The investigation of the reduction mechanism of the 5a-reductase enzyme of Penicillium decumbens /

The 5a-reductase of Penicillium decumbens ATCC 10436 was used as a model for the mammalian enzyme to investigate the mechanism of reduction of testosterone to 5adihydrotestosterone . The purpose of this study was to search for specific 5a-reductase inhibitors which antagonize prostate cancer . In a whole-cell biotransformation mode, this organism reduced testosterone (1) to 5a-dihydrosteroids (8) and 5aandrostane- 3, 17-dione (9) in yields of 28% and 37% respectively. Control experiments have shown that 5aandrostane- 3, 17-dione (9) can be produced from the corresponding alcohol (8) in a subsequent reaction separate from that catalysed by the 5a-reductase enzyme . Androst-4- ene-3, 17-dione (2) is reduced to give only (9) with a recovery of 80% The stereochemistry of the reduction was determined by 500 MHz ^H NMR analysis of the products resulting from the deuterium labelled substrates. The results were obtained by an analysis of the NOE difference spectra, double-quantum filtered phase sensitive COSY 2-D spectra, and ^^c-Ir 2-D shift correlation spectra of deuterium labelled products. According to the unambiguous assignment of the signals due to H-4a and H-4Ii in 5a-dihydro steroids, the NMR data show clearly that addition of hydrogen to the 4{5)K bond has occurred in a trans manner at positions 413 and 5a. To Study the reduction mechanism of this enzyme, several substrates were prepared as following; 3-methyleneandrost-4-en- 17fi-ol(3), androst-4-en-17i5-ol(5) , androst-4-en-3ii, 17fi-diol (6) and 4, 5ii-epoxyandrostane-3, 17-dione (7) . Results suggest that this enzyme system requires an oxygen atom at the 3-position of the steroid in order to bind the substrate. Furthermore, the mechanism of this 5a-reductase may proceed via direct addition of hydrogen at the 4,5 position without involvement of a carbonyl group as an intermediate.

Broad reduction and adoption in ring-billed gulls (Larus Delaworensis): the potential for inergenerational conflict

Patterns of intra-clutch egg size variation and intra-clutch hatch intervals in the Ring-billed gull (Larus delawarensis) were documented during the peak nesting period of two consecutive breeding seasons, at a colony near Port Colborne, Ontario. Egg size decreased with laying order; third laid eggs were significantly smaller than first laid eggs. Hatching of the third egg was delayed from that of first and second eggs. Intraclutch egg size differences established initial size disparities among chicks at hatch. Hatch intervals further exaggerated size disparities during the early post brood completion period. Competitive asymmetries among chicks were associated with increased mortality rates among third hatched chicks despite the lack of evidence of a sibling feeding hierarchy. Fledging success in 1987 was greater than in 1988. A "brood reduction strategy" appears to have enabled parents in 1987, to obtain an extra unit of reproductive fitness, while in 1988 parents were often unable to raise the entire brood and third chicks likely represented insurance reproductive value. Experimental broods (1988) were created in which hatch intervals were double those of natural intervals. The size disparities among chicks were significantly greater than in control broods, and the pattern of mortality among chicks suggested that first chicks benefited at a cost to second and third chicks. Parents of peak experimental broods achieved a fledging success rate similar to that of control broods. Characteristics of chick adoptions were also recorded. In each study year, 9 chicks abandoned their natal territories, 6 of which were adopted. Chicks consistently established themselves into broods where they were older than resident chicks. No direct evidence of cost to foster parents, or benefits to adopted chicks was obtained, although fledging success of adopted chicks was high.

Exchange energy calculation of He-He with supermolecular one-matrix

Exch~nge energy of the He-He system is calculated using the one-density matrix which has been modified according to the supermolecular density formula quoted by Kolos. The exchange energy integrals are computed analytically and by the Monte Carlo method. The results obtained from both ways compared favourably,with the results obtained from the SCF program HONDO

Feeding rates, parental investment, and brood reduction in Caspian terns (Sterna caspia)

Fresh egg-weights and feeding rates to chicks were related to chick survival as one means of quantifying apportionment of parental investment wi thin broods of Caspian Terns (SterDI casRla) at a colony in Georgian Bay. Lake Huron, during 1978 and 1979. Ftrst-laid eggs from 2-egg clutches were Significantly heavier and usually hatched one to three days earlier than second-laid eggs in both years of the study. In both years, first-hatched chicks were larger and generally better fed than second-hatched siblings. The disparity between feedIng rates of first- and second-hatched ehicks was greater in 1979. Brood feeding I rates correlated positively with the percentage of food fed to the least-fed sibUng through the period of B-chick ages zero to 10 days in 1978. I suggest that after this age period, parental control over whlcb cbick was fed diminished. In 1978, 10 of 16 secondhatched chicks were fed more than their older siblings during their first 5 days. 'lb.is is interpreted as a parental response to reduce the competitive advantage of the larger first-hatched chicks. Most chick losses were apparently caused by starvation or preda. tion. In 1979, seeorvl-hatched chick disappearance (due to predation) was -related to low feeding rates, whereas first-hatched chick disappearance was related to low fresh egg-weights.. First-hatched chicks survived better than second-hatched chicks both years, and more pairs fledged two chicks in 1978. Maximum estimated feeding rates at the nest and fledging ages suggested that food was more avatlable in 1978 than in 1979. In 1979, second eggs apparently functioned as "insurance" eggs. When the first-laid egg falled to hatch, or the first-hatched chick died, the second-hatched chick was often successfully fledged. When first-hatched chicks survived, the second-hatched chick usually starved or was preyed upon, reducing the brood to one chick. Parental investment patterns favored first-hatched chicks. Brood reduction, when employed, discouraged total nest failure, however, under appropriate conditions, brood reduction was avoided and full broods (or two chicks) were fledged.

Investigations into the determinations of hydride-forming elements

Analytical methods for the determination of trace amounts of germanium, tin and arsenic were established using hydride generation coupled with direct current plasma atomic emission spectrometry. A continuous gas flowing batch system for the hydride generation was investigated and was applied to the determination of germanium(Ge), tin(Sn), antimony(Sb) and lead(Pb) (Preliminary results suggest that it is also applicable to arsenic)As) ). With this system, the reproducibility of signals was improved and the determination was speeded up, compared with the conventional batch type hydride generation system. Each determination was complete within one minute. Interferences from a number of transition metal ions, especially from Pd(II), Pt(IV), Ni(II), Cu(II), Co(II), and Fe(II, III), have proven to be very serious under normal conditions, in the determination of germanium, tin, and arsenic. These interference effects were eliminated or significantly reduced in the presence of L-cystine or L-cysteine. Thus, a 10-1000 fold excess of Ni(II), Cu(II), Co(II), Fe(II), Pt(IV), Pd(II), etc. can be tolerated without interference, In the presence of L-cystine or L-cysteine, compared with absence of interference reducing agent. The methods for the determination of Ge, Sn, and As were examined by the analyses of standard reference materials. Interference effects from the sample matrix, for example, in transition metal-rich samples, copper, iron and steel, were eliminated by L-cystine (for As and Sn) and by LI cysteine (for Ge). The analysis of a number of standard reference materials gave excellent results of As and Sn contents in agreement with the certified values, showing there was no systematic interference. The detection limits for both germanium and tin were 20 pg ml- I . Preliminary studies were carried out for the determination of antimony and lead. Antimony was found to react with NaBH4, remaInIng from the previous determinations, giving an analytical signal. A reversed injection manner, i.e., injection of the NaBH4 solution prior to the analyte solution was used to avoid uncertainty caused by residual NaBH4 present and to ensure that an excess of NaB H4 was available. A solution of 0.4% L-cysteine was found to reduce the interference from selected transition metal ions, Co(II), Cu(II), Ni(II) and Pt(IV). Hydrochloric acid - hydrogen peroxide, nitric acid - ammonium persulphate, and potassium dichromate malic acid reaction systems for lead hydride generation were compared. The potassium dichromate - malic acid reaction medium proved to be the best with respect to reproducibility and minimal interference. Cu(II), Ni(II), and Fe(II) caused strong interference In lead determinations, which was not reduced by L-cysteine or Lcystine. Sodium citrate, ascorbic acid, dithizone, thiosemicarbazide and penicillamine reduced interferences to some extent. Further interference reduction studies were carried out uSIng a number of amino acids, glycine, alanine, valine, leucine and histidine, as possible interference reducing agents in the determination of germanium. From glycine, alanine, valine to leucine, the interference reduction effect in germanium determinations decreased. Histidine II was found to be very promising In the reduction of interference. In fact, histidine proved more efficient than L-cystine and L-cysteine In the reduction of interference from Ni(II) in the determination of germanium. Signal enhancement by easily ionized elements (EIEs), usually regarded as an interference effect in analysis by DCP-AES, was studied and successfully applied to advantage in improving the sensitivity and detection limit in the determination of As, Ge, Sn, Sb, and Pb. The effect of alkali and alkaline-earth elements on the determination of the above five hydride forming elements was studied. With the appropriate EIE, a signal enhancement of 40-115% was achieved. Linear calibration and good reproducibility were also obtained in the presence of EIEs. III

Study of the application of the high performance liquid chromatography-particle beam interface-mass spectrometry technique on some pesiticides and the reduction phenomena in the system

This work includes two major parts. The first part of the work concentrated on the studies of the application of the highperfonnance liquid chromatography-particle beam interface-mass spectrometry system of some pesticides. Factors that have effects on the detection sensitivity were studied. The linearity ranges and detection limits of ten pesticides are also given in this work. The second part of the work concentrated on the studies of the reduction phenomena of nitro compounds in the HPLC-PB-MS system. Direct probe mass spectrometry and gas chromatography-mass spectrometry techniques were also used in the work. Factors that have effects on the reduction of the nitro compounds were studied, and the possible explanation is proposed. The final part of this work included the studies of reduction behavior of some other compounds in the HPLC-PB-MS system, included in them are: quinones, sulfoxides, and sulfones.

Participants' perceptions of their involvement in a cardiovascular disease risk factor reduction program

A cardiovascular disease risk factor reduction program was implemented in the Niagara region. To gain an understanding of this program from the participants ' perspective, 10 participants of the program were interviewed to document their perceptions of what they learned in the program, their perceptions of their behaviour change and their perceptions of factors that facilitated or impeded any behaviour change. The learning style inventory and PET test were also given to the participants to further understand their perceptions. Findings unique to this study highlighted aspects of the andragogical model, self-directed learning theory, learning style preference and psychological type that were prominent in the participants' comments and perspectives. Implications for practice, theory development and further research are suggested.

Generator Matrix Based Search for Extremal Self-Dual Binary Error-Correcting Codes

Self-dual doubly even linear binary error-correcting codes, often referred to as Type II codes, are codes closely related to many combinatorial structures such as 5-designs. Extremal codes are codes that have the largest possible minimum distance for a given length and dimension. The existence of an extremal (72,36,16) Type II code is still open. Previous results show that the automorphism group of a putative code C with the aforementioned properties has order 5 or dividing 24. In this work, we present a method and the results of an exhaustive search showing that such a code C cannot admit an automorphism group Z6. In addition, we present so far unpublished construction of the extended Golay code by P. Becker. We generalize the notion and provide example of another Type II code that can be obtained in this fashion. Consequently, we relate Becker's construction to the construction of binary Type II codes from codes over GF(2^r) via the Gray map.

A Brief Statement of the Transactions and Accounts of Qr. M. Gen. James Thomas, attached to the Army on the Niagara Frontier, in the year 1812-1813 (1815)

A principle cause of the failure of the campaign on the Niagara Frontier in 1812 was the deficiency of subsistence for the troops; as quartermaster general, Thomas received much of the blame. His defense is offered here.

Shares Certificate - Gladstone Mines and Reduction Company

A shares certificate for Gladstone Mines and Reduction Company in the amount of 200 shares. The certificate is dated 13 March 1925 and is signed by the secretary F.J. Carr and the president Charles Stoddart. The price is one dollar per share and it is made out to W.H. Cowan.

alpha-Tocopherol's Antioxidant Role: A Biophysical Perspective

I present evidence of an antioxidant mechanism for vitamin E that correlates strongly with its physical location in a model lipid bilayer. These data address the overlooked problem of the physical distance between the vitamin's reducing hydrogen and lipid acyl chain radicals. The combined data from neutron diffraction, NMR and UV spectroscopy experiments, all suggest that reduction of reactive oxygen species and lipid radicals occurs specifically at the membrane's hydrophobic-hydrophilic interface. The latter is possible when the acyl chain adopts conformations in which they snorkel to the interface from the hydrocarbon matrix. Moreover, not all model lipids are equal in this regard, as indicated by the small differences in the vitamin's location. The present result is a clear example of the importance of lipid diversity in controlling the dynamic structural properties of biological membranes. Importantly, these results suggest that measurements of alpha-tocopherol oxidation kinetics, and its products, should be revisited by taking into consideration the physical properties of the membrane in which the vitamin resides.