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201.
202.
Zhu Y Nikolic D Van Breemen RB Silverman RB 《Journal of the American Chemical Society》2005,127(3):858-868
Nitric oxide synthases (NOS) are hemoproteins that catalyze the reaction of L-arginine to L-citrulline and nitric oxide. N-(3-(Aminomethyl)benzyl)acetamidine (1400W) was reported to be a slow, tight-binding, and highly selective inhibitor of iNOS in vitro and in vivo. Previous mechanistic studies reported that 1400W was recovered quantitatively after iNOS fully lost its activity and modification to iNOS was not detected. Here, it is shown that 1400W is a time-, concentration-, and NADPH-dependent irreversible inactivator of iNOS. HPLC-electrospray mass spectrometric analysis of the incubation mixture of iNOS with 1400W shows both loss of heme cofactor and formation of biliverdin, as was previously observed for iNOS inactivation by another amidine-containing compound, N5-(1-iminoethyl)-L-ornithine (L-NIO). The amount of biliverdin produced corresponds to the amount of heme lost by 1400W inactivation of iNOS. A convenient MS/MS-HPLC methodology was developed to identify the trace amount of biliverdin produced by inactivation of iNOS with either 1400W or L-NIO to be biliverdin IXalpha out of the four possible regioisomers. Two mechanisms were previously proposed for iNOS inactivation by L-NIO: (1) uncoupling of the heme peroxide intermediate, leading to destruction of the heme to biliverdin; (2) abstraction of a hydrogen atom from the amidine methyl group followed by attachment to the heme cofactor, which causes the enzyme to catalyze the heme oxygenase reaction. The second mechanistic proposal was ruled out by inactivation of iNOS with d3-1400W, which produced no d2-1400W. Detection of carbon monoxide as one of the heme-degradation products further excludes the covalent heme adduct mechanism. On the basis of these results, a third mechanism is proposed in which the amidine inactivators of iNOS bind as does substrate L-arginine, but because of the amidine methyl group, the heme peroxy intermediate cannot be protonated, thereby preventing its conversion to the heme oxo intermediate. This leads to a change in the enzyme mechanism to one that resembles that of heme oxygenase, an enzyme known to convert heme to biliverdin IXalpha. This appears to be the first example of a compound that causes irreversible inactivation of an enzyme without itself becoming modified in any way. 相似文献
203.
Kaale E Govaerts C Hoogmartens J Schepdael AV 《Rapid communications in mass spectrometry : RCM》2005,19(20):2918-2922
Aminoglycoside antibiotics are widely used to treat serious Gram-negative and Gram-positive bacterial infections. The lack of a UV chromophore presents a problem in the analysis of aminoglycosides. Derivatization with 1,2-phthalic dicarboxaldehyde (OPA) in the presence of a thiol made it possible to introduce a UV chromophoric thioisoindole moiety. A qualitative mass spectrometry study was carried out to confirm the molecular identity of the products formed. The conditions described earlier to derivatize gentamicin and kanamycin yielded products in which all primary amino groups are fully derivatized. On the other hand, with tobramycin and amikacin, there was also formation of incompletely derivatized products that contained one thioisoindole group less than the fully derivatized product. This study has therefore brought an additional insight into the nature of the OPA-aminoglycoside derivatives studied. 相似文献
204.
Liquid-liquid cloud point diagrams of solutions of nearly monodisperse samples of polystyrene (PS), and binary mixtures of nearly monodisperse PS’s, both in methylcyclohexane (MCH), were determined for several polymer molecular weights (Mw) at 0.1 MPa. The bimodal mixtures (PS[Mw(1),ρ(1)] + PS[Mw(2),ρ(2)], Mw(1)=90×103 g/mol, Mw(2)=13×103 g/mol, 5.78 × 103 g/mol, and 2.2 × 103 g/mol, ρ=1.06) were prepared constraining 〈Mw〉=38.6×103 g/mol, ρ=Mw/Mn is the polydispersity index. In each case the cloud point curves (CPC’s) for the bimodal mixtures are strongly skewed, lying well above CPC for 〈Mw〉 when φ<φCRITICAL, and below CPC for 〈Mw〉 when φ>φCRITICAL; φ is volume fraction polymer in the polymer/solvent mixture. The experimental results are discussed in the context of empirical and mean-field representations. 相似文献
205.
A. Zwijnenburg H.O. Van Oven C.J. Groenenboom H.J. De Liefde Meijer 《Journal of organometallic chemistry》1975,94(1):23-27
(Cyclopentadienyl)(1-methylallyl)(butadiene)titanium, C13H18Ti, has been obtained from the reaction between (C5H5)TiCl3 or (C5H5)TiCl2 and 1-methylallylmagnesium bromide in ether. The brown compound is diamagnetic and thermally stable, but very sensitive to oxygen. The nature of the new compound has been elucidated from its reaction with bromine and by IR, 1H and 13C NMR, and mass spectral analysis. 相似文献
206.
The uptake of several actinides [U(VI), Th(IV), Am(III), Cm(III)] and fission products was investigated from nitric acid solutions by two novel extraction chromatographic sorbents containing 2-(2-hexyloxy-ethyl)-N,N'-dimethyl-N,N'-dioctyl-malonamide (DMDOHEMA) and N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA), respectively. The kinetics of the uptake of actinides was studied. The sorption of metal ions fromz simulated Low Level Liquid Waste (LLLW) solutions was evaluated. The results of these experiments revealed that the actinides and lanthanides could be separated from the bulk of other fission products in simulated LLLW solutions on both sorbents.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
207.
Experimental investigations on binary liquid mixtures near the critical mixing point are presently leading to a controversy about the anomaly in the thermal conductivity. A photopyroelectric technique is used to determine the thermal conductivity and the effusivity of the binary liquid mixture n-butoxyethanol-water at its critical concentration near the critical mixing point. It is proven that, contrary to previous reports, there is no critical enhancement in the thermal conductivity. The specific heat capacity is calculated from these results and compared with the results from measurements performed by adiabatic scanning calorimetry. 相似文献
208.
De Vriendt K Sandra K Desmet T Nerinckx W Van Beeumen J Devreese B 《Rapid communications in mass spectrometry : RCM》2004,18(24):3061-3067
The use of electrospray ionization mass spectrometry (ESI-MS) for studying non-covalent interactions between macromolecules and ligands is well established. ESI-MS can be a useful tool for the determination of dissociation constants between molecules in the gas phase. We validate this method by studying the binding of the catalytic domain of cellobiohydrolase I (CBH I) from Trichoderma reesei to the disaccharide inhibitor cellobiose. The method was further applied to study two newly synthesized cellobiose derivatives (m-iodobenzyl 2-deoxy-2-azido-beta-cellobioside and p-benzyloxybenzyl beta-cellobioside). In a titration experiment, peak areas of different charge states of the free enzyme and the complex were summed in order to determine the dissociation constant. For cellobiose and m-iodobenzyl 2-deoxy-2-azido-beta-cellobioside, the calculated values are in good agreement with those reported from either displacement titration or equilibrium binding experiments in solution. Due to non-specific binding, the dissociation constant of p-benzyloxybenzyl beta-cellobioside does not correspond with the solution-based value. Our results indicate the need for careful interpretation of data sets when using nanoESI to study non-covalent interactions. 相似文献
209.
It is shown that on the superacid cyclization of esters of bishomobicyclogeranylgeranic and E,E-bishomofarnesic acids fully cyclized hydroxyesters are formed in good yield, while on the interaction of esters of 6-hydroxy- and 6-acyloxy-15-bishomobicyclogeranylgeranic acids with a superacid no carbocyclization takes place. 相似文献
210.
Anna Worobiec Lucyna Samek Zoya Spolnik Velichka Kontozova Elzbieta Stefaniak René Van Grieken 《Mikrochimica acta》2006,156(3-4):253-261
The St. Michael Archangel’s Church in Szalowa, Poland, was selected for closer investigation with respect to the indoor/outdoor
air exchange and its influence on the air quality and work arts preservation. Chemical composition, size and abundance of
particulate matter and concentration of gases NO2, SO2, O3 inside and outside the church were determined. To study seasonal variation of the weather condition (temperature, inversion
level, wind direction) and the influence of seasonal sources of the air pollution (like heating of the nearby houses), samples
were collected in winter and summer time. It was stated that suspended particulate matter inside the wooden church has in
general an outdoor source. Several groups of particles were distinguished such as the organic ones, soil dust, nitrates and
sulphates. In case of organic and soil dust particles, the concentration inside was higher than outside. From the results,
in comparison to literature data, one can conclude that accumulation of particulate suspended matter in the church is more
intense than in other types of buildings. Gaseous pollutants were detected but their concentration was negligible. 相似文献