4,6,8,10,16-penta- and 4,6,8,10,16,18-hexamethyldocosanes from the cane beetle Antitrogus parvulus - Cuticular hydrocarbons with unprecedented structure and stereochemistry

[GRAPHICS] The major cuticular hydrocarbons from the cane beetle species Antitrogus parvulus were deduced to be 4,6,8,10,16,18-hexa- and 4,6,8,10,16-pentamethyldocosanes 2 and 3, respectively. Isomers of 2,4,6,8-tetramethylundecanal 27, 36, and 37, derived from 2,4,6-trimethylphenol, were coupled with the phosphoranes 28 and 29 to furnish alkenes and, by reduction, diastereomers of 2 and 3. Chromatographic and spectroscopic comparisons confirmed 2 as either 6a or 6b and 3 as either 34a or 34b.

Novel cuticular hydrocarbons from the cane beetle Antitrogus parvulus - 4,6,8,10,16-penta- and 4,6,8,10,16,18-hexamethyldocosanes - Unprecedented anti-anti-anti-stereochemistry in the 4,6,8,10-methyltetrad

[GRAPHICS] The major cuticular hydrocarbons from the cane beetle species Antitrogus parvulus are 4,6,8,10,16-penta- and 4,6,8,10,16,18-hexamethyldocosanes, I and 2, respectively. Stereoisomers of 2,4,6,8-tetramethylundecanal of established relative stereochemistry were derived from 2,4,6-trimethylphenol and were then coupled with appropriate methyl-substituted phosphoranes 62 and 25 to furnish alkenes, which on reduction provided diastereomers of I and 2, respectively. Capillary gas chromatography, mass spectrometry, and high resolution C-13 NMR spectroscopy confirmed 1 as either 84a or 84b and 2 as either 15a or 15b. The novelty of these structures and their relative stereochemistry is briefly related to polyketide assembly.

Isomers of 1,4,8,11-tetraazacyclotetradecane-6,13-dicarboxylate characterized as cobalt(III) complexes

The major trans (1) and minor cis (2) isomers of 1,4,8,11-tetraazacyclotetradecane-6,13-dicarboxylate have been characterized as the complexes [Co(1)](ClO4) and [Co(H-2)(OH2)]Cl(ClO4).H2O. The former crystallized in the C-2/c space group and the latter in the P2(1)/c space group, with cell parameters a 16.258(7), b 9.050(3), c 15.413(6) Angstrom, beta133.29(3)degrees, and a 9.694(4), b 16.135(1), c 12.973(5) Angstrom, beta 93.00(2)degrees, respectively. Their characterization completes identification of the respective trans and cis isomers for the series of C-pendant macrocycles also including 1,4,8,11-tetraazacyclotetradecane-6-amine-13-carboxylate ((3), (4)) and 1,4,8,11-tetraazacyclotetradecane-6,13-diamine ((5), (6)). The complexes show limited distortion from octahedral geometry with the strain in the presence of the coordinated C-pendant carboxylate significantly reduced compared with that for the C-pendant amine in analogues, a consequence mainly of six-membered as opposed to five-membered chelate rings involving the pendant donor. A comparison of the physical properties for the trans isomers of the octahedral complexes of (1), (3), and (5), which reflect progressively increasing strain, is presented.

Improved slope adjustment functions for soil erosion prediction

Numerous studies in the last 60 years have investigated the relationship between land slope and soil erosion rates. However, relatively few of these have investigated slope gradient responses: ( a) for steep slopes, (b) for specific erosion processes, and ( c) as a function of soil properties. Simulated rainfall was applied in the laboratory on 16 soils and 16 overburdens at 100 mm/h to 3 replicates of unconsolidated flume plots 3 m long by 0.8 m wide and 0.15 m deep at slopes of 20, 5, 10, 15, and 30% slope in that order. Sediment delivery at each slope was measured to determine the relationship between slope steepness and erosion rate. Data from this study were evaluated alongside data and existing slope adjustment functions from more than 55 other studies from the literature. Data and the literature strongly support a logistic slope adjustment function of the form S = A + B/[1 + exp (C - D sin theta)] where S is the slope adjustment factor and A, B, C, and D are coefficients that depend on the dominant detachment and transport processes. Average coefficient values when interill-only processes are active are A - 1.50, B 6.51, C 0.94, and D 5.30 (r(2) = 0.99). When rill erosion is also potentially active, the average slope response is greater and coefficient values are A - 1.12, B 16.05, C 2.61, and D 8.32 (r(2) = 0.93). The interill-only function predicts increases in sediment delivery rates from 5 to 30% slope that are approximately double the predictions based on existing published interill functions. The rill + interill function is similar to a previously reported value. The above relationships represent a mean slope response for all soils, yet the response of individual soils varied substantially from a 2.5-fold to a 50-fold increase over the range of slopes studied. The magnitude of the slope response was found to be inversely related ( log - log linear) to the dispersed silt and clay content of the soil, and 3 slope adjustment equations are proposed that provide a better estimate of slope response when this soil property is known. Evaluation of the slope adjustment equations proposed in this paper using independent datasets showed that the new equations can improve soil erosion predictions.

Muscle metabolism during constant- and alternating-intensity exercise around critical power

Few studies have focused on the metabolic responses to alternating high- and low-intensity exercise and, specifically, compared these responses to those seen during constant-load exercise performed at the same average power output. This study compared muscle metabolic responses between two patterns of exercise during which the intensity was either constant and just below critical power (CP) or that oscillated above and below CP. Six trained males (mean +/- SD age 23.6 +/- 2.6 y) completed two 30-minute bouts of cycling (alternating and constant) at an average intensity equal to 90% of CR The intensity during alternating exercise varied between 158% CP and 73% CP. Biopsy samples from the vastus lateralis muscle were taken before (PRE), at the midpoint and end (POST) of exercise and analysed for glycogen, lactate, PCr and pH. Although these metabolic variables in muscle changed significantly during both patterns of exercise, there were no significant differences (p > 0.05) between constant and alternating exercise for glycogen (PRE: 418.8 +/- 85 vs. 444.3 +/- 70; POST: 220.5 +/- 59 vs. 259.5 +/- 126mmol.kg(-1) dw), lactate (PRE: 8.5 +/- 7.7 vs. 8.5 +/- 8.3; POST: 49.9 +/- 19.0 vs. 42.6 +/- 26.6 mmol.kg(-1)dw), phosphocreatine (PRE: 77.9 +/- 11.6 vs. 75.7 +/- 16.9; POST: 65.8 +/- 12.1 vs. 61.2 +/- 12.7mmol.kg(-1)dw) or pH (PRE: 6.99 +/- 0.12 vs. 6.99 +/- 0.08; POST: 6.86 +/- 0.13 vs. 6.85 +/- 0.06), respectively. There were also no significant differences in blood lactate responses to the two patterns of exercise. These data suggest that, when the average power output is similar, large variations in exercise intensity exert no significant effect on muscle metabolism.

The fornax spectroscopic survey: the number of unresolved compact galaxies

We describe a sample of 13 bright (18.5 < B-J < 20.1), compact galaxies at low redshift (0.05 < z < 0.21) behind the Fornax Cluster. These galaxies are unresolved on UK Schmidt sky survey plates, and so they would be missing from most galaxy catalogs compiled from this material. The objects were found during initial observations of The Fornax Spectroscopic Survey. This project is using the Two-degree Field spectrograph on the Anglo-Australian Telescope to obtain spectra for a complete sample of all 14,000 objects, stellar and nonstellar, with 16.5 < B-J < 19.7, in a 12 deg(2) area centered on the Fornax Cluster of galaxies. The surface density of compact galaxies with magnitudes 16.5 < B-J < 19.7 is 7 +/- 3 deg(-2), representing 2.8% +/- 1.6% of all local (z < 0.2) galaxies to this limit. There are 12 +/- 3 deg(-2) with 16.5 < B-J < 20.2. They are luminous (-21.5 < M-B < -18.0, for H-o = 50 km s(-1) Mpc(-1)), and most have strong emission lines (H alpha equivalent widths of 40-200 Angstrom) and small sizes typical of luminous H II galaxies and compact narrow emission line galaxies. Four out of 13 have red colors and early-type spectra, and so they are unlikely to have been detected in any previous surveys.

Modeling the optical constants of GaP, InP, and InAs

An extension of the Adachi model with the adjustable broadening function, instead of the Lorentzian one, is employed to model the optical constants of GaP, InP, and InAs. Adjustable broadening is modeled by replacing the damping constant with the frequency-dependent expression. The improved flexibility of the model enables achieving an excellent agreement with the experimental data. The relative rms errors obtained for the refractive index equal 1.2% for GaP, 1.0% for InP, and 1.6% for InAs. (C) 1999 American Institute of Physics. [S0021-8979(99)05807-7].

Ni-II and Zn-II complexes of the hexadentate macrocyclic ligand cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetra- decane-6,13-diamine

The title pendent-arm macrocyclic hexaamine ligand binds stereospecifically in a hexadentate manner, and we report here its isomorphous Ni-II and Zn-II complexes (both as perchlorate salts), namely (cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine-kappa(6)N)nickel(II) diperchlorate, [Ni(C12H30N6)](ClO4)(2), and (cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine-kappa(6)N)zinc(II) diperchlorate, [Zn(C-12 H30N6)](ClO4)(2). Distortion of the N-M-N valence angles from their ideal octahedral values becomes more pronounced with increasing metal-ion size and the present results are compared with other structures of this ligand.

Determination of the stability constants of mercury(II) complexes of mixed donor macrobicyclic encapsulating ligands

The reactions of mercury(II) with the mixed donor encapsulating ligands 3,6,16-trithia-6,11,19-triazabicyclo[6.6.6]icosane (AMN(3)S(3)sar) and 1-amino-8-methyl-6,19-dithia-3,10,13,16-tetraazabicyclo[6.6.6]icosane (AMN(4)S(2)sar) have been studied. NMR ligand-ligand competition experiments with the ligands 1,4,8,11-tetraazaeyclotetradecane ([14]aneN(4)), 1-thia-4,7,10-triazacyclododecane ([12]aneN(3)S) and ethylenediaminetetraacetic acid (EDTA) with AMN(3)S(3)sar and Hg(II) indicated that [14]aneN(4) would be an appropriate competing ligand for the, determination of the Hg(II) stability constant. Calculations indicated the ratio of concentrations of AMN3S3sar, [14]aneN(4) and Hg(II) required for the determination of the stability constant ranged from 1:1:1 to 1:5:1. Refinement of the titration curves yielded log(10)K[Hg(AMN(3)S(3)sar)](2+) = 17.7. A similar competition titration resulted in the determination of the stability constant for the AMN(4)S(2)sar system as log(10)K[Hg(AMN(4)S(2)sar)](2+) = 19.5. The observed binding constants for the mixed N/S donor systems and the hexaaza analogues sar (3,6,10,13,16,19-hexaazabicyclo [6.6.6]icosane) and diamsar (1,8-diamino-3,6,10,13,16,19 -hexazabicyclo [6.6.6] icosane (log(10)K-[Hg(diamsar)](2+) = 26.4; log(10)K[Hg(sar)](2+) = 28.1) differ by approximately ten orders of magnitude. The difference is ascribed not to a cryptate effect but to a mismatch in the Hg-N and Hg-S bond lengths in the N/S systems.

D-amino acid residue in the C-type natriuretic peptide from the venom of the mammal, Ornithorhynchus anatinus, the Australian platypus

The C-type natriuretic peptide from the platypus venom (OvCNP) exists in two forms, OvCNPa and OvCNPb, whose amino acid sequences are identical. Through the use of nuclear magnetic resonance, mass spectrometry, and peptidase digestion studies, we discovered that OvCNPb incorporates a D-amino acid at position 2 in the primary structure. Peptides containing a D-amino acid have been found in lower forms of organism, but this report is the first for a D-amino acid in a biologically active peptide from a mammal. The result implies the existence of a specific isomerase in the platypus that converts an L-amino acid residue in the protein to the D-configuration. (C) 2002 Federation of European Biochemical Societies. Published by Elsevier Science B.V. All rights reserved.

N-methylation of diamino-substituted macrocyclic complexes: Intramolecular cyclisation

Two new macropolycyclic hexaamines L(2) and L(4) as their copper(II) complexes have been isolated as products from the condensation of the diamino-substituted macrocyclic complex trans-(6,13-dimethyl-1,4,8,11-tetraazacyclo-tetradecane-6,13-diamine)copper(II) [CuL(1)](2+) with aqueous formaldehyde. Both of the complexes exhibit methylene bridges between the pendant amine and the adjacent co-ordinated macrocyclic N-donors. Their crystal structures have been determined: [CuL(2)(NCS)][SCN], triclinic, space group P (1) over bar, a = 7.133(2), b = 9.813(2), c = 16.745(3) Angstrom, alpha = 101.05(2), beta = 99.36(2), gamma = 99.77(2)degrees, Z = 2; [CuL(4)Cl][ClO4]. H2O, triclinic, space group P (1) over bar, a = 9.3327(8), b = 10.8989(6), c = 12.672(1) Angstrom, alpha = 68.591(6), beta = 78.899(6), gamma = 87.384(6)degrees, Z = 2. The complexes exhibit square-pyramidal geometries, and significantly lower-energy electronic maxima relative to their parent complex [CuL(1)](2+). Electrochemistry of [CuL(2)](2+) revealed a reversible Cu-II-Cu-I redox couple, by contrast to those of macromonocyclic analogues.

The relationship between plasma potassium concentration and muscle torque during recovery following intense exercise

The present study investigated the relationship between plasma potassium ion concentration ([K+]) and skeletal muscle torque during three different 15-min recovery periods after fatigue induced by four 30-s sprints. Four males and one female completed the multiple sprint exercise on three separate days; recovery was passive, i.e. no cycling exercise (PRec), active cycling at 30% peak oxygen consumption (V) over dot(2peak) (30% Rec) and active cycling at 60% (V) over dot(2peak) (60% Rec). Plasma [K+] was measured from blood sampled from an antecubital vein of subjects at rest and at 0, 3, 5, 10 and 15 min into each recovery. Isokinetic leg strength was measured at rest and at 1, 6, 11 and 16 min during each recovery. Following the exhaustive sprints; [K+] increased significantly from an average mean (SEM) resting value of 3.81 (0.07) mmol.l(-1) to 4.48 (0.19) mmol.l(-1) (P < 0.01). In all recovery conditions, plasma [K+] returned to resting levels within 3 min following the fourth sprint. However, in the two active recovery conditions plasma [K+] increased over the remainder of the recovery periods to 4.36 (0.12) mmol.l(-1) in the 30% Rec condition and 4.62 (0.12) mmol.l(-1) in the 60% Rec condition, the latter being significantly higher than the former (P < 0.01). The maximum torque measured following the sprints decreased significantly, on average, to 61.1 (8.36)% of peak levels (P < 0.01). After 15 min of recovery, maximum torque was highest in the 30% Rec condition at 92.13 (3.06)% of peak levels (P < 0.01), compared to 85.23 (3.64)% and 85.71 (0.82)% for the PRec and 60% Rec conditions, respectively. In contrast to the significant differences in plasma [K+] across all three recovery conditions, muscle torque recovery was significantly different in only the 30% Rec condition. In summary, recovery of peak levels of muscle torque following fatiguing exercise does not appear to follow changes in plasma [K+].

A Century of Change in Coral Reef Status in Southeast and Central Pacific: Polynesia Mana Node, Cook Islands, French Polynesia, Kiribati, Niue, Tokelau, Tonga, Wallis and Futuna

The Polynesia Mana Node of the southeast and central Pacific contains 7 independent or autonomous countries or territories with only 6,000 km2 of land on 347 islands, but surrounded by 12 million km2 of EEZ. These seas contain 13,000 km2 of coral reefs as the main natural ecosystem providing food resources and opportunities for development, especially for tourism and pearl culture for 500,000 inhabitants. During the 19th and first half of the 20th centuries, there was major exploitation by the colonial powers of mother-of-pearl oysters for the button industry, as well as guano, sandalwood and trepang. The Polynesian people were largely involved in a subsistence economy and all coral reefs and lagoons were healthy. During the last two decades of the 20th, all countries experienced rapid development and urbanization, rising populations, and some increased agriculture. These developments were limited to a few islands of each country (i.e. 15 islands amongst the 347) with resulting degradation of the coral reefs around these sites. The other islands remained mostly uninhabited and pristine, and continued with a subsistence economy. Generally, there was more damage to the coral reefs through natural events such as cyclones and coral bleaching, than by human activities. There is however, an urgent need to combat the threats on some islands from increased sedimentation, over-fishing, dredging and nutrient pollution.

Effect of Rosiglitazone on Insulin Sensitivity and Body Composition in Type 2 Diabetic Patients

Objective: To investigate the effects of rosiglitazone (RSG) on insulin sensitivity and regional adiposity (including intrahepatic fat) in patients with type 2 diabetes. Research Methods and Procedures: We examined the effect of RSG (8 mg/day, 2 divided doses) compared with placebo on insulin sensitivity and body composition in 33 type 2 diabetic patients. Measurements of insulin sensitivity (euglycemic hyperinsulinemic clamp), body fat (abdominal magnetic resonance imaging and DXA), and liver fat (magnetic resonance spectroscopy) were taken at baseline and repeated after 16 weeks of treatment. Results: There was a significant improvement in glycemic control (glycosylated hemoglobin -0.7 +/- 0.7%, p less than or equal to 0.05) and an 86% increase in insulin sensitivity in the RSG group (glucose-disposal rate change from baseline: 17.5 +/- 14.5 mumol glucose/min/kg free fat mass, P < 0.05), but no significant change in the placebo group compared with baseline. Total body weight and fat mass increased (p &LE; 0.05) with RSG (2.1 +/- 2.0 kg and 1.4 +/- 1.6 kg, respectively) with 95% of the increase in adiposity occurring in nonabdominal regions. In the abdominal region, RSG increased subcutaneous fat area by 8% (25.0 +/- 28.7 cm(2), p = 0.02), did not alter intra-abdominal fat area, and reduced intrahepatic fat levels by 45% (-6.7 +/- 9.7%, concentration relative to water). Discussion: Our data indicate that RSG greatly improves insulin sensitivity in patients with type 2 diabetes and is associated with an increase in adiposity in subcutaneous but not visceral body regions.