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PubMed1999

High sensitivity immunoassays using particulate fluorescent labels.

The use of polystyrene fluorescent microspheres as sensitive labels in direct-detection (not enzymatically amplified) heterogeneous equilibrium "sandwich" immunoassays in 96-well plates is described. With mouse IgG as a model antigen, a fluorescent particulate label is more sensitive than a corresponding soluble reporter. The limit of detection of mouse IgG in the multiparametrically optimized assay was 0.2 ng/ml (7.6 x 10(8) antigens/ml) for the particulate reporter and 50 ng/ml (1.9 x 10(11) antigens/ml) for the soluble reporter. The sensitivities of assays using the particulate label were dependent on the surface densities of the capture and reporter antibodies and the concentration of reporter beads. Sensitivity was improved by adding the preformed reporter antibody/fluorescent microsphere complex to trapped antigen on the well surfaces instead of sequentially adding the reporter antibody and then the fluorescent microspheres. Maximal (equilibrium) binding of the particulate reporter to captured antigen occurred after 20 h with a concentration of 1.4 x 10(9) reporter beads/ml. Thus, particulate fluorescent labels provide high sensitivity in direct-detection immunoassays.

Animals↗

PubMed2005

Protein C production: metal ion/protein interfacial interaction in immobilized metal affinity chromatography.

Protein C (PC) is an essential blood factor in the human blood coagulation cascade. PC can help achieve blood hemostasis in many deadly disease conditions such as sepsis, cancer, HIV, etc.; reduced oxygen transport due to blood agglutination within the body can cause tissue death and organ failure as a result of low oxygen transport. Our goal is to produce large quantities of low cost zymogen PC for the treatment and prevention of blood clotting resulting from many disease states, as well as provide an effective therapy for PC deficiency. Current studies show that Immobilized Metal Affinity Chromatography (IMAC) has high specificity and can be used for difficult separations among homologous proteins at relatively low cost compared to current methods, such as Immunoaffinity Chromatography. Thus, we are investigating the optimization of IMAC for the separation and purification of PC from Cohn fraction IV-I. Molecular interactions within the chromatography column involve many parameters that include: the use and type of chromatographic gel and buffer solution, the pH, temperature, metal ion, chelator, and the sequence and structure of the protein itself. These parameters all influence the protein's interaction with the column. Experimental equilibrium isotherms show that PC has primary and secondary binding characteristics, demonstrating that the interaction is not just a simple process of one protein binding to one metal ion. Understanding the thermodynamics of interfacial interaction between proteins and surface-bound Cu2+ is essential to optimizing IMAC for PC purification, as well as for separation of other proteins in general. Hence we are undertaking theoretical and experimental studies of IDA-Cu/PC adsorption. The differences in structures of PC and other critical homologous blood factors are examined using the protein visualization program Cn3D. A better understanding of the interfacial phenomena will help determine the most effective conditions to achieve our goal.

Adsorption↗

PubMed2006

Systematic QM/MM investigation of factors that affect the cytochrome P450-catalyzed hydrogen abstraction of camphor.

The hydrogen abstraction reaction of camphor in cytochrome P450(cam) has been investigated in the native enzyme environment by combined quantum mechanical/molecular mechanical (QM/MM) calculations and in the gas phase by density functional calculations. This work has been motivated by contradictory published QM/MM results. In an attempt to pinpoint the origin of these discrepancies, we have systematically studied the factors that may affect the computed barriers, including the QM/MM setup, the optimization procedures, and the choice of QM region, basis set, and protonation states. It is found that the ChemShell and QSite programs used in the published QM/MM calculations yield similar results at given geometries, and that the discrepancies mainly arise from two technical issues (optimization protocols and initial system preparation) that need to be well controlled in QM/MM work. In the course of these systematic investigations, new mechanistic insights have been gained. The crystallographic water 903 placed near the oxo atom of Compound I lowers the hydrogen abstraction barrier by ca. 4 kcal/mol, and thus acts as a catalyst for this reaction. Spin density may appear at the A-propionate side chain of the heme if the carboxylate group is not properly screened, which might be expected to happen during protein dynamics, but not in static equilibrium situations. There is no clear correlation between the computed A-propionate spin density and the hydrogen abstraction barrier, and hence, no support for a previously proposed side-chain mediated transition state stabilization mechanism. Standard QM/MM optimizations yield an A-propionate environment close to the X-ray structure only for protonated Asp297, and not for deprotonated Asp297, but the computed barriers are similar in both cases. An X-ray like A-propionate environment can also be obtained when deprotonated Asp297 is included in the QM region and His355 is singly protonated, but this Compound II-type species with a closed-shell porphyrin ring has a higher hydrogen abstraction barrier and should thus not be mechanistically relevant.

Binding Sites↗

PubMed2005

Entropic interaction chromatography: separating proteins on the basis of size using end-grafted polymer brushes.

Partitioning of a macromolecule into the interfacial volume occupied by a grafted polymer brush decreases the configurational entropy (DeltaSbrush(c)) of the terminally attached linear polymer chains due to a loss of free volume. Self-consistent field theory (SCF) calculations are used to show that DeltaSbrush(c) is a strong function of both the size (MWp) of the partitioning macromolecule and the depth of penetration into the brush volume. We further demonstrate that the strong dependence of DeltaSbrush(c) on MWp provides a novel and powerful platform, which we call entropic interaction chromatography (EIC), for efficiently separating mixtures of proteins on the basis of size. Two EIC columns, differing primarily in polymer grafting density, were prepared by growing a brush of poly(methoxyethyl acrylamide) chains on the surface of a wide-pore (1,000-A pores, 64-microm diameter rigid beads) resin (Toyopearl AF-650M) bearing surface aldehyde groups. Semipreparative 0.1-L columns packed with either EIC resin provide reduced-plate heights of 2 or less for efficient separation of globular protein mixtures over at least three molecular-weight decades. Protein partitioning within these wide-pore EIC columns is shown to be effectively modeled as a thermodynamically controlled process, allowing partition coefficients (K(P)) and elution chromatograms to be accurately predicted using a column model that combines SCF calculation of K(P) values with an equilibrium-dispersion type model of solute transport through the column. This model is used to explore the dependence of column separation efficiency on brush properties, predicting that optimal separation of proteins over a broad MWp range is achieved at low to moderate grafting densities and intermediate chain lengths.

Acrylamides↗

PubMedDate not supplied

Cluster scanning in body CT.

Rapid, dynamic computed tomography (CT) is essential in scanning the body in order to maintain adequate contrast enhancement during the entire examination. In the case of the liver, this is most critical in order to complete scanning prior to the equilibrium phase when lesions are less conspicuous or may be missed entirely. This technical note describes the application of "cluster scanning" to conventional scanning in order to optimize body CT by decreasing the total exam time.

Humans↗

PubMed1977

Single and multiple turnover reactions in the ubiquinone-cytochrome b-c2 oxidoreductase of Rhodopseudomonas sphaeroids: the physical chemistry of the major electron donor to cytochrome c2, and its coupled reactions.

We have examined the thermodynamic properties of the physiological electron donor to ferricytochrome c2 in chromatophores from the photosynthetic bacterium Rhodopseudomonas sphaeroides. This donor (Z), which is capable of reducing the ferricytochrome with a halftime of 1-2 ms under optimal conditions, has an oxidation-reduction midpoint potential of close to 150 mV at pH 7.0, and apparently requires two electrons and two protons for its equilibrium reduction. The state of reduction of Z, which may be a quinone.protein complex near the inner (cytochrome c2) side of the membrane, appears to govern the rate at which the cyclic photosynthetic electron transport system can operate. If Z is oxidized prior to the flash-oxidation of cytochrome c2, the re-reduction of the cytochrome takes hundreds of milliseconds and no third phase of the carotenoid bandshift occurs. In contrast if Z is reduced before flash activation, the cytochrome is rereduced within milliseconds and the third phase of the carotenoid bandshift occurs. The prior reduction of Z also has a dramatic effect on the uncoupler sensitivity of the rate of electron flow; if it is oxidized prior to activation, uncoupler can stimulate the cytochrome rereduction after several turnovers by less than tenfold, but if it is reduced prior to activation, the stimulation after several turnovers can be as dramatic as a thousandfold. The results suggest that Z plays a central role in controlling electron and proton movements in the ubiquinone cytochrome b-c2 oxido-reductase.

Bacterial Chromatophores↗

PubMed2005

Multiple charging of poly(propylene glycol) by binary mixtures of cations in electrospray.

Single, double and triple charging of poly(propylene glycol) (PPG) (Mn = 1900 g/mol) in the presence of binary mixtures of cations (Li+, Na+, K+, Cs+, and NH4+) under electrospray ionization (ESI) conditions were investigated. For these studies, sodium ion was selected as the reference cation, and the resulting ion-intensities were evaluated as a function of the [Na+]/[C+] ratio (where C+ is the other cation, i.e., Li+, K+, Cs+ and NH4+). A linear relationship was found between INa+/IC+)and [Na+]/[C+] (INa+ and IC+ stand for the intensity of the singly charged PPG molecules cationized with Na+ and C+ ions, respectively). The slope of the INa+/IC+--[Na+]/[C+] plot (alpha) indicates the binding selectivity of Na+ ions to PPG chains with respect to cation C+. In the case of the doubly charged PPG chains, the INaNa2+/INaC2+ and INaC2+/ICC2+ versus [Na+]/[C+] ratio also yield straight lines with slopes of approximately alpha/2 and 2alpha, respectively (INaNa2+, INaC2+ and ICC2+ are the intensity of the doubly charged PPG chains cationized with two Na+ ions, Na+ and C+ ions, and two C+ ions, respectively). Similarly, linear dependences with the [Na+]/[C+] ratio for the corresponding intensity ratios of the triply charged PPG were found. Based on the value of alpha, the selectivity of the cations was found to increase in the order of Li+ < Cs+ approximately Na+ < K+ approximately NH4+. The observed relative ion intensities are interpreted on the basis of the solution state equilibrium between PPG and the cations. In addition, the investigations showed that the abundances of the doubly and triply charged PPG-containing mixed cations can be optimized in a simple way using the value of alpha.

Journal Article↗

PubMed2005

Investigations of the transfructosylation reaction by fructosyltransferase from B. subtilis NCIMB 11871 for the synthesis of the sucrose analogue galactosyl-fructoside.

The exo-fructosyltransferase produced from B. subtilis NCIMB 11871 strain transfers the fructose moiety from donor alpha12 linked saccharides such as sucrose, raffinose and stachyose to the acceptor d-galactose, leading to the sucrose analogue, galactosyl-fructoside. Here, we report detailed kinetic studies. The enzyme showed a remarkably high optimal temperature at 50 degrees C and was effectively immobilised on Eupergit C 250 L and Trisopor-Amino. This is also the first report about the equilibrium of the transfructosylation reaction, its activation energy determination, the structure of the product and its preparative scale isolation.

Bacillus subtilis↗

PubMed1998

Separation of polystyrene microbeads using dielectrophoretic/gravitational field-flow-fractionation.

The characterization of a dielectrophoretic/gravitational field-flow-fractionation (DEP/G-FFF) system using model polystyrene (PS) microbeads is presented. Separations of PS beads of different surface functionalization (COOH and none) and different sizes (6, 10, and 15 microm in diameter) are demonstrated. To investigate the factors influencing separation performance, particle elution times were determined as a function of particle suspension conductivity, fluid flow rate, and applied field frequency and voltage. Experimental data were analyzed using a previously reported theoretical model and good agreement between theory and experiment was found. It was shown that separation of PS beads was based on the differences in their effective dielectric properties. Particles possessing different dielectric properties were positioned at different heights in a fluid-flow profile in a thin chamber by the balance of DEP and gravitational forces, transported at different velocities under the influence of the fluid flow, and thereby separated. To explore hydrodynamic (HD) lift effects, velocities of PS beads were determined as a function of fluid flow rate in the separation chamber when no DEP field was applied. In this case, particle equilibrium height positions were governed solely by the balance of HD lift and gravitational forces. It was concluded that under the experimental conditions reported here, the DEP force was the dominant factor in controlling particle equilibrium height and that HD lift force played little role in DEP/G-FFF operation. Finally, the influence of various experimental parameters on separation performance was discussed for the optimization of DEP/G-FFF.

Electrophoresis↗

PubMed2002

Biomechanical analysis of the canine hind limb: calculation of forces during three-legged stance.

This paper presents a three-dimensional biomechanical model of the canine hind limb, and describes the process of determining the muscle forces and joint reaction forces and moments occurring in the hind limb during three-legged stance. The model was based on anatomical and morphometric data presented in a previous paper. Equations of equilibrium were formulated for the different components of the hind limb. Since the number of unknowns exceeded the number of equations, the problem was statically indeterminate. Two optimization techniques were applied to solve this statically indeterminate problem. The resultant hip-joint reaction force (acting on the acetabulum) predicted by these optimization methods ranged between 0.73 and 1.04 times body weight, and was directed dorsally, medially and caudally. The resultant knee-joint reaction force (acting on the femur) ranged between 1.05 and 1.08 times body weight, and was directed dorsally, laterally and cranially. The largest muscle forces predicted by the minimization of maximal muscle stress (MMMS) criterion were in the biceps femoris (0.24 times body weight), rectus femoris (0.15 times body weight), medial gluteal (0.18 times body weight), semi-membranosus (0.09 times body weight), the lateral and intermediate vastus (0.18 times body weight) and the medial vastus (0.17 times body weight). The largest muscle forces predicted by the minimization of the sum of muscle forces (MSMF) criterion were in the biceps femoris (0.29 times body weight), lateral and intermediate vastus (0.45 times body weight)), and the deep gluteal (0.16 times body weight). The magnitudes and directions of the forces in the joints of the canine hind limb, as well as in the muscles that surround these joints, provide a database needed for future biomechanical analyses of the physiology and pathophysiology of the canine hind limb.

Animals↗

PubMed2001

Using of surfactant modified Fe-pillared bentonite for the removal of pentachlorophenol from aqueous stream.

The first part of this work considers the preparing of the adsorbent type Montm-FeOH-CTAC. After purification of two types Algerian bentonites (Maghnia and Mostaghanem) and preparation of cationic polyhydroxy ferric solution, we have optimized following parameters: CTAC/Montm.-FeOH = 7 mmol.g-1 and pH = 3.4, in order to obtain the adsorbent with maximum uptake of PCP. The study of the different experimental equilibrium isotherms showed clearly the high efficiency of these new adsorbents toward PCP, with significant quantities adsorbed especially onto Maghnia samples in acidic environment. Using two mathematical models Langmuir and Freundlich was found to be the Freundlich the best fitted. A comparative study of PCP adsorption onto the two modified clays and an activated carbon in the same conditions has been done.

Adsorption↗

PubMed1999

IAEA/EPA international climatic test program for integrating radon detectors. International Atomic Energy Agency/Environmental Protection Agency.

As an element of the joint IAEA-EPA International Radon Metrology Evaluation Program, a climatic test of long-term integrating radon detectors was conducted at the U.S. EPA Radiation and Indoor Environments National Laboratory. The objective of this study was to test the performance of commonly used commercially available long-term 222Rn detector systems under extreme climatological conditions using filtered polycarbonate CR-39 plastic analyzed by the manufacturer using the track-etch method, unfiltered LR-115 film analyzed by the manufacturer, and Teflon based electrets analyzed in the field by EPA using the manufacturer's equipment. The EPA environmental radon chambers were used to expose detectors to extreme cold and dry (less than 4.0 degrees C air temperature and 25% relative humidity) and hot and humid (greater than 35 degrees C air temperature and 85% relative humidity) climatic conditions. During phase I detectors were exposed to low temperatures and low humidities, and during phase II detectors were exposed to high temperatures and high humidities. Typical indoor equilibrium fractions (near 50%) and radon concentrations of about 150 Bq m(-3) were maintained for each phase, which lasted 90 d. The results indicated that the optimal detector for extreme climatic conditions is dependent on the relative importance of bias and precision. Overall, however, the filtered track-etch type detector produced the most reliable results under the extreme conditions.

Air Microbiology↗

PubMed1982

Properties of thyrotrophin receptors in human thyroid membranes.

The influence of pH, salts, temperature and time of incubation on the binding of [125I]thyrotrophin to its human thyroid receptor was studied. Optimal binding was achieved at pH 7.0--7.6. Pre-incubation of membrane receptors at pH 6.0 resulted in a 60% loss of binding. There was dynamic equilibrium, as demonstrated by kinetic experiments. Scatchard analysis yielded non-linear plots with apparent affinity constants of 1.9 x 10(9) M-1 and 3.7 x 10(7) M-1. The concentration of [125I]thyrotrophin used in the experiments (1.2--2.2 pM) approximated normal human serum thyrotrophin concentration.

Cell Membrane↗

PubMed2003

[Cu adsorption by phaeozem and burazem].

Studies on the thermodynamics and kinetics of copper (Cu2+) adsorption by phaeozem and burozem showed that that the adsorption of Cu2+ by these two soils was increased with the increasing concentration of Cu2+ within the range of Cu2+ concentrations used in the experiment, but the amount of Cu2+ adsorbed and fixed on phaeozem was much higher than that on burozem. When the test Cu2+ concentration in adsorption equilibrium was 95 mg.kg-1, its adsorption by burozem was nearly 3720 mg.kg-1, whereas by phaeozem was as high as 6076 mg.kg-1. Under the highest CuCl2 treatment of 400 mg.kg-1, Cu2+ adsorbed by phaeozem and burozem was 6159.0 mg.kg-1 and 4736.6 mg.kg-1, respectively. The adsorption of Cu2+ by the test soils could significantly conform to the Freundlich and Temkin equation, while Langmuir equation was not applicable to describe the isothermal adsorption processes of Cu2+ by the two soils. The adsorption of Cu2+ by the test soils was very rapid, which could reach its balance after 15-20 min. The adsorption within the first 2 min at its beginning stage accounted for 90% of the Cu equilibrium adsorption. The adsorptive rate of Cu2+ by phaeozem was decreased more quickly than that by burozem with the time. The two-constant equation was the optimal model to describe the adsorption of Cu2+. The other models in point were first-order dynamic equations and Elovich equations, whereas parabolic diffusion equations were not suitable ones.

Adsorption↗

PubMed2005

[SNP genotyping by multiplex amplification and microarrays assay and forensic application].

OBJECTIVE: Research on the application feasibility of SNP genotyping for forensic identification by microarrays. METHODS: Oligonucleotide microarrays which could detect 31 different SNPs were used. Population studies on 31 SNP loci was carried out in a sample of 109 unrelated Chinese Han individuals using oligonucleotide microarrays for genotype detection. The method was also applied to cases. RESULTS: No deviations from Hardy-Weinberg equilibrium could be found at the 31 SNP loci 4 loci were medium informative and 27 were high informative. The combination discrimination power (CDP) of the 31 optimal informative SNPs was 0.9999999999979. The matching probability was 2.13 x 10(-12). The average exclusion probability in duos and trios were 0.9609 and 0.9970 respectively. CONCLUSION: The data and case application demonstrated that SNP typing by oligonucleotide probe microarrays was a useful technique for paternity testing and individual identification.

Asian People↗

PubMed1982

Thermodynamics of growth. Non-equilibrium thermodynamics of bacterial growth. The phenomenological and the mosaic approach.

Microbial growth is analyzed in terms of mosaic and phenomenological non-equilibrium thermodynamics. It turns out that already existing parameters devised to measure bacterial growth, such as YATP, mu, and Q substrate, have as thermodynamic equivalents flow ratio, output flow and input flow. With this characterisation it becomes possible to apply much of the already existing knowledge of phenomenological non-equilibrium thermodynamics to bacterial growth. One of the conclusions is that the frequent observation that YATP is only 50% of its theoretical maximum does not mean that the microbe corresponds to a thermodynamic system that has been optimized for maximal output power, as has been suggested. Rather, at least in some cases, it corresponds to a system that has been optimized towards maximum growth rate. When the degree of reduction of the (single) carbon source is significantly smaller than that of the biomass produced, the efficiency of biomass synthesis has been kept as high (i.e., about 24%) as is consistent with maximization of the growth rate at optimal efficiency. Mosaic thermodynamics allows an analysis of processes which in microbial metabolism may be responsible for any particular growth behaviour. Equations are derived that predict the effect of uncoupling through leaks, futile cycling, or 'slip' on microbial growth. It turns out that uncoupling is expected to affect both the growth rate-independent and the growth rate-dependent 'maintenance coefficient'. The effect on the latter is different when catabolic substrate limits growth than when anabolic substrate limits growth. In the latter case, the growth rate-dependent maintenance coefficient is negative. It is concluded that mosaic non-equilibrium thermodynamics will be a powerful theoretical tool especially in future experimental analyses of the metabolic basis for microbial growth characteristics and growth regulation.

Adenosine Triphosphate↗

PubMed1999

o-, m-, and p-Carboranes and Their Anions: Ab Initio Calculations of Structures, Electron Affinities, and Acidities.

Ab initio geometry optimizations have been performed for o-, m-, and p-C(2)B(10)H(12) carborane cages and their mono- and dianions at the Hartree-Fock 3-21G, 6-31G, and 6-31G levels. The para-compound is the most stable with a calculated DeltaH(para-meta) value of -10 kJ/mol and a calculated DeltaG(975K)(para-meta) value of -3 kJ/mol. These small calculated energy differences disagree with the experimental heats of formation, which suggest DeltaH to be ca. -65 kJ/mol, but they agree with equilibrium gas mixture measurements at 975 K, which suggest a DeltaG value of ca. -1 kJ/mol. Electron distributions, electron affinities, and acidic properties of the carboranes are presented. The structures of the mono- and dianions were determined by optimization, starting from the three neutral carborane cages; we find three energy minima for the C(2)B(10)H(12)(2)(-) ion. The lowest-energy dianion is a nido-structure topped by a six-membered ring with the two C atoms in the meta position. The captured electrons become distributed over all the H atoms.

Journal Article↗

PubMed2006

Contact time optimization of two-stage batch adsorber design using second-order kinetic model for the adsorption of phosphate onto alunite.

The adsorption of phosphate onto alunite in a batch adsorber has been studied. Four kinetic models including pseudo first- and second-order equation, intraparticle diffusion equation and the Elovich equation were selected to follow the adsorption process. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated and discussed. It was shown that the adsorption of phosphate onto alunite could be described by the pseudo second-order equation. Adsorption of phosphate onto alunite followed the Langmuir isotherm. A model has been used for the design of a two-stage batch adsorber based on pseudo second-order adsorption kinetics. The model has been optimized with respect to operating time in order to minimize total operating time to achieve a specified amount of phosphate removal using a fixed mass of adsorbent. The results of two-stage batch adsorber design studies showed that the required times for specified amounts of phosphate removal significantly decreased. It is particularly suitable for low-cost adsorbents/adsorption systems when minimising operating time is a major operational and design criterion, such as, for highly congested industrial sites in which significant volume of effluent need to be treated in the minimum amount of time.

Adsorption↗