that the 5% HFP sample has a higher crystallinity relative to the 15% HFP sample for each preparation method. In addition, different crystal phases form in the samples resulting from the different preparation methods. Fourier transform infrared results suggest that the slow‐cooled samples are in the nonpolar α phase, whereas the quenched and solvent‐cast samples are more likely in the polar β phase. The slow‐cooled samples do not show a switching peak in their nonpolar α‐phase crystalline state. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2793–2799, 2001     

Experimental validation of distinct element simulation for dynamic wheel–soil interaction

The deformation behaviour of the soil during dynamic wheel–soil interaction was studied by using the discontinuum modelling technique, distinct or discrete element method (DEM). The simulation model was developed using DEM for two types of soil, soil-A (coarse sand) and soil-B (medium sand). A transparent sided soil bin was used to observe the soil deformation. Three CCD video camera photographic images of the validation experiments were analyzed and compared with the simulation program results.This paper presents the simulation and validation results for two types of soil at three different vertical loadings of 4.9, 9.8 and 14.7 N. Wheel sinkage, vertical and horizontal draft force acting on the rigid wheel and the soil deformation images from the validation experiments were some of the data used to compare the simulation program results with the validation experiments. The simulation program was helpful to understand the complex deformation behaviour of the soils. The simulated results for the deformation behaviour of soil-B showed better correlation with the validation experiments than soil-A. The results obtained have also been compared with the previous work on DEM to explain phenomena such as the high simulated sinkage of the rigid wheel.     

Structure and semisynthesis of platensimide A, produced by Streptomyces platensis

Platensimycin and platencin are novel natural product antibiotics that inhibit bacterial growth by inhibiting condensing enzymes FabF and FabF/FabH of fatty acid biosynthesis pathways, respectively. Continued search for the natural congeners of these compounds led to the isolation of platensic acid, the free C-17 tetracyclic enoic acid, and platensimide A, a 2,4-diaminobutyric acid amide derivative. Isolation, structure, semisynthesis, and activity of these compounds are described.     

A computational analysis of ortho-lithiation in aromatic systems

We have analyzed the ability of a tertiary amide group to activate an ortho position on aromatic system toward an electrophilic attack using an ab initio SCF molecular orbital method. The molecular electrostatic potential was used to analyze the electronic nature of the ortho-lithiated intermediate complex and possible sites for electrophilic attack.     

Isolation, enzyme-bound structure, and activity of platensimycin A1 from Streptomyces platensis

Inhibition of fatty acid synthesis is emerging as a valuable target for antibacterial agents. Platensimycin and platencin are novel natural products that were reported recently to inhibit the FabF and FabF/FabH condensing enzymes, respectively, present in the fatty acid biosynthetic pathway. Selective inhibition of these enzymes by platensimycin and platencin accounts for their potent antibiotic activity. We have continued our quest to find additional members of this class of compounds leading to discovery of platensimycin A₁, a hydroxylated congener. We report herein the isolation, structure, antibacterial and enzymatic activities, and co-crystal structure bound to Escherichia coli FabF. The lower activity of platensimycin A₁ suggests that substitution at C-14 is detrimental for the activity.     

Fabrication of cuprous and cupric oxide thin films by heat treatment

Cuprous oxide (Cu₂O) and cupric oxide (CuO) thin films were prepared by thermal oxidation of copper films coated on indium tin oxide (ITO) glass and non-alkaline glass substrates. The formation of Cu₂O and CuO was controlled by varying oxidation conditions such as, oxygen partial pressure, heat treatment temperature, and oxidation time. The microstructure, crystal direction, and optical properties of copper oxide films were measured with X-ray diffraction, atomic force microscopy, and optical spectroscopy. The results indicated that the phase-pure Cu₂O and CuO films were produced in the oxidation process. Optical transmittance and reflectance spectra of Cu₂O and CuO clearly exhibited distinct characteristics related to their phases. The electrical properties indicated that these films formed ohmic contacts with Cu and ITO electrode materials. Multilayers of Cu₂O/CuO were fabricated by choosing the oxidation sequence. The experimental results in this paper suggest that the thermal oxidation method can be employed to fabricate device quality Cu₂O and CuO films that are up to 200–300 nm thick.