Gene/Protein Disease Symptom Drug Enzyme Compound
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In these experiments, a few bilayers of D(2)O were vapor-deposited on a pure crystalline H(2)O ice film or an ice film doped with a small amount of HCl. Upon deposition, H/D isotopic exchange quickly converted the D(2)O layer into an HDO-rich mixture layer. Infrared absorption spectroscopy followed the changes of the HDO from the initial HDO mixture layer to HDO isolated in the H(2)O ice film. This was possible because isolated HDO in H(2)O ice has a unique, sharp peak in the O-D stretch region that can be distinguished from the broad peak due to the initial HDO mixture layer. The absorbance of isolated HDO displayed first-order kinetics and was attributed to diffusion of HDO from the HDO-rich mixture layer into the underlying H(2)O ice film. While negligible diffusion was observed for pure ice films and for ice films with HCl concentrations up to 1 x 10(-4) mole fraction, diffusion of HDO occurred for higher concentrations of (2-20) x 10(-4) mole fraction HCl with a concentration-independent rate constant. The diffusion under these conditions followed Arrhenius behavior for T = 135-145 K yielding E(a) = 25 +/- 5 kJ/mol. The mechanism for the HDO diffusion involves either (i) molecular self-diffusion or (ii) long-range H/D diffusion by a series of multiple proton hop and orientational turn steps. While these spectroscopic results compare favorably with recent studies of molecular self-diffusion in low-temperature ice films, the diffusion results from all the ice film studies at low temperatures (ca. T < 170 K) differ from earlier bulk ice studies at higher temperatures (ca. T > 220 K). A comparison and discussion of the various diffusion studies are included in this report.
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PMID:Diffusion of HDO in pure and acid-doped ice films. 1698 39

The mixed self-assembled monolayers (SAM) prepared from long chain alkanethiols, HS(CH(2))(11)NH(2) and HS(CH(2))(10)COOH, on gold are employed as the model surface for investigating the interactions between the biological environment and synthetic surface. A distinctive SAM preparation scheme was utilized in this investigation. The triethylamine was added to the alkanethiol solution during SAM formation and then followed by additional rinsing of SAM with 10% CH(3)COOH or 1% HCl ethanolic solution. The contact angle values of NH(2) + COOH mixed SAMs were between those of the pure SAMs, except that it was prepared with solution mole fraction of amine-terminated alkanethiol at 0.2. X-ray photoelectron spectroscopy (XPS) analysis has indicated that these two distinctive SAM preparation procedures had both resulted in a reduction in oxidized sulfur species on pure --NH(2) terminated SAM. However, the procedure utilizing 1% HCl ethanolic washing solution was more effective in reducing the unbound thiol fraction and to form a pure --NH(2) SAM with better quality. XPS analysis has also revealed that the surface of NH(2) + COOH mixed SAMs was "amine-rich". In vitro platelet adhesion assay has shown that the amount of adherent platelets on pure positive charged --NH(2) terminated SAM is less than that on anionic --COOH terminated counterpart in both acidic ethanolic washing schemes. Moreover, the lowest platelet adhesion density was noted on the mixed SAM surfaces with surface amine mole fraction at 0.51 and 0.57. This finding suggests that the surface charge with near neutrality might be of importance in reducing platelet adhesion and activation on artificial biomaterial.
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PMID:Surface characterization and platelet adhesion studies for the mixed self-assembled monolayers with amine and carboxylic acid terminated functionalities. 1732 42

The reaction rate between atmospheric hydrogen chloride (HCl) and chlorine nitrate (ClONO(2)) is greatly enhanced in the presence of ice particles; HCl dissolves readily into ice, and the collisional reaction probability for ClONO(2) on the surface of ice with HCl in the mole fraction range from approximately 0.003 to 0.010 is in the range from approximately 0.05 to 0.1 for temperatures near 200 K. Chlorine (Cl(2)) is released into the gas phase on a time scale of at most a few milliseconds, whereas nitric acid (HNO(3)), the other product, remains in the condensed phase. This reaction could play an important role in explaining the observed depletion of ozone over Antarctica; it releases photolytically active chlorine from its most abundant reservoir species, and it promotes the formation of HNO(3) and thus removes nitrogen dioxide (NO(2)) from the gas phase. Hence it establishes the necessary conditions for the efficient catalytic destruction of ozone by halogenated free radicals. In the absence of HCl, ClONO(2) also reacts irreversibly with ice with a collision efficiency of approximately 0.02 at 200 K; the product hypochlorous acid (HOCI) is released to the gas phase on a time scale of minutes.
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PMID:Antarctic stratospheric chemistry of chlorine nitrate, hydrogen chloride, and ice: release of active chlorine. 1774 62

The crux of this research was the pragmatic investigation into the formulation of a reconstitutable multiparticulate anti-tuberculosis drug delivery system for facilitated administration for the attainment of segregated gastrointestinal (GI) delivery of rifampicin (RIF) and isoniazid (INH) in order to address issues of unacceptable RIF bioavailability on coadministration with INH. Ionotropically crosslinked polymeric enterospheres for delivery of INH to the small intestine were developed via a response surface methodology for the design and optimization of the formulation and processing variables. A 3(4) Box-Behnken statistical design was constructed. The concentration of zinc sulfate salting-out and crosslinking electrolyte, the crosslinking reaction time, the drying temperature (DT), and the concentration of triethyl citrate plasticizer were varied for determination of their effect on the molar amount of zinc (n(Zn)) incorporated in the crosslinked enterosphere, drug entrapment efficiency (DEE), and mean dissolution time (MDT) at t(2h) in acidic media (0.1 M HCl). Complexometric determination of zinc cations (Zn(2+)) revealed that 23.70-287.89 mol of Zn(2+) per mole of polymer were implicated in crosslink formation. DEE of 27.92% to 99.77% were obtained. Drug release at t(2h) ranged from 1.67% to 73.04%. The salting-out and crosslinking agent significantly affected n(Zn) (p = 0.034) and the DEE (p = 0.000), as did the concentration of plasticizer employed (p = 0.000 and 0.002, respectively). High DTs (>42.5 degrees C) also significantly improved DEE (p = 0.029). ZnSO(4) had a significant effect on the MDT (p = 0.000). A dry dispersible multiparticulate system incorporating the optimally designed INH-loaded enterospheres and RIF was developed. Bivariate regression analysis of UV spectrophotometric absorbance data allowed in vitro resolution of RIF and INH release at simulated gastric pH.
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PMID:Formulation and statistical optimization of a novel crosslinked polymeric anti-tuberculosis drug delivery system. 1787 85

The design and application of a novel automated room-temperature laser spectrometer are reported. The compact instrument is based on difference-frequency generation in bulk LiNbO(3). The instrument employs a tunable cw external-cavity diode laser (795-825 nm) and a pulsed diode-pumped Nd:YAG laser (1064 nm). The generated mid-IR nanosecond pulses of 50-microW peak power and 6.5-kHz repetition rate, continuously tunable from 3.16 to 3.67 microm, are coupled into a 36-m multipass cell for spectroscopic studies. On-line measurements of methane are performed at concentrations between 200 ppb (parts in 10(9) by mole fraction) and approximately 1%, demonstrating a large dynamic range of 7 orders of magnitude. Furthermore computer-controlled multicomponent analysis of a mixture containing five trace gases and water vapor with an overall response time of 90 s at an averaging time of only approximately 30 s is reported. A minimum detectable absorption coefficient of 1.1 x 10(-7) cm(-1) has been achieved in an averaging time of 60 s, enabling detection limits in the ppb range for many important trace gases, such as CH(4), C(2)H(6), H(2)CO, NO(2), N(2)O, HCl, HBr, CO, and OCS.
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PMID:On-line multicomponent trace-gas analysis with a broadly tunable pulsed difference-frequency laser spectrometer. 1832 56

Saturating wood particles with HCl gas under pressure was found to be an effective pretreatment prior to subjecting wood to dilute acid hydrolysis. Pretreament is necessary to release sugars from wood because of the tight lattice structure of cellulose. The HCl gas makes the cellulose more susceptible to subsequent acid hydrolysis and the glucose yield is doubled when dilute acid hydrolysis is preceded by HCl saturation at high pressure. The saturation was most effectively performed in a fluidized bed reactor, with pure HCl gas fluidizing an equal volume of ground wood plus inert particles. The fluidized bed effectively dissipated the large amount of heat released upon HCl absorption into the wood. Batch reaction times of 1 h at 315 psia gave glucose yields of 80 degrees and xylose yields of 95 degrees after dilute acid hydrolysis. A model was developed which proposed gas diffusing through the solid as limiting the reaction rate and this was found to effectively describe the HCl-wood reaction in the fluidized bed. The HCl was found to form a stable adduct with the lignin residue in the wood, in a ratio of 3.33 mole of lignin monomer. The adduct was broken upon the addition of water.
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PMID:Production of sugars from wood using high-pressure hydrogen chloride. 1854 4

A procedure is described for the extractive spectrophotometric determination of nickel and palladium with quinoline-2-aldehyde thiosemicarbazone. At pH 7.5 nickel forms a 1:2 complex which is soluble in chloroform and has an absorption maximum at 460 nm. Palladium forms a 1:2 complex with maximum absorbance at 510 nm which can be extracted into MIBK from 1M HCl. Both complexes are stable and conform to Beer's law. The molar absorptivities for nickel and palladium are 1.58 x 10(4) and 2.6 x 10(3) 1.mole(-1). cm(-1) respectively. The proposed method is suitable for detection and determination of nickel and palladium in the presence of associated metal ions. The results of the analysis of synthetic mixtures and standard samples are reported.
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PMID:Quinoline-2-aldehyde thiosemicarbazone (QAT) as spectrophotometric reagent for palladium and nickel. 1896 96

This paper shows that the sensitivity of the Cr(III, VI)-Chrome Azurol S (CAS)-cetylpyridinium bromide (CPB)-hydroxylamine hydrochloride system can be increased and the wavelength of maximum absorption slightly shifted by addition of zinc(II) and that the analytical data are practically identical for both Cr(III) and Cr(VI), indicating that under the conditions used both initial oxidation states of chromium yield the same final oxidation state, Cr(III). On the basis of the Cr(III, VI)-CAS-CPB-NH(2)OH.HCl-Zn systems a new, highly sensitive and selective method for spectrophotometric determination of microamounts of Cr(III, VI) has been developed, with molar absorptivity of 1.27 x 10(5) 1. mole(-1) . cm(-1) for the complex at 620 nm and linear calibration up to 0.4 mug/ml chromium. Various foreign ions do not interfere. The method can be applied to direct determination of chromium in steels.
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PMID:Spectrophotometric determination of chromium(III, VI) by use of chromium(III, VI)-Chrome AzurolS-cetylpyridinium bromide-hydroxylamine hydrochloride-zinc(II) system. 1896 73

A solution of n-octylaniline in chloroform extracts rhenium selectively from 0.12-0.16 M nitric acid medium. Rhenium from the organic phase is backstripped with 5% aqueous ammonia solution and estimated spectrophotometrically with 5-chloro-2-hydroxythiobenzhydrazide (5-Cl-2-OHTBH). 5-Cl-2-OHTBH forms a blue complex with rhenium on heating in the acidity range 0.40-3.5 M HCl. The complex is extracted into chloroform and its absorbance is measured at 580 nm. The complex is stable for more than 12 h with a molar extinction coefficient of 9.0 x 10(3)l mole(-1) cm(-1) and a Sandell sensitivity of 0.019 mug cm(2).
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PMID:Spectrophotometric estimation of rhenium with 5-chloro-2-hydroxythiobenzhydrazide after its extraction separation using n-octylaniline. 1896 8

Although addition of mineral acids to WS(4)(2-) in water is known to lead to aggregation and formation of various polynuclear thiotungstate anions, acid hydrolysis of the MoS(4)(2-) anion is reported to give mainly MoS(3) or MoS(2) as hydrolysis products. Knowledge of the resulting product(s) from such reactions has implications on the use of tetrathiomolybdate (MoS(4)(2-)) as both a potential anti-tumor drug and for the treatment of Wilson's disease. In this investigation, reaction of HCl with MoS(4)(2-) in water was monitored as a function of time. Reaction mixtures of both 1:1 and 2:1 mole ratios of the acid to MoS(4)(2-) were examined, as well as MoS(4)(2-) reactions in simulated human stomach fluids at pH of approximately 2 and 3. Monitoring by electrospray mass spectrometry (ESMS), Fourier transform infrared (FTIR), and UV-visible spectroscopy clearly has revealed the formation of complex mixtures of polynuclear thiomolybdates (Mo(2)-Mo(18)). Generally, a two-stage consecutive reaction sequence occurs. A faster stage (k=7.0-7.9 x 10(-2)min(-1)), which seems to extend to trinuclear thiomolybdate species, followed by a slower second stage (k=5.4-15.2 x 10(-4)min(-1)) to higher polynuclear thiomolybdates. Under acidic conditions (e.g. pH approximately 3) that could also mimic some human stomach fluids, and under anaerobic atmosphere where the generated hydrogen sulfide is prevented from escaping from the reaction vessel, Mo(3)S(9)(2-) predominates over an extended reaction period. In similar reactions under aerobic conditions and where the hydrogen sulfide is irretrievably lost from the reaction mixture the binuclear (Mo(2)O(a)S(10-a)(2-);a=0-3) and trinuclear (Mo(3)O(b)S(9-b)(2-);b=1-3) anions predominate.
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PMID:Reactivity and kinetic studies of (NH4)2(MoS4) in acidic aqueous solution: possible relevance to the angiostatic function of the MoS4(2-) ligand. 1902 49


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