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121.
122.
The adsorption of neutral glycine onto amorphous silica was investigated both theoretically and experimentally. DFT calculations were performed at the BLYP-631++G** level using a cluster approach. Several possible configurations involving the formation of H bonds between glycine and one, two, or three silanol groups (SiOH) were considered. The most favorable bonding of glycine with one silanol group (45 kJ mol(-1)) occurs through the COOH moiety, thus forming a cycle in which the CO group is an H-bond acceptor whereas the acidic OH group is an H-bond donor. With two or three silanol groups, additional H bonds are formed between the amine moiety and the silanol groups, which leads to an increased adsorption energy (70 and 80 kJ mol(-1) for two and three silanol groups, respectively). Calculated nu(CO), delta(HNH), and delta(HCH) values are sensitive to the adsorption mode. A bathochromic shift of nu(CO) as compared to the nu(CO) of free glycine (calculated in the 1755-1790 cm(-1) range) is found for glycine in interaction with silanol(s). The more H bonds are formed between the COOH moiety and silanol groups, the higher the bathochromic shift. For delta(HNH), no shift is found for glycine adsorbed on one and two silanol groups (where the amine is either not bound or an H-bond donor), whereas a bathochromic shift is calculated with three silanols when the amine moiety is an H-bond acceptor. Experimental FTIR spectra performed at room temperature for glycine adsorbed at 160 degrees C on Aerosil amorphous silica exhibit bands at 1371, 1423, 1630, and 1699 cm(-1). The experimental/calculated frequencies have their best correspondence for glycine adsorbed on two silanol groups. It is important to note that the forms giving the best correspondence to experimental frequencies are the most stable ones. 相似文献
123.
Elizabeth Nunes Fernandes Mariele Nair de Campos Moura Jos Luis F. Costa Lima Boaventura F. Reis 《Microchemical Journal》2004,77(2):107-112
An automatic flow procedure for the determination of glycerol in wines by employing a flow system based on multicommutation and enzymatic reaction is described. Glycerol dehydrogenase was immobilized on aminopropyl glass beads and packed into a column that was coupled to the flow system. The NADH produced by the enzymatic reaction was monitored by spectrophotometry at 340 nm and its radiation absorption presented a relationship with glycerol concentration. The system manifold comprised a set of three-way solenoid valves controlled by a microcomputer, which was furnished with electronic interfaces and runs a software that was designed to carry out on-line sample dilution, reagent addition, and data acquisition. The procedure allows the determination of glycerol in wine samples without any prior pretreatment. The procedure presented as profitable features a linear response range between 2.0 and 10.0 g l−1 glycerol (R=0.998), a detection limit of 0.006 g l−1 glycerol, a relative standard deviation of 1.8% (n=14) for a typical wine sample presenting 5.3 g l−1 glycerol, a sampling throughput of 33 determinations per hour, and a NAD+ consumption of 0.8 mg per determination. The results were compared with those obtained using a reference method and no significant difference at 90% confidence level was observed. 相似文献
124.
Santiago MB Vélez MM Borrero S Díaz A Casillas CA Hofmann C Guadalupe AR Colón JL 《Electroanalysis》2006,18(6):559-572
We present a carbon paste electrode (CPE) modified using the electron mediator bis(1,10‐phenanthroline‐5,6‐dione)(2,2′‐bipyridine)ruthenium(II) ([Ru(phend)2bpy]2+) exchanged into the inorganic layered material zirconium phosphate (ZrP). X‐Ray powder diffraction showed that the interlayer distance of ZrP increases upon [Ru(phend)2bpy]2+ intercalation from 10.3 Å to 14.2 Å. The UV‐vis and IR spectroscopies results showed the characteristic peaks expected for [Ru(phend)2bpy]2+. The UV‐vis spectrophotometric results indicate that the [Ru(phend)2bpy]2+ concentration inside the ZrP layers increased as a function of the loading level. The exchanged [Ru(phend)2bpy]2+ exhibited luminescence even at low concentration. Modified CPEs were constructed and analyzed using cyclic voltammetry. The intercalated mediator remained electroactive within the layers (E°′=–38.5 mV vs. Ag/AgCl, 3.5 M NaCl) and electrocatalysis of NADH oxidation was observed. The kinetics of the modified CPE shows a Michaelis–Menten behavior. This CPE was used for the oxidation of NADH in the presence of Bakers' yeast alcohol dehydrogenase. A calibration plot for ethanol is presented. 相似文献
125.
The photophysical properties of Piroxicam , a nonsteroidal anti-inflammatory drug (NSAID), were investigated at different pHext values in reversed micelles of Aerosol-OT (AOT) in iso -octane, using both steady-state and picosecond time-resolved fluorescence spectroscopy. In contrast with the very complex data obtained in aqueous media, where several prototropic species are in equilibrium, the reversed micellar system essentially favors two species. The absorption spectra shows only one isosbestic point at λ= 348 nm. Excited-state intramolecular proton transfer (ESIPT), also detected in water, is promoted at low water pool contents measured by ω0 = [H2 O]/[AOT]. A strongly shifted (λem = 470 nm) tautomeric emission is found. Upon the gradual increase of ω0 , striking differences with pHext are found. At pHext = 4, the drug preferentially locates itself in the interfacial region partitioning between a hydrophobic and a hydrophilic domain. Global analysis was applied to the decay data and the results were interpreted by the "two-state excited-state" formalism. At pHext = 7, the anionic species is prevalent and the probe locates itself deeper inside the water core of the reversed micelles. Thus, a strong dependence on water content is detected, approaching a behavior similar to that observed in free aqueous solutions. 相似文献
126.
127.
Hair color changes and protein damage caused by ultraviolet radiation 总被引:12,自引:0,他引:12
Santos Nogueira AC Joekes I 《Journal of photochemistry and photobiology. B, Biology》2004,74(2-3):109-117
Ultraviolet and visible radiations are known to damage hair. However, quantitative data relating damage to hair type, proteins and color to the radiation wavelength are missing. We studied the effect of UV plus visible, UVA plus visible, visible mercury-vapor lamp radiation and sunlight on (blended) virgin dark-brown, blond and red hair and (one head) virgin black and curly dark-brown hair. All hair types showed a substantial increase in protein loss in water after lamp and sun irradiation. The damaging effect of UVB was about 2-5 times higher than that of UVA plus visible radiation, depending on the hair type. Significant color changes were also observed in every hair type, after lamp and sun irradiation, being more pronounced for the light colored hairs. The luminosity difference parameter was the major contributor to the hair color changes, but significant changes in the red-green and yellow-blue parameters of every hair were observed. In this case, the damaging effect is ascribable mainly to UVA radiation. No significant changes in the mechanical properties or topography were observed in any case. We discuss these results in terms of hair type and composition and melanin types. 相似文献
128.
Esteso Ana Alemany M. M. E. Ortiz Angel Liu Shaofeng 《Central European Journal of Operations Research》2022,30(3):1101-1127
Central European Journal of Operations Research - Agri-food production must increase while food waste needs to be reduced for improving the position of farmers. To do so it is necessary to... 相似文献
129.
Ana M. Vargas 《Rendiconti del Circolo Matematico di Palermo》1995,44(2):273-282
LetM
e
0
be the maximal operator over segments of length 1 with directions belonging to a Cantor set. It has been conjectured that
this operator is bounded onL
2. We consider a sequence of operators over finite sets of directions converging toM
e
0
. We improve the previous estimate for the (L
2,L
2)-norm of these particular operators. We also prove thatM
e
0
is bounded from some subsets ofL
2 toL
2. These subsets are composed of positive functions whose Fourier transforms have a very weak decay or are supported in a vertical
strip.
Partially supported by Spanish DGICYT grant no. PB90-0187. 相似文献
130.
LetEçS 1 be a set with Minkowski dimensiond(E)1. We consider the Hardy-Littlewood maximal function, the Hilbert transform and the maximal Hilbert transform along the directions ofE. The main result of this paper shows that these operators are bounded onL rad p (R2) forp>1+d(E) and unbounded whenp<1+d(E). We also give some end-point results. 相似文献