Iron(II)/reductant(DH2)-induced activation of dioxygen for the hydroxylation and ketonization of hydrocarbons; mimics for the cytochrome P-450 hydroxylase/reductase system

Several metal complexes [(FeII(DPAH)2 (DPAH2 = 2,6-dicarboxyl pyridine), FeII(PA)2 (PAH = picolinic acid), FeII(bpy)2(2+), FeII(OPPh3)4(2+), (Cl8TPP)FeIIIX (X = Cl, OH, SCH2Ph) [Cl8TPP = tetrakis (2,6-dichlorophenyl)porphyrin], (TPP) FeIIICl (TPP = tetraphenylporphyrin), and CuI(tpy)2+ (typ = 2,2'-6,2"-terpyridine)] in combination with one of several reductants [DH2; PhNHNHPh (mimic of dihydroflavin), PhNHNH2, ascorbic acid (H2asc), and PhCH2SH (model ligand for cysteine residue)] catalytically activate O2 (1 atm) for the hydroxylation of saturated hydrocarbons (e.g. c-C6H12-->c-C6H11OH). This chemistry closely parallels that of cytochrome P-450 proteins, and both appear to involve a Fenton-like reactive intermediate), [LxFeOOH(DH)]. With cyclohexane as the substrate the dominant product is its ketone (as well as significant amounts of its hydroperoxide). 1,4-Cyclohexadiene (with two double-allylic carbon centers) undergoes dehydrogenation to give benzene, but also yields substantial amounts of phenol via ketonization of an allylic carbon. The 1:1 FeII(bpy)2(2+)/(PhNHNH2 or H2asc), FeII(PA)2/H2asc, and (Cl8TPP)FeIIICl/PhNHNH2 combinations initiate the autoxidation of 1,4-cyclohexadiene with turnover numbers (moles of product per mole of reductant) from 71 to 26, respectively (alpha-tocophenol reduces the turnover numbers by 20-80%). With respect to aerobic biology, the present results indicate that dysfunctional transition metals (degradation products of metalloproteins) in combination with biological reductants activate O2 for reaction with organic substrates. The level of activation is similar to that for Fenton reagents and cytochrome P-450 hydroxylases. Hence, dysfunctional transition metals, reductants, and O2 are a hazardous combination within a biological matrix.     

The testing of bulls for the polledness gene]

Main regularities have been stated concerning the poll gene inheritance by the progeny of breeding bulls mated with cows of various (homozygous and heterozygous) genotypes by the "poll" or "hornedness" genes.     

The role of protein kinase in C ischemic/reperfused preconditioned isolated rat hearts

Protein kinase C (PKC) has been implicated in the preconditioning-induced cardiac protection in ischemic/reperfused myocardium. We studied the effect of PKC inhibition with calphostin C (25, 50, 100, 200, 400, and 800 nM), a potent and specific inhibitor of PKC, in isolated working nonpreconditioned and preconditioned ischemic/reperfused hearts. In the nonpreconditioned groups, all hearts underwent 30 min of normothermic global ischemia followed by 30 min of reperfusion. In the preconditioned groups, hearts were subjected to four cycles of ischemic preconditioning by using 5 min of ischemia followed by 10 min reperfusion, before the induction of 30 min ischemia and reperfusion. At low concentrations of calphostin C (25, 50, and 100 nM), the PKC inhibitor had no effect on the incidence or arrhythmias or postischemic cardiac function in the nonpreconditioned ischemic/reperfused groups. With 200 and 400 nM of calphostin C, a significant increase in postischemic function and a reduction in the incidence of arrhythmias were observed in the nonpreconditioned ischemic/reperfused groups. Increasing the concentration of calphostin C to 800 NM, the recovery of postischemic cardiac function was similar to that of the drug-free control group. In preconditioned hearts, lower concentrations (< 100 nM) of calphostin C did not change the response of the myocardium to ischemia and reperfusion in comparison to the preconditioned drug-free myocardium. Two hundred and 400 nM of the PKC inhibitor further reduced the incidence of ventricular fibrillation (VF) from the preconditioned drug-free value of 50% to 0 (p < 0.05) and 0 (p < 0.05), respectively, indicating that the combination of the two, preconditioning and calphostin C, affords significant additional protection. Increasing the concentration of calphostin C to 800 nM blocked the cardioprotective effect of preconditioning (100% incidence of VF). The recovery of cardiac function was similarly improved at calphostin C doses of 200 and 400 nM and was reduced at 800 nM (p < 0.05). With 200 and 400 nM of calphostin C, both cytosolic and particulate PKC activity were reduced by approximately 40 and 60%, respectively, in both preconditioned and preconditioned/ischemic/reperfused hearts. The highest concentration of calphostin C (800 nM) resulted in almost a complete inhibition of cytosolic (100%) and particulate (85%) PKC activity correlated with the abolition of preconditioning-induced cardiac protection. In conclusion, calphostin C protects the ischemic myocardium obtained from intact animals, provides significant additional protection to preconditioning at moderate doses, and blocks the protective effect of preconditioning at high concentrations. The dual effects of calphostin C appear to be strictly dose and "enzyme inhibition" related.     

Thermal comfort and sensation in men wearing a cooling system controlled by skin temperature

OBJECTIVE: The study was done to determine whether thermal comfort (TC), thermal sensation (TS), and subjective factors gauging environmental stress were negatively affected with different cooling methods in men exercising in chemical protective clothing. BACKGROUND: Previous studies have reported that intermittent regional cooling improved the efficacy of cooling as compared with constant cooling (CC), but no studies have addressed whether there is any improvement in thermal comfort. METHODS: Eight male volunteers exercised at moderate work intensity (425 W) in three microclimate cooling tests. The circulating fluid in the cooling garment was provided during exercise to the head (6% body surface area [BSA]), torso (22% BSA), and thighs (44% BSA) and manipulated under three methods: (a) CC, (b) pulsed cooling (PC), and (c) PC activated by mean skin temperature (T(sk)) control (PC(skin)). TC and TS ratings were recorded every 20 min during the 80-min test. RESULTS: TC and TS ratings were not different for PC(skin) and CC; thus the participants perceived PC(skin) as being similar to CC. TS was significantly warmer with PC than with PC(skin) and CC (p < .001). In PC(skin), T(sk) was significantly higher than in PC and CC (p < .001), and PC(skin) was rated as being not as warm as PC according to TS. CONCLUSION: This indicates that the PC(skin) method was perceived as being as cool as CC and cooler than PC. APPLICATION: These findings indicate that the PC(skin) cooling method is an acceptable alternative to CC and PC based on human perceptions.     

Intermittent microclimate cooling during exercise-heat stress in US army chemical protective clothing

The effectiveness of intermittent, microclimate cooling for men who worked in US Army chemical protective clothing (modified mission-oriented protective posture level 3; MOPP 3) was examined. The hypothesis was that intermittent cooling on a 2 min on-off schedule using a liquid cooling garment (LCG) covering 72% of the body surface area would reduce heat strain comparably to constant cooling. Four male subjects completed three experiments at 30 degrees C, 30% relative humidity wearing the LCG under the MOPP 3 during 80 min of treadmill walking at 224 +/- 5 W . m(-2). Water temperature to the LCG was held constant at 21 degrees C. The experiments were; 1) constant cooling (CC); 2) intermittent cooling at 2-min intervals (IC); 3) no cooling (NC). Core temperature increased (1.6 +/- 0.2 degrees C) in NC, which was greater than IC (0.5 +/- 0.2 degrees C) and CC (0.5 +/- 0.3 degrees C) ( p < 0.05). Mean skin temperature was higher during NC (36.1 +/- 0.4 degrees C) than IC (33.7 +/- 0.6 degrees C) and CC (32.6 +/- 0.6 degrees C) and mean skin temperature was higher during IC than CC ( p < 0.05). Mean heart rate during NC (139 +/- 9 b . min(-1)) was greater than IC (110 +/- 10 b . min(-1)) and CC (107 +/- 9 b . min(-1)) ( p < 0.05). Cooling by conduction (K) during NC (94 +/- 4 W . m(-2)) was lower than IC (142 +/- 7 W . m(-2)) and CC (146 +/- 4 W . m(-2)) ( p < 0.05). These findings suggest that IC provided a favourable skin to LCG gradient for heat dissipation by conduction and reduced heat strain comparable to CC during exercise-heat stress in chemical protective clothing.     

The 3'-terminal sequence of mitochondrial 13S ribosomal RNA

We have examined the 3'-terminal sequence of the "small" structural ribosomal RNA ("13S") of hamster cell mitochondria, using a procedure involving [3H]isoniazide labeling of samples subjected to sequential periodate oxidation and beta-elimination. The terminus was found to be PyUAUUAOH, which is similar, but not identical, to the corresponding terminus of eukaryotic cytoplasmic 18S rRNA.     

Piezoelectric paint: Ceramic-polymer composites for vibration sensors

A piezoelectric ceramic-polymer composite has been developed for use as a novel thick film strain sensor for vibration monitoring of structures. The material is in the form of a paint that can be applied to a wide range of substrates using conventional spraying equipment. The sensor properties depend on the morphology of the composite and on the electrodes that are used to couple it to the charge amplifier. Electrodes of various kinds have been tested. Interaction between the electrode and the piezoelectric paint sometimes occurs (for example, the organic vehicle for spray-coated electrodes may interact with the paint binder). The morphologies of the piezoelectric paint and of the electrode materials have been studied using light optical microscopy and scanning electron microscopy to investigate the effect of different compositions and of different processing conditions (e.g., paint mixing schedule). Preliminary work is reported on the characteristics of the piezoelectric particles and on the effect of heat treatment applied to anneal out defects produced by milling. X-ray analysis and particle size analysis have been used to characterize the changes that take place on heat treatment. X-ray diffractometry has also been used to follow the effect of poling on the paint sensors. At the present state of development, sensors made using the paint have a dynamic range of at least 40–4000 microstrain and a bandwidth of at least 1 Hz–2 kHz, and piezoelectric coefficient d ₃₁ of approximately 20 pC/N. The sensors are resistant to outdoor exposure and a successful field trial has been conducted.