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Synthesis of L-fucose 2-, 3-, and 4-sulphates.

Treatment of L-fucose with an excess pf pyridine-sulphur trioxide gave an equilibrium mixture of mono-, di-, and tri-sulphates. L-Fucose was sulphated under optimal conditions for monosulphate formation, and the monoester fraction was isolated by chromatography on DEAE-cellulose. The isomeric L-fucose 2-, 3-, and 4-sulphates (1-3) were separated on a DEAE-cellulose column by elution with borate buffer. The structures of 1-3 were established by electrophoresis, colour tests, periodate oxidation, and, for the 2-isomer, by comparison with a specimen of 1 that had been definitively synthesised via methyl 3,4-O-isopropylidene-alpha-L-fucopyranoside (6) and methyl alpha-L-fucopyranoside 2-(barium sulphate) (5). The latter was rapidly hydrolysed in hot, dilute acetic acid to 1 and methyl alpha-L-fucopyranoside (4).

Chemical Phenomena↗

Pore structure and adsorption performance of the activated carbons prepared from plum kernels.

According to iodine number, amount of methylene blue adsorption, the BET specific surface area, and the yield, the conditions for preparing activated carbons as adsorbents from plum kernels were optimized. The activation temperature and time tested were in the ranges 750-900 degrees C and 1-4 h, respectively. Adsorption isotherms of two commercial dyes and phenol from water on such activated carbons were measured at 30 degrees C. It was shown that the optimal activation temperature and time depended on the molar mass of the solutes, and all equilibrium isotherms could be fitted by the Langmuir equation. The experimental results indicated that the prepared activated carbons were economically promising for adsorption removal of dyes and phenol, in contrast to other commercial adsorbents.

Adsorption↗

Hand trajectory formation during whole body reaching movements in man.

End-effector trajectory formation was studied during a reaching movement using the whole body. The movements of various parts of the body were measured with the optoelectronic ELITE system. Wrist reaching movement paths showed noticeable curvatures. The analysis of various marker onset latencies revealed that the wrist was the last to move, always after the head, knee or trunk, suggesting a subordinate role of the focal component with respect to the primary role of the equilibrium component. These results suggest that reaching wrist movements are subjected to whole-body equilibrium constraints in addition to constraints placed upon end-effector kinematics or the dynamic optimization of upper-limb movements.

Adult↗

The design of a panel study under an alternating Poisson process assumption.

We discuss the design of a panel study for the estimation of the average durations in the two states of an alternating Poisson process. Two types of designs are examined. The first fixes the number of follow-up waves but permits the total length of follow-up to vary, and the second varies the number of follow-up waves with fixed length. Simple expressions for nearly optimal designs are presented, and we compare these with designs allowing for continuous observation. Both equilibrium and nonequilibrium cases are examined. An example is given using morbidity data to illustrate how these results can be applied.

Follow-Up Studies↗

Haemodiafiltration.

Using haemodiafiltration--a combination of haemodialysis and haemofiltration--an increased clearance rate for middle and small molecules can be obtained compared to the single technique alone. Low molecular weight substances are removed mainly by diffusion, and middle molecules predominantly by convection. Using currently available equipment the duration of therapy can thus be reduced by at least one-third, compared with haemodialysis, without deterioration in the patient's general condition. The withdrawal of large volumes of fluid is markedly better tolerated by the patient than with other short-time blood purification procedures. With the aid of haemodiafiltration both molecular groups can be diminished independently of each other according to individual demand, thereby leading to optimization of dialysis therapy.

Acid-Base Equilibrium↗

Linear two-step gradient counter-current chromatography analysis based on a recursive solution of an equilibrium stage model.

The implementation of gradients in continuously operated chromatographic counter-current processes has recently attracted considerable interest as a method to improve the performance of this effective separation method. If liquid mobile phases are applied it is advantageous to set the solvent strength in the desorbent stream higher than that in the feed stream. As a consequence. the components to be separated are more retained in the adsorption zones and more easily eluted in the desorption zones. Due to the additional degrees of freedom the design and the optimization of such a two-step gradient counter-current process is difficult. In this paper a steady state equilibrium stage model is used to simulate the process under linear conditions. A simple solution of the underlying model equations is presented capable to describe efficiently the unit for large stage numbers typically encountered in chromatographic columns. Due to the rapidity of the algorithm developed a broad range of operating conditions can be evaluated systematically for different types of gradients. The impact of (a) the functional dependence of the adsorption equilibrium constants on the solvent composition, (b) the number of equilibrium stages and (c) the specification of purity requirements is illustrated and discussed based on results of parametric calculations. The results achieved emphasize the potential of two-step gradient counter-current chromatography.

Countercurrent Distribution↗

[Correlation of acid-base equilibrium and glycolysis during muscle activity].

Interdependence between acid-base equilibrium of blood and accumulation of lactate depending on the intensity of exertion during swimming and individual reaction to the exertion has been analyzed when examining high-qualification sportsmen. Prognostication and optimization criteria of acidosis prophylaxis are suggested.

Acid-Base Equilibrium↗

Exchange between inorganic phosphate and adenosine triphosphate in (Na+,K+)-ATPase.

(Na+,K+)-ATPase is able to catalyze a continuous ATP in equilibrium Pi exchange in the presence of Na+ and in the absence of a transmembrane ionic gradient. At pH 7.6 the Na+ concentration required for half-maximal activity is 85 mM and at pH 5.1 it is 340 mM. In the presence of optimal Na+ concentration, the rate of exchange is maximal at pH 6.0 and varies with ADP and Pi concentration in the assay medium. ATP in equilibrium Pi exchange is inhibited by K+ and by ouabain.

Adenosine Diphosphate↗

Apparent and true enantioselectivity in enantioseparations.

The separation factor of two compounds in chromatography is the ratio of their equilibrium constants or retention factors. This parameter is universally employed to investigate their resolution and to optimize the experimental conditions of their analysis. In enantioseparations, the situation is more complex because there is a mixed retention mechanism. The retention factor is the sum of two contributions, one enantioselective, the other nonselective. Although both contribute to retention, the latter being identical for the two enantiomers and does not contribute to their separation. We show how these two contributions can be measured and how it becomes necessary to distinguish between the apparent, alpha(app), and the true, alpha(true), separation factors. The existence of nonselective sites is responsible for alpha(app) being less than alpha(true). Depending on the difference between these two factors, the more effective approach to improve a separation is either to increase the enantioselectivity or to reduce the nonselective interactions. Practical applications to separations of different beta-blockers on cellobiohydrolase are discussed. The apparent enantioselectivity of alprenolol is larger and increases faster with increasing pH than that of the more hydrophobic propranolol, in spite of the importance of hydrophobic interactions in the enantioselective mechanism. These two unexpected properties are discussed and explained.

Adrenergic beta-Antagonists↗

Spreading and staining of human metaphase chromosomes on aminoalkylsilane-treated glass slides.

The properties of aminoalkylsilane-treated glass slides for the preparation of metaphase spreads and their staining quality have been studied and compared with those of slides which had only been cleaned in ethanol/ether. The parameters investigated were: (1) the average area of metaphases from cultures of blood from both healthy donors and haematology patients; (2) the influence of the positively charged 'coating' on the quality of quinacrine- and Giemsa-banding patterns; (3) non-specific background staining for these banding methods; (4) the number of metaphases as compared to the number of interphase cell nuclei per area of preparation; and (5) the Feulgen-staining intensities of chromosomes and chicken erythrocyte nuclei. The quality of metaphase preparations and the differential staining of chromosomes is better on aminoalkysilane-treated glass slides than that of preparations on routinely cleaned normal microscope slides. In the preparations on aminoalkylsilane-treated slides, the distribution of the cells over the glass surface is more homogeneous; and no influence could be detected on the relative frequency of metaphases as compared to the number of non-divided cell nuclei; the average area per metaphase is increased by about 10% and consequently the number of overlapping chromosomes is decreased. Preparations on aminoalkylsilane-treated glass, after Q-, G- and DAPI-banding procedures, always showed less binding of the staining compounds to the glass slide (a cleaner background) than those on routinely cleaned microscope glass slides. The Feulgen-pararosaniline staining intensities of human metaphase chromosomes and chicken erythrocyte nuclei are the same on aminoalkylsilane-treated slides and on routinely cleaned glass slides. Furthermore, the reproducibility and constancy of quinacrine banding was improved by development of an equilibrium staining method which does not require a washing procedure. The medium, containing 0.002% quinacrine, allows optimal staining results to be obtained for microphotography purposes within 30 min of staining (for visual inspection at least 90 min is required) and is used as the embedding medium. In combination with aminoalkylsilane-treated glass slides, this procedure leads to a clean background and reproducible banding patterns of excellent quality, the results being better and more constant than those of methods described before.

Azure Stains↗

Action of phospholipase A2 on bilayers. Effect of fatty acid and lysophospholipid additives on the kinetic parameters.

Action of pig pancreatic phospholipase A2 on the ternary codispersions of diacylphosphatidylcholine, 1-acyllysophosphatidylcholine and fatty acids is examined. The binding and kinetic constants are found to be the same under a variety of conditions. These parameters and the catalytic turnover number change with the phase-transition temperature of the ternary codispersions, and optimal binding, kinetic and catalytic constants are seen in the phase-transition range where an equilibrium exists between laterally separated phases. The effect of changing the structure of any of the three components is also via a change in the phase-transition temperature of their ternary codispersions. These observations suggest that the binding of pig pancreatic phospholipase A2 to the defect sites on the substrate interface determines the substrate concentration dependence of the initial rate of hydrolysis, and the catalytic turnover by the bound enzyme also depends upon the phase state of the bilayer. An additive-induced stabilization of the defects in the substrate bilayer is postulated to account for the enhanced binding of the enzyme to the bilayer.

Animals↗

Carbohydrate-enzyme conjugates for competitive EIA.

Enzyme glycoconjugates prepared from oligosaccharides or polysaccharides are efficient and durable reagents for direct, competitive enzyme immunoassays based on solid phase antibody. This assay format facilitates simple measurement of association constants and relative inhibitory power of oligosaccharides, while also providing a sensitive quantitative assay of bacterial polysaccharide antigens. Enzyme-saccharide conjugates were prepared by established glycoconjugate methodologies, and protocols for their optimal use were established by investigating the effects of solid phase antibody concentration on the kinetic equilibrium of binding for different antigen-enzyme conjugate concentrations, in the presence and absence of inhibitor. Four discrete monoclonal antibody-carbohydrate antigen systems were studied and it is demonstrated for each, that the relative inhibitory power of oligosaccharides may be readily measured in a convenient assay format, and that association constants can be extrapolated from the same assay data.

Alkaline Phosphatase↗

Recovery of Acinetobacter radioresistens lipase by hydrophobic adsorption to n-hexadecane coated on nonwoven fabric.

A simple and clean adsorption/desorption process was proposed for recovering Acinetobacter radioresistens lipase from fermentation broth. The adsorbent used was n-hexadecane coated on a hydrophobic nonwoven fabric (NWF). n-Hexadecane has a melting point of 16-18 degrees C, and its affinity for lipase decreases markedly from liquid to solid state. Accordingly, performing the adsorption and desorption above and below, respectively, the melting point would need no extraneous materials for separation. The adsorption isotherms at various temperatures were found to follow the Langmuir model. Simulation of the batch adsorption/desorption process showed that there exists an optimal amount of adsorbent for both concentration factor and enzyme recovery; the process is restrained by equilibrium. The performance of column adsorption/desorption could also be simulated using the adsorption isotherm, and it was shown that the concentration factor was proportional to the amount of adsorbent used. The benefits of this process include easy preparation of adsorbent, low operational cost, no extraneous materials needed, negligible enzyme denaturation, high efficiency, and simple process simulation.

Acinetobacter↗

Interaction between antibodies and hapten-protein conjugates of different composition: theoretical predictions and experimental data.

Mathematical models of competitive ELISAs with labelled antibody and with labelled antigen taking into account bivalent interactions between antibodies and hapten-protein conjugates were developed and analyzed. It was shown that in the kinetic model of the immunochemical reaction the conjugate composition influenced the amplitude of detected signal but not ELISA sensitivity. In the equilibrium model decreased sensitivity correlated with bivalent complexes formation. The predictions were tested experimentally using 2,4-dichlorophenoxyacetic acid (2,4-D) and testosterone as haptens. It was confirmed that increasing of the hapten : protein ratio resulted in formation of bivalent complexes with antibodies. The equilibrium binding constants for these complexes were two orders of magnitude higher than for monovalent ones. Optimal conjugate compositions have been chosen for ELISA of these haptens.

Animals↗

Tendon transfer for median nerve palsy.

A large number of tendon transfers have been described that restore opposition to the thumb and provide thumb and finger flexion. To provide optimal results following tendon transfers, one needs to follow the principles of tendon transfer: normal tissue equilibrium, movable joints, and a scar-free bed. Once these are present, we must look to available tables to determine an appropriate tendon transfer, matching up the lost muscle mass, fiber length, and cross-sectional area and then pick out muscle-tendon units of similar size, strength, and potential excursion. For low median nerve palsy (Table 4), we have found from our experimental and clinical studies that the FDS of the long and ring fingers or the wrist extensors (ECR or ECRL) best approximate the force and motion required for full thumb opposition and strength. These transfers are preferred in median nerve palsy or combined median ulnar nerve palsy when both strength and motion are required. In circumstances where only thumb mobility is desired, the EIP is an ideal transfer. Also, the extensor digitorum quinti (EDQ) and ADQ have sufficient mean fiber length (muscle excursion) to provide full thumb opposition. The palmaris longus transfer (Camitz transfer) is an abduction rather than an opposition transfer and should be reserved for selected cases of long-term carpal tunnel syndrome. For high median nerve palsy (Table 5), transfers of the brachioradialis or ECRL to restore lost thumb flexion (FPL) and side-to-side transfer of the FDP of the index finger are generally sufficient. A separate transfer to restore independent flexion of the index finger could be performed by utilizing the pronator teres or extensor carpi radialis ulnaris tendon muscle units. As they combine a proper direction of action, pulley location, and tendon insertion, tendon transfers for median nerve palsy are usually quite successful. In considering any of these elective procedures, however, it is important to remember that tendon transfers are muscle balance operations. The effect of transfer on restoring function must be carefully studied to assess the loss of function that such a transfer may endure.

Hand↗

[Metabolic disorders and current treatment of the surgical patient with pancreatitis].

Very frequently in acute and chronic pancreatitis, the surgical treatment is indispensable. The disease itself is accompanied by metabolic disturbances, protein deficiency, hepatic lesion, by diabetes and malabsorption syndrome. Following the laboratory parameters we were able to perform partial or total hyperalimentation, correction of acid-base dis-equilibrium and to obtain the positive nitrogen balance, and in this way keep the patients in optimal conditions pre- and postoperatively.

Acute Disease↗

Tissue impedance as a function of temperature and time.

Tissue impedance dependence on temperature has been measured for six tissue types. The information was gathered using an automated laboratory under computer control. This information is needed to be able to input these values into a computer model that predicts temperature distribution produced by delivery of radio frequency energy. Due to the thermal dose of time and temperature, tissue properties change and no published data are available that document this. Since there are no theoretical predictions, empirical data were measured to supply this information. Using an aluminum cylindrical cavity of volume 1.69 cm3, muscle, liver, brain, and fat tissue impedance were measured at 500 kHz over a range of temperatures. All tests began at room temperature where baseline measurements were made. The cylinder was then placed in a constant temperature water bath at between 30 and 90 degrees C. The tests were run for a period of 10 to 30 minutes. Temperature homogeneity was carefully studied throughout the volume of the cylinder. It was found that thermal equilibrium occurred within four minutes. Special care was taken with the tissue sample in regard to optimize moisture and freshness, and minimize fat content. Grain orientation was also taken into consideration depending on the test. For all tissue types, resistivity decreased initially as the sample temperature equilibrated with the bath temperature. For temperatures less than 75 degrees C, resistivity values remained approximately constant over time.

Adipose Tissue↗

Steady state kinetics and binding of eukaryotic cytochromes c with yeast cytochrome c peroxidase.

1. The steady state kinetics for the oxidation of ferrocytochrome c by yeast cytochrome c peroxidase are biphasic under most conditions. The same biphasic kinetics were observed for yeast iso-1, yeast iso-2, horse, tuna, and cicada cytochromes c. On changing ionic strength, buffer anions, and pH, the apparent Km values for the initial phase (Km1) varied relatively little while the corresponding apparent maximal velocities varied over a much larger range. 2. The highest apparent Vmax1 for horse cytochrome c is attained at relatively low pH (congruent to 6.0) and low ionic strength (congruent to 0.05), while maximal activity for the yeast protein is at higher pH (congruent to 7.0) and higher ionic strength (congruent to 0.2), with some variations depending on the nature of the buffering ions. 3. Direct binding studies showed that cytochrome c binds to two sites on the peroxidase, under conditions that give biphasic kinetics. Under those ionic conditions that yield monophasic kinetics, binding occurred at only one site. At the optimal buffer concentrations for both yeast and horse cytochromes c, the KD1 and KD2 values approximate the Km1 and Km2 values. At ionic strengths below optimal, binding becomes too strong and above optimal, too weak. 4. Under ionic conditions that are optimal and give monophasic kinetics with horse cytochrome c but are suboptimal for the yeast protein, yeast cytochrome c strongly inhibits the reaction of horse cytochrome c with peroxidase, uncompetitively at one site and competitively at a second site. The appearance of the second site under monophasic conditions is interpreted as an allosteric effect of the inhibitor binding to the first site. 5. The simplest model accounting for these observations postulates two kinetically active sites on each molecule of peroxidase, a high affinity and a low affinity site, that may correspond to the free radical and the heme iron (IV) of the oxidized enzyme, respectively. Both oxidizing equivalents may be discharged at either site. Furthermore, the enzyme appears to exist as an equilibrium mixture of a high ionic strength form, EH and a low ionic strength form, EL, the former reacting optimally with yeast cytochrome c, and the latter with horse cytochrome c.

Animals↗