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At least 109 records · Page 6Linked to original sources
PubMed1999

Upper gut dysmotility in slow-transit constipation: is it evidence for a pan-enteric neurological deficit in severe slow transit constipation?

Although constipation is common only a small fraction meet the criteria of slow transit constipation. Those that do are resistant to treatment and present a significant clinical problem to the physician and surgeon. Evidence has been accumulating over many years that the impaired colonic motility is part of a generalized motility defect. There are several reports of oesophageal dysmotility, delayed gastric emptying and slow small bowel transit. These abnormalities are not secondary to a distended colon since they are still seen after colonic cleansing and even after colectomy. The manometric abnormalities of small bowel motility are hard to assess unless done over a prolonged period (24 h) because of the great variability observed. The clinical picture of slow transit constipation is quite different from chronic intestinal pseudo-obstruction and the manometric abnormalities are much less obvious. The possibility of an underlying autonomic disturbance warrants further study.

Colon↗
PubMed1989

The variability in oro-cecal transit time assessed using a bean-based test meal and its use in the study of the effect of metoclopramide and BRL 24924 on transit time.

The inter and intra subject variation in the oro-cecal transit time assessed using the bean/breath hydrogen method was studied and analyzed to allow estimation of the number of patients/subjects required to show a drug-induced difference for given levels of statistical significance and power. Thus at the conventional 5% level of significance and for a test with 90% power, a dozen subjects should be sufficient to show a drug-induced change which is 25% or greater. Two crossover studies are described using 20 mg metoclopramide and 2 mg BRL 24924, orally, against placebo to investigate their action on oro-cecal transit time. Metoclopramide, 20 mg, produced a 45% reduction in the transit time compared with placebo. BRL 24924, 2 mg, in a similar study showed a 71% reduction.

Adult↗
PubMed1989

Theory of cooperative transitions in protein molecules. I. Why denaturation of globular protein is a first-order phase transition.

A theory of equilibrium denaturation of proteins is suggested. According to this theory, a cornerstone of protein denaturation is disruption of tight packing of side chains in protein core. Investigation of this disruption is the object of this paper. It is shown that this disruption is an "all-or-none" transition (independent of how compact is the denatured state of a protein and independent of the protein-solvent interactions) because expansion of a globule must exceed some threshold to release rotational isomerization of side chains. Smaller expansion cannot produce entropy compensation of nonbonded energy loss; this is the origin of a free-energy barrier (transition state) between the native and denatured states. The density of the transition state is so high that the solvent cannot penetrate into protein in this state. The results obtained in this paper make it possible to present in the following paper a general phase diagram of protein molecule in solution.

Kinetics↗
PubMed1990

Superoxide anion radical induces lipid phase transitions that mimic temperature-induced phase-transition phenomenon of membrane lipids.

A biological membrane is shown to undergo lipid-phase transition leading to increased membrane fluidity when exposed to extraneously generated superoxide anion radical. This phase-transition is several folds higher in magnitude when compared to the temperature-induced fluidity change at the transition temperatures. This finding could have significant importance since an altered membrane configuration may involve aspects of biochemistry, biophysics or physiology.

Animals↗
PubMedDate not supplied

The transition to a nursing home: meeting the family's needs. Family members face their own transition when a loved one enters a nursing home.

The lack of preparation for the experience of admission to a nursing home, as represented by these family members, indicates there is a need for nursing interventions targeted to the family before the admission of a loved one to the nursing home. The program could address information and problem solving, as well as provide emotional support. The day of admission is too late to prepare for this experience. Access to families occurs before any admission to LTCFs. Nurses in acute care and home care are in a position to inform, assist, and advocate for families in this decision-making and admission process. The family members we questioned have provided some of the content for an educational preparation program that may be useful to all families. The responses also indicate that each family will have its own concerns and functional relationships that would alter specific content. Maslow's framework could aid the identification of needs and direct the specific interventions to empower the family to cope with this transition. A few guidelines have been suggested in this article to stimulate discussion about the family's transition to the nursing home. Appraisal of a family's perceptions about the use of nursing homes may alert the nurse to potential conflicts and areas of uncertainty. These assessments provide direction for family interventions that may alleviate the extent of uncertainty and conflict before the admission and serve as ongoing family-centered activity in the nursing home. The view of this experience as a family transition also supports the concept of continuity of care through nursing interventions.

Family↗
PubMed1988

Reconstruction by site-directed mutagenesis of the transition state for the activation of tyrosine by the tyrosyl-tRNA synthetase: a mobile loop envelopes the transition state in an induced-fit mechanism.

Site-directed mutagenesis of the tyrosyl-tRNA synthetase followed by kinetic studies has shown that residues which are distant from the active site of the free enzyme are brought into play as the structure of the enzyme changes during catalysis. Positively charged side chains which are in mobile loops of the enzyme envelope the negatively charged pyrophosphate moiety during the transition state for the formation of tyrosyl adenylate in an induced-fit mechanism. Residues Lys-82 and Arg-86, which are on one side of the rim of the binding site pocket, and Lys-230 and Lys-233, which are on the other side, have been mutated to alanine residues and also to asparagine or glutamine. The resultant mutants still form 1 mol of tyrosyl adenylate/mol of dimer but with rate constants up to 8000 times lower. Construction of difference energy diagrams reveals that all the residues specifically interact with the transition state for the reaction and with pyrophosphate in the E.Tyr-AMP.PPi complex. Yet, the epsilon-NH3+ groups of Lys-230 and Lys-233 in the crystalline enzyme are at least 8 A too far away to interact with the pyrophosphate moiety in the transition state at the same time as do Lys-82 and Arg-86. Binding of substrates must, therefore, induce a conformational change in the enzyme that brings these residues into range. Consistent with this proposal is the observation that all four residues are in flexible regions of the protein.(ABSTRACT TRUNCATED AT 250 WORDS)

Amino Acyl-tRNA Synthetases↗
PubMed2003

Do enzymes change the nature of transition states? Mapping the transition state for general acid-base catalysis of a serine protease.

The properties of the transition state for serine protease-catalyzed hydrolysis of an amide bond were determined for a series of subtilisin variants from Bacillus lentus. There is no significant change in the structure of the enzyme upon introduction of charged mutations S156E/S166D, suggesting that changes in catalytic activity reflect global properties of the enzyme. The effect of charged mutations on the pK(a) of the active site histidine-64 N(epsilon)(2)-H was correlated with changes in the second-order rate constant k(cat)/K(m) for hydrolysis of tetrapeptide anilides at low ionic strength with a Brønsted slope alpha = 1.1. The solvent isotope effect (D)2(O)(k(cat)/K(m))(1) = 1.4 +/- 0.2. These results are consistent with a rate-limiting breakdown of the tetrahedral intermediate in the acylation step with hydrogen bond stabilization of the departing amine leaving group. There is an increase in the ratio of hydrolysis of succinyl-Ala-Ala-Pro-Phe-anilides for p-nitroaniline versus aniline leaving groups with variants with more basic active site histidines that can be described by the interaction coefficient p(xy) = delta beta(lg)/delta pK(a) (H64) = 0.15. This is attributed to increased hydrogen bonding of the active site imidazolium N-H to the more basic amine leaving group as well as electrostatic destabilization of the transition state. A qualitative characterization of the transition state is presented in terms of a reaction coordinate diagram that is defined by the structure-reactivity parameters.

Amino Acid Sequence↗
PubMed2002

Reactivity of 3d transition metal cations in diethylene glycol solutions. Synthesis of transition metal ferrites with the structure of discrete nanoparticles complexed with long-chain carboxylate anions.

Study of the reactivity of 3d transition metal cations in diethylene glycol solutions revealed several key features that made it possible to develop a new method for synthesis of the nanocrystalline transition metal ferrites. The 3-7 nm particles of [MFe2O4]n[O2CR]m, where M = Mn, Fe, Co, Ni, and Zn, ligated on their surface with long-chain carboxylate anions, have been obtained in an isolated yield of 75-90%. The key features are the following. Complexation of the first-row transition metal cations with diethylene glycol at a presence of alkaline hydroxide is sufficient to enable control over the rate of their hydrolysis. The reaction of hydrolysis leads to the formation of metal oxide nanocrystals in colloidal solution. The nanoparticles growth is terminated by an added long-chain carboxylic acid, which binds to their surface and acts as a capping ligand. The isolated nanocrystalline powders are stable against agglomeration and highly soluble in nonpolar organic solvents.

Journal Article↗
PubMed2002

Physical organic chemistry of transition metal carbene complexes. 25. Kinetic and thermodynamic acidities of substituted (methylthiophenylcarbene)pentacarbonyl tungsten(0) and (Benzoxymethylcarbene)pentacarbonyl tungsten(0) in aqueous acetonitrile. Evidence for transition state imbalances.

A kinetic study of the reversible deprotonation of substituted (methylthiophenylcarbene)pentacarbonyltungsten(0) ((CO)(5)W=C(SC(6)H(4)Z)CH(3)) and of substituted (benzoxymethylcarbene)pentacarbonyltungsten(0) ((CO)(5)W=C(OCH(2)C(6)H(4)Z)CH(3)) by primary aliphatic and secondary alicyclic amines in 50% MeCN-50% water (v/v) at 25 degrees C is reported. From the dependence of the deprotonation rate constants on amine basicity and on carbene complex acidity (variation of Z), Brønsted beta(B) and alpha(CH) values, respectively, were obtained. The alpha(CH) values were found to be smaller than the beta(B) values. These results indicate a transition state imbalance in which the loss of the carbene complex stabilizing pi-donor effect of the OCH(2)Ar and SAr groups lags behind the proton transfer. These findings confirm a previously formulated hypothesis as to how pi-donor groups attached to the carbene carbon of carbene complexes can affect transition state imbalances and mask the experimental manifestation of such imbalances. It is also shown that the transition state structure of the reactions examined in this work is subject to changes with changing amine basicity and carbene complex acidity; these changes can be expressed by p(xy)() cross correlation coefficients, which are positive.

Journal Article↗
PubMedDate not supplied

Nursing home transition: providing assistance to caregivers in transition program.

Transition from a skilled nursing facility or rehabilitation center to the community can be fragmented and insufficiently case managed, resulting in inadequate care recommendations, patient-caregiver distress, a delay in discharge, and a higher risk of nursing home readmission. The Providing Assistance to Caregivers in Transition (PACT) program is an interdisciplinary case management program designed to enhance nursing home discharge planning and case management support for the transitional period following a return to the community. During the PACT program's initial 24 months of operation, 38 of 42 opened cases were assisted in a discharge to the community. Of these, 30 remained at home for at least 6 months, 5 were readmitted within 6 months, and 3 others died. Caregivers reported satisfaction with instrumental (e.g., information about care options, facilitation of referrals to services) and emotional support. Nursing home cooperation was mixed. More work is needed to develop a broader referral base for the program.

Activities of Daily Living↗
PubMed1999

Experimental observation of a torus-doubling transition to chaos near the ferroelectric phase transition of a KH2PO4 crystal.

A ferroelectric KH2PO4 crystal is implemented in a simple series connection of an RLC circuit and the transition to chaos near the phase-transition temperature is investigated. The torus-doubling scenario to chaos, the theory of which was expounded by Kaneko for high-dimensional dynamical systems, has been found in the crystal. These experimental results suggest that observation of the nonlinear dynamical behavior in condensed matter can give much information about the correlation between the generation of nonlinearity and the order-parameter dynamics of the crystal near the phase-transition temperature.

Journal Article↗
PubMed1999

Coupling between a first-order gas-liquid phase transition and a second-order orientational transition in Langmuir monolayers.

The Ginzburg-Landau theory is developed to investigate coupling between a gas-liquid first-order phase transition (FOPT) and an orientational second-order phase transition (SOPT) in Langmuir monolayers. It is found that the coupled SOPT and FOPT takes place simultaneously if the uncoupled FOPT occurs prior to the SOPT with compression, and that in the opposite case, the coupling makes the FOPT take place at a lower pressure, but still behind the SOPT. Gas-liquid phase separation always leads to a decrease in the averaged order parameter of the orientational phase transition, which is qualitatively consistent with experimental data.

Journal Article↗
PubMed2003

Effect of a quenched random field on a continuous symmetry breaking transition: nematic to smectic-A transition in octyloxycyanobiphenyl-aerosil dispersions.

High-resolution x-ray diffraction and ac-calorimetric experiments have been carried out on the liquid-crystal octyloxycyanobiphenyl in which aerosil particles are dispersed. The measurements were made over a temperature range around the bulk nematic to smectic-A transition temperature. At this transition the liquid crystal breaks translational symmetry in a single direction. The silica particles, which hydrogen bond together to form a very low density gel, provide the quenched disorder. The random gel leads to observable broadening of the x-ray reflection from the smectic layers. The structure factor is well described by modeling the effect of the aerosils as a quenched random field. Dispersed aerosils are thought to pin both the direction of the translational ordering and the position of the layers. The latter appears to have the greatest effect on the x-ray line shape. We show that the aerosil surface area, as verified by small-angle scattering, equates to the variance of the random field. Calorimetric results reveal substantial change in the specific heat peak associated with the nematic to smectic-A transition. As the concentration of aerosil increases, the specific heat peak remains sharp yet decreases in magnitude and shifts in temperature in a nonmonotonic fashion. In this regime, the critical exponent alpha becomes progressively smaller. For the samples with the largest concentrations of aerosil particles the C(p)(N-A) peak becomes highly smeared and shifts smoothly to lower temperatures.

Journal Article↗
PubMed1990

Structural transition of bovine plasma albumin in the alkaline region--the N-B transition.

Bovine plasma albumin (BPA) has approximately one SH group (Cys-34) which catalyzes the intramolecular SH, S-S exchange reaction in the alkaline region at low ionic strength, resulting in the formation of the aged form. So, the N-B transition at ionic strength above 0.20 and below 0.10 was studied using BPA and iodoacetamide-blocked BPA (IA-BPA), respectively. (1) pH profiles of [theta]262 and [theta]268 of BPA in 0.20 M KCl showed the characteristic changes in the pH region 7.0-9.0, corresponding to the N-B transition. On going from pH 7.0 to 9.0 in 0.10 M KCl or NaCl, IA-BPA did not show significant changes in rotational relaxation times of tryptophyl fluorophors, CD-resolved secondary structures, spin-echo 1H-n.m.r. spectra and cross-relaxation times (TIS) between irradiated and observed protein protons, which might reflect the rigidity of the domains and/or subdomains. On the other hand, rotational relaxation times of 1-anilino-8-naphthalenesulfonate-IA-BPA complex (IA-BPA-ANS0.9, molar ratio of ANS to IA-BPA = 0.9/1) showed significant decreases from 131 to 114 ns on going from the N- to the B-forms in 0.10 M KCl. The above results and reported experimental evidence might indicate that on going from the N- to the B-forms in 0.10 M KCl or NaCl, the mutual movement of subdomains, connected with a flexible hinge region (Brown & Shockley (1982)) might increase without loss in the helicity and the rigidity of subdomains. (2) The N-B transition of IA-BPA in the absence of salt was quite different from those in 0.10 M KCl or NaCl. Decreases in the helicity and the intramolecular rigidity, as monitored by TIS-measurements, were observed on going from the N- to the B-forms.

Animals↗
PubMed1998

H-NMR and CD studies on the structural transition of serum albumin in the acidic region--the N-->F transition.

Helical content (f(alpha)) of bovine mercaptalbumin (BMA) showed the characteristic two-step decrease in the acidic region, one corresponding to the N-->F transition (pH 4.40-->3.75; f(alpha), 0.68-->0.58) and the other to the F-->E transition (the acid-expansion) (pH 3.60-->2.90; falpha, 0.58-->0.48). However, falpha of human serum albumin (HSA) mainly decreased in the N-->F transition (N-->F, pH 4.6-->3.4; falpha, 0.70-->-0.55 and F-->E, below pH 3.0; falpha, 0.55-->0.52). The difference in pH-profile of f(alpha) between BMA and HSA might be due to the microheterogeneity. The 1H-NMR spectra and cross-relaxation times (T(IS)) from irradiated to observed protein protons, which reflect the structural fluctuation and/or mobilability in proteins, were measured on the N-, F-, E-forms of HSA and BMA, and the N*-form (8.23 M urea, neutral pD) of iodoacetamide-blocked HSA (IA-HSA) and bovine serum albumin (IA-BSA). The 1H-NMR spectra and elongations of T(IS) values for the F- and E-forms of HSA and the E-form of BMA were quite similar to those for the N*-form of IA-HSA and IA-BSA, indicating the liberation of the intramolecular motion in the F- and E-forms. Those for the F-form of BMA were intermediate between the N- and E-form. The present results together with the reported data on hydrodynamic radii and D-H exchange reaction, indicate that the F-form of HSA and presumably BMA has a native-like globule form with a highly helical state and fluctuating tertiary structure. Thus, all of the present findings on the F-form of serum albumin seem to be in accord with the structural features for the F-form suggested by Foster's group (1-3, 19, 20, 22, 23) and the molten globule state demonstrated by Dolgikh et al. (40), and Ohgushi and Wada (36, 37).

Animals↗
PubMed1978

Transitional steady-state investigations during aerobic-anaerobic transition of glucose utilization by Escherichia coli K-12.

Transitional steady-state investigations during changes in oxygen tension under aerobic and during aerobic-anaerobic transition conditions were carried out with the aim of finding an indicator system which separates the equilibrium from the non-equilibrium state. Of the parameters used i.e. biomass formation, CO2 production, Q02, NADH oxidase, succinate dehydrogenase, phosphofructokinase, glyceraldehyde-3 phosphate dehydrogenase, 6-phosphogluconate dehydrogenase and 2-oxoglutarate dehydrogenase, only the three enzymes requiring NADH or NADP for their function fulfilled the requirements. Biomass production and CO2 formation were useful only during the aerobic-anaerobic transition period. In each case the response was immediate and the indicator systems demonstrated that a new steady state of oxygen was always obtained after 11 h which, at the specific growth rate used, was equivalent to at least two volume replacements of the growth vessel.

Aerobiosis↗
PubMed1993

pH-induced structural transitions of bovine serum albumin. Histidine pKa values and unfolding of the N-terminus during the N to F transition.

1. Titration curves have been constructed for all the resolvable resonances of defatted bovine serum albumin [pH meter readings in 2H2O solution (pH*) 2-10], including complete curves for six His residues and partial curves for a further four. Three His residues have unusually low pKa values (less than 5.5). 2. Abrupt discontinuities in the titration curves of nearly all resonances were observed near pH 4.3 (N to F transition), together with a marked loss of chemical shift dispersion at low pH*. No such loss of dispersion occurs in the high pH region previously associated with the N to B transition (approximately pH 8). The NMR data provide strong evidence that the N to F transition is not localised in domain III as had been previously suggested. 3. A localised unfolding of the N-terminal region occurs below pH* 4.5.

Histidine↗