4-[2-(1-Acetyl-2-oxopropylidene)-hydrazino]-N-(pyrimidin-2-yl)benzenesulfonamide

In the title compound, C15H15N5O4S, the dihedral angle between the pyrimidine and benzene rings is 84.56 (2)degrees. Intramolecular hydrazine-carbonyl N-H center dot center dot center dot O and intermolecular sulfonamide-pyridimine N-H center dot center dot center dot N hydrogen bonds stabilize the molecular and crystal structures, respectively.

Conformations of the amino aterminal tetrapeptide of emerimicins and antiamoebins in solution and in the solid state

The conformations of Boc-l-Phe-(AiB)3-OH (1) and Boc-l-Phe-(Aib)3-OMe (2) which correspond to the amino terminal sequence of the emerimicins and antiamoebins have been studied in solution using 270 MHz 1H n.m.r. In dimethyl sulphoxide solution both peptides show the presence of two strongly solvent shielded Aib NH groups, consistent with a consecutive β-turn conformation, involving the Aib(3) and Aib(4) NH groups in intramolecular 4 → I hydrogen bonds. This folded conformation is maintained for 2 in chloroform solution. Nuclear Overhauser effect studies provide evidence for a Type II Phe-Aib β-turn. An X-ray diffraction study of Boc-(d,l)-Phe-(Aib)3-OH establishes a single type III(III′) β-turn conformation with Aib(2)-Aib(3) as the corner residues. A single intramolecular 4 → I hydrogen bond between Phe(I) CO and Aib(4) NH groups is observed in the crystal. The solution conformation may incorporate a consecutive type II-III′ structure for the Phe(1)-Aib(2)-Aib(3) segment, with the initial type II β-turn being destabilized by intermolecular interactions in the solid state.

Cresols - An investigation into their electronic structure and spectra

The three isomeric cresols were subjected to the all-valence-electron CNDO/2 andPPP-CI calculations. Results from this study were used: (i) to compare the electronic structures of these isomers vis-Ã-vis parent compounds-phenol and toluene, (ii) to obtain a quantitative picture of their chemical reactivities and electronic absorption spectra. Using the sgr-core charges derived from CNDO/2 calculations and subsequently revising the valence-state ionisation potential and one-center-two-electron repulsion integrals, thePPP-CI calculations were performed on the title compounds according toNishimoto andForster scheme. In these calculations the pseudo-unsaturated nature of the methyl group has been given due consideration. In spectral assignment, compared to the conventionalPPP approach, the CNDO/2-basedPPP-CI method gave a better agreement with the experimental data.

Dietary composition manipulation to enhance the performance of juvenile barramundi (Lates calcarifer Bloch) reared in cool water

Barramundi Lates calcarifer reared in cool water (20-22 degrees C) grow slowly and feed is used poorly compared with fish in warm water (28-32 degrees C). Two comparative slaughter growth assays were carried out with juvenile barramundi to see if increasing the digestible energy (DE) and/or the n-3 highly unsaturated fatty acid (n-3 HUFA) content of the feed would improve growth of fish raised in cool water. Increasing the DE content of the feed from 15 to 17 or 19 MJ kg(-1) while maintaining a constant protein to energy ratio in Experiment 1 brought about significant improvements in feed conversion ratio (FCR) (from 2.01 to 1.19) and daily growth coefficient (DGC; from 0.69 to 1.08%/day) for fish at 20 degrees C. For fish at 29 degrees C, improvements, while significant, were of a lesser magnitude: from 1.32 to 0.97 for FCR and from 3.24 to 3.65%/day for DGC. Increasing the absolute amount of dietary n-3 HUFA, expressed as the sum of eicosapentaenoic and docosahexaenoic fatty acids, from 0.5% to 2.0% in Experiment 2 improved DGC linearly and FCR curvilinearly for fish at 29 degrees C whereas at 20 degrees C, DGC was not affected while FCR improved slightly (from 1.83 to 1.68). Feed conversion ratio was optimized with a dietary n-3 HUFA of about 1.5%. Providing barramundi with a feed that is high in DE (viz 19 MJ kg(-1)) and a digestible protein to DE ratio of 22.5 g MJ(-1) is a practical strategy for improving the productivity of barramundi cultured in cool water whereas increasing dietary n-3 HUFA conferred very little additional benefit.

Cyclic Peptide Disulfides - Solution And Solid-State Conformation Of Boc-Cys-Pro-Aib-Cys-S-S-Bridge-Nhme,A Disulfide-Bridged Peptide Helix

The solution and solid-state conformations of the peptide disulfide Boc-Cys-Pro-Aib-Cys-NHMe have been determined by NMR spectroscopy and X-ray diffraction. The Cys(4) and methylamide NH groups are solvent shielded in CDCI3 and (CD,),SO, suggesting their involvement in intramolecular hydrogen bonding. On the basis of known stereochemical preferences of Pro and Aib residues, a consecutive @-turn structure is favored in solution. X-ray diffraction analysis reveals a highly folded 310 helical conformation for the peptide, with the S-S bridge lying approximately parallel to the helix axis, linking residues 1 and 4. The backbone conformational angles are Cys(1) 4 = -121.1', $ = 65.6"; Pro(2) 4 = -58.9', 4 = -34.0'; Aib(3) 4 = -61.8', $ = -17.9'; Cys(4) 4 = -70.5', $ = -18.6'. Two intramolecular hydrogen bonds are observed between Cys(1) CO--HN Cys(4) and Pro(2) CO--HNMe. The disulfide bond has a right-handed chirality, with a dihedral angle (xss) of 82'.

Noble Metal Ionic Catalysts

Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NOx, and unburned hydrocarbons-need to be fully converted to CO2, N-2, and H2O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al2O3 or SiO2 promoted by CeO2. However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce1-xMxO2-delta and Ce1-x-yTiyMxO2-delta (M = Pt, Pd, Rh; x = 0,01-0.02, delta approximate to x, y = 0.15-0.25) oxides in fluorite structure, In these oxide catalysts, pt(2+), Pd2+, or Rh3+ ions are substituted only to the extent of 1-2% of Ce4+ ion. Lower-valent noble metal ion substitution in CeO2 creates oxygen vacancies. Reducing molecules (CO, H-2, NH3) are adsorbed onto electron-deficient noble metal ions, while oxidizing (02, NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NOx reduction (with >80% N-2 selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO2 or Ce1-xTixO2 were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the more expensive Pt and Rh metals are not necessary in exhaust catalysts. We have also grown these nanocrystalline ionic catalysts on ceramic cordierite and have reproduced the results we observed in powder material on the honeycomb catalytic converter. Oxygen in a CeO2 lattice is activated by the substitution of Ti ion, as well as noble metal ions. Because this substitution creates longer Ti-O and M-O bonds relative to the average Ce-O bond within the lattice, the materials facilitate high oxygen storage and release. The interaction among M-0/Mn+, Ce4+/Ce3+, and Ti4+/Ti3+ redox couples leads to the promoting action of CeO2, activation of lattice oxygen and high oxygen storage capacity, metal support interaction, and high rates of catalytic activity in exhaust catalysis.

Rapid internal drainage rates in Ferrosols

Adoption of conservation tillage practices on Red Ferrosol soils in the inland Burnett area of south-east Queensland has been shown to reduce runoff and subsequent soil erosion. However, improved infiltration resulting from these measures has not improved crop performance and there are suggestions of increased loss of soil water via deep drainage. This paper reports data monitoring soil water under real and artificial rainfall events in commercial fields and long-term tillage experiments, and uses the data to explore the rate and mechanisms of deep drainage in this soil type. Soils were characterised by large drainable porosities (≥0.10 m3/m3) in all parts of the profile to depths of 1.50 m, with drainable porosity similar to available water content (AWC) at 0.25 and 0.75 m, but >60% higher than AWC at 1.50 m. Hydraulic conductivity immediately below the tilled layer in both continuously cropped soils and those after a ley pasture phase was shown to decline with increasing soil moisture content, although the rate of decline was much greater in continuously cropped soil. At moisture contents approaching the drained upper limit (pore water pressure = -100cm H2O), estimates of saturated hydraulic conductivity after a ley pasture were 3-5 times greater than in continuously cropped soil, suggesting much greater rates of deep drainage in the former when soils are moist. Hydraulic tensiometers and fringe capacitance sensors monitored during real and artificial rainfall events showed evidence of soils approaching saturation in the surface layers (top 0.30-0.40 m), but there was no evidence of soil moistures exceeding the drained upper limit (i.e. pore water pressures ≤ -100 cm H2O) in deeper layers. Recovery of applied soil water within the top 1.00-1.20 m of the profile during or immediately after rainfall events declined as the starting profile moisture content increased. These effects were consistent with very rapid rates of internal drainage. Sensors deeper in the profile were unable to detect this drainage due to either non-uniformity of conducting macropores (i.e. bypass flow) or unsaturated conductivities in deeper layers that far exceed the saturated hydraulic conductivity of the infiltration throttle at the bottom of the cultivated layer. Large increases in unsaturated hydraulic conductivities are likely with only small increases in water content above the drained upper limit. Further studies with drainage lysimeters and large banks of hydraulic tensiometers are planned to quantify drainage risk in these soil types.

Helical conformations of three crystalline pentapeptide fragments of suzukacillin, a membrane channel forming polypeptide

The crystal structures of three pentapeptide fragments of suzukacillin-A have been determined. Boc-Aib-Pro-Val-Aib-Val-OMe (peptide 1–5) adopts a distorted helical conformation, stabilized by three intramolecular hydrogen bonds (two 5→1, one 4→1). Boc-Ala-Aib-Ala-Aib-Aib-OMe (peptide 6–10) and Boc-Leu-Aib-Pro-Val-Aib-OMe (peptide 16–20) adopt 310 helical structures stabilized by three and two 4→1 intramolecular hydrogen bonds, respectively. These structures provide substantial support for a largely helical conformation for the suzukacillin membrane channel.

The structure of monopotassium phosphoenolpyruvate

CaH406P-.K +, M r = 206.10, is orthorhombic, space group Pbca (from systematic absences), a = 14.538(4), b = 13.364(5), c = 6.880 (6)A, U = 1383.9 A 3, D x = 2.07 Mg m -a, Z = 8, ~.(Mo Ka) = 0.7107/~, p(MO Ka) = 1.015 mm -1. The final R value is 0.042 for a total of 1397 reflections. The high energy P-O(13) and the enolic C(1)-O(13) bonds are 1.612 and 1.374 A respectively. The enolpyruvate moiety is essentially planar. The orientation of the phosphate with respect to the pyruvate group in PEP.K is distinctly different from that in the PEP-cyclohexylammonium salt, the torsion angle C (2)-C (1)-O(13)- P being -209.1 in the former and -90 ° in the latter. The K + ion binds simultaneously to both the phosphate and carboxyl ends of the same PEP molecule. The ester O(13) is also a binding site for the cation. The K + ion is coplanar with the pyruvate moiety and binds to 0(22) and O(13) almost along their lone-pair directions. The carbonyl 0(22) prefers to bind to the K + ion rather than take part in the formation of hydrogen bonds usually observed in carboxylic acid structures.

Crystal and molecular structure of the quinoxaline antibiotic analog TANDEM (des-N-tetramethyltriostin A)

The crystal structure of TANDEM (des-N-tetramethyltriostin A), a synthetic analogue of the quinoxaline antibiotic triostin A, has been determined independently at -135 and 7 'C and refined to R values of 0.088 and 0.147, respectively. The molecule has approximate 2-fold symmetry, with the quinoxaline chromophores and the disulfide cross-bridge projecting from opposite sides of the peptide ring. The quinoxaline groups are nearly parallel to each other and separated by about 6.5 A. The peptide backbone resembles a distorted antiparallel 13 ribbon joined by intramolecular hydrogen bonds N-H(LVal)--O(L-Ala). At low temperatures, the TANDEM molecule is surrounded by a regular first- and second-order hydration sphere containing 14 independent water molecules. At room temperature, only the first-order hydration shell is maintained. Calculations of the interplanar separation of the quinoxaline groups as a function of their orientation with respect to the peptide ring support the viability of TANDEM to intercalate bifunctionally into DNA.

Structure of a peptide oxazolone: 2-(1'-benzyloxycarbonylamino-1'-methylethyl)-4,4-dimethyl-5-oxazolone

C16H20N204, monoclinic, P21, a = 6.270 (1),b= 11.119(3),c= ll.640(4)A, fl= 100.7 (2)°,Dm = 1-27 (flotation), Dc = 1-26 Mg m -3, Z = 2. The structure has been refined to a final R value of 0.041 for 1584 independent counter-measured reflections. The oxazolone ring in the molecule is nearly planar. The exocyclic O atom is 0.065 A out of the plane defined by the other four atoms in the ring belonging to the lactone group. The difference in length between the two adjacent C-O bonds in the ring is small, but significant. The crystal structure is stabilized by van der Waals interactions and a N--H... N hydrogen bond.

A novel conformation of valinomycin in its barium complex

Knowledge of the molecular mechanisms involved in ionophore-mediated cation transport would be valuable for under-standing many essential functions of biological membranes1−3. Cations are transported in several stages, such as formation of the ionophore−cation complex, diffusion across the cell membrane and subsequent release of the cation. Several conformational rearrangements are involved in this process, and so a detailed understanding of all the conformational possibilities of the ionophore seems to be essential for elucidating the molecular mechanism of ion transport. We are carrying out spectroscopic and crystallographic studies to explore the possible conformational stages of ionophores by complexing them, in different solvents, with cations of various sizes and charges. We report here a novel conformation of the ionophore valinomycin in its barium complex. It can be described as an extended depsipeptide chain, without internal hydrogen bonds, wound in the form of an ellipse with the two barium ions located at the foci.

1-Benzoyl-3-methyl-2,6-diphenyl-4-piperidone

In the title moleclue, C25H23NO2, the 4-piperidone ring adopts a boat conformation. The molecular conformation is stabilized by an intramolecular C-H center dot center dot center dot O hydrogen bond. In the crystal, molecules are connected through weak intermolecular C-H center dot center dot center dot O hydrogen bonds.

Anthraquinones from the Fungus Dermocybe sanguinea as Textile Dyes

This study is based on the multidiciplinary approach of using natural colorants as textile dyes. The author was interested in both the historical and traditional aspects of natural dyeing as well as the modern industrial applications of the pure natural compounds. In the study, the anthraquinone compounds were isolated as aglycones from the ectomycorrhizal fungus Dermocybe sanguinea. The endogenous beta-glucosidase of the fungus was used to catalyse the hydrolysis of the O-glycosyl linkage in emodin- and dermocybin-1-beta-D-glucopyranosides. The method, in which 10.45 kg of fresh fungi was starting material, yielded two fractions: 56.0 g of Fraction 1 (94% of the total amount of pigment,) consisting almost exclusively of the main pigments emodin and dermocybin, and 3.3 g of Fraction 2 (6%) consisting mainly of the anthraquinone carboxylic acids. The anthraquinone compounds in Fractions 1 and 2 were separated by one- and two-dimensional thin-layer-chromatography (TLC) using silica plates. 1D TLC showed that neither an acidic nor a basic solvent system alone separated completely all the anthraquinones isolated from D. sanguinea, in spite of the variation of the rations of the solvent components in the systems. Thus, a new 2D TLC technique was developed, applying n-pentanol-pyridine-methanol (6:4:3, v/v/v) and toluene-ethyl acetate-ethanol-formic acid (10:8:1:2, v/v/v/v) as eluents. Fifteen different anthraquinone derivatives were completely separated from one another. Emodin, physcion, endocrocin, dermolutein, dermorubin, 5-chlorodermorubin, emodin-1-beta-D-glucopyranoside, dermocybin-1-beta-D-glucopyranoside and dermocybin, and five new compounds, not earlier identified in D. sanguinea, 7-chloroemodin, 5,7-dichloroemodin, 5,7-dichloroendocrocin, 4-hydroxyaustrocorticone and austrocorticone, were separated and identified on the basis of their Rf-values, UV/Vis spectra and mass spectra. One substance remained unidentified, because of its very low concentration. The anthraquinones in Fractions 1 and 2 were preparatively separeted by liquid-liquid partition, with isopropylmethyl ketone and aqueous phosphate buffer as the solvent system. Advantage was taken of the principle of stepwise pH-gradient elution. The multiple liquid-liquid partition (MLLP) offered an excellent method for the preparative separation of compounds, which contain acidic groups such as the phenolic OH and COOH groups. Due to their strong aggregation properties, these compounds are, without derivatization, very difficult to separate on a preparative scale by chromatographic methods. By the MLLP method remarkable separations were achieved for the components in each mixture. Emodin and dermocybin were both obtained from Fraction 1 in a purity of at least 99%. Pure emodin and dermocybin were applied as mordant dyes to wool and polyamide and as disperse dyes to polyester and polyamide, using the high temperature (HT) technique. A mixture of dermorubin and 5-chlorodermorubin was applied as an acid dye to wool. In these experiments, synthetic dyes were used as references. Experiments were also performed using water extract of the air-dried fungi as dye liquor for wool and silk. The main colouring compounds in the crude water extract were emodin and dermocybin, which indicated that the O-glycosyl linkages in emodin- and dermocybin-1-beta-D-glucopyranosides were broken by the beta-glucosidase enzyme. Apparently, the hydrolysis occurred during the drying of the fungi and during the soaking of the dried fruit bodies overnight when preparing the dyebath. The colour of each dyed material was investigated in terms of the CIELAB L*, a* and b* values, and the colour fastness to light, washing and rubbing was tested according to the ISO standards. In the mordant dyeing experiments, emodin dyed wool and polyamide yellow and red, depending on the pH of the dyebath. Dermocybin gave purple and violet colours. The colour fastness of the mordant-dyed fabrics varied from good to moderate. The fastness properties of the natural anthraquinone carboxylic acids on wool were good, indicating the strength of the ionic bonds between the COO- groups of the dyes and the NH3+ groups of the fibres. In the disperse dyeing experiments, emodin dyed polyester bright yellow and dermocybin bright reddish-orange, and the fabrics showed excellent colour fastness. In contrast, emodin and dermocybin successfully dyed polyamide brownish-orange and wine-red, respectively, but with only moderate fastness. In industrial dyeing processes, natural anthraquinone aglycone mixtures dyed wool and silk well even at low concentrations of mordants, i.e. with 10% of the weight of the fibre (owf) of KAl(SO4)2 and 1 or 0.5% owf of other mordants. This study showed that purified natural anthraquinone compounds can produce bright hues with good colour-fastness properties in different textile materials. Natural anthraquinones have a significant potential for new dyeing techniques and will provide useful alternatives to synthetic dyes.

Structure of the disodium salt of glucose 1-phosphate hydrate, 2Na+.C6H11O9P2-.3.5H2O

Mr= 367.2, monoclinic, C2, a = 8.429 (1),b= 10.184(2), c= 16.570(2)A, /~= 99.18 (1) °, U= 1404.2 A 3, z = 4, D m = 1.73, D x = 1.74 Mg m -3,Cu K~, 2 = 1.5418 A, g = 2.99 mm -1, F(000) = 764,T= 300K, final R for 1524 observed reflections is0.069. The endocyclic C-O bonds in the glucose ring are nearly equal with C(5)-O(5)= 1.445 (10) and C(1)-O(5)= 1.424(10). The pyranose sugar ring adopts a 4C 1 chair conformation. The conformation about the exocyclic C(5)-C(6) bond is gauche-gauche, in contrast to gauche-trans observed in the structure of the dipotassium salt of glucose 1-phosphate. The phosphate ester bond, P-O(1), is 1.641 (6)A, slightly longer than the 'high-energy' P-,.O bond in the monopotassium salt of phosphoenolpyruvate [1.612 (6)A]. Two sodium ions are six coordinated while the third has only five neighbours.