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At least 757 records · Page 42Linked to original sources
PubMed1987

Characterization of long-range electron transfer in mixed-metal [zinc,iron] hybrid hemoglobins.

Measurements characterizing electron transfer from a photoexcited zinc protoporphyrin triplet (3ZnP) to a ferriheme electron acceptor within the [alpha 1,beta 2] electron-transfer complex of [FeIII,Zn] hybrid hemoglobins are reported. Analytical results demonstrate that the hybrids studied are pure, homogeneous proteins with 1:1 ZnP:FeP content. Within the T quaternary structure adopted by these hybrids, the optical spectrum of a FeIIIP is perturbed by the protein environment. Room temperature kinetic studies of the rate of 3ZnP decay as a function of the heme oxidation and ligation state demonstrate that quenching of 3ZnP by FeIII(H2O)P occurs by long-range intramolecular electron transfer with rate constant kt = 100 (+/- 10) s-1 and is not complicated by spin-quenching or energy-transfer processes; results are the same for alpha(Zn) and beta(Zn) hybrids. Replacement of H2O as a ligand to the ferriheme changes the 3ZnP----FeIIIP electron-transfer rate constant, kt, which demonstrates that electron transfer, not conformational conversion, is rate limiting. However, the trend is not readily explained by simple considerations of spin-state and bonding geometry: kt decreases in the order imidazole greater than H2O greater than F- approximately CN- approximately N3-. The reverse electron-transfer process FeIIP----ZnP+ has not been observed directly but has been shown to be much more rapid, with rate constant kb greater than 10(3) s-1, consistent with the possible importance of "hole" superexchange in electron tunneling within protein complexes.

Electron Transport↗
PubMed1988

Complementary oligodeoxynucleotide probes of RNA conformation within the Escherichia coli small ribosomal subunit.

The large RNA molecule within each ribosomal subunit is folded in a specific and compact form. The availability of specific 16S RNA sequences on the surface of the small ribosomal subunit has been probed by using complementary oligodeoxynucleotides. The hybridization of 8-15-nucleotide-long oligomers to their RNA complements within the subunit was quantitated by using a nitrocellulose membrane filter binding assay. The probes have been grouped into classes on the basis of sequence-specific binding ability under different conditions of ionic environment, incubation temperature, and subunit activation state [as defined by the ability to bind phenylalanyl-tRNA in response to a poly(uridylic acid) message]. Oligodeoxynucleotides complementary to nucleotides flanking 7-methylguanosine residue 527 and to the 3'-terminal sequence bound 30S subunits regardless of the activation state. Oligodeoxynucleotides that complement 16S ribosomal RNA residues 1-16, 60-70, 685-696, and 1330-1339 and the sequence adjacent to the colicin E3 cleavage site at residue 1502 all bound efficiently only to subunits in an inactivated conformation. Probes complementary to residues 1-11 and 446-455 bound only inactivated subunits, and then with low efficiency. Sequences complementary to nucleotides 6-16, 99-109, 1273-1281, and 1373-1383 bound 30S subunits poorly regardless of the activation state. With one exception, each probe was bound by native or heat-denatured 16S ribosomal RNA (as determined by size-exclusion chromatography). We conclude that complementary oligodeoxynucleotide binding efficiency is a sensitive measure of the availability of specific RNA sequences under easily definable conditions.

Base Sequence↗
PubMed1988

Transcription of left-handed Z-DNA templates: increased rate of single-step addition reactions catalyzed by wheat germ RNA polymerase II.

Wheat germ RNA polymerase II is able to transcribe polynucleotide templates in the poly-[d(G-C)] family, adopting either the right-handed B or left-handed Z conformations depending on the ionic environment and temperature. Thus, with poly[d(G-C)] either the B state (in MgCl2) or the associated Z* state (in MnCl2) can be established. Poly[d(G-m5C)] adopts the Z form readily in MgCl2, and poly-[d(G-br5C)] can be regarded as being "constitutively" in the Z state. In transcription studies with CpG as a primer and templates in the left-handed conformation, it is found that the rate of productive elongation, i.e., the synthesis of poly[r(G-C)], is depressed, in accordance with the results of previous studies. However, with a single triphosphate substrate, CTP, the rate of formation of the first phosphodiester bond, i.e., the synthesis of CpGpC, is about 4-fold greater with both the Z and Z* templates than with B-DNA. This transcriptional activity is also catalytic in the sense that product concentrations exceed that of the enzyme. The synthesis of CpGpC is reduced in the presence of GTP. However, the apparent Km value for GTP utilization is lower for the trinucleotide synthesis (0.1 microM) than that obtained for productive elongation (0.8 microM), a result that also holds for B-DNA templates. All transcription reactions are specifically inhibited by the fungal toxin alpha-amanitin, and, in the case of the left-handed templates, by monoclonal anti-Z-DNA antibodies. The relative probabilities of single-step addition and productive elongation imply that the major distinction between transcription of templates in the B and Z conformations involves a step following the synthesis of the first phosphodiester bond. As a result, fully competent elongation complexes do not form on the left-handed DNA.

Chlorides↗
PubMed2005

Arsenate adsorption mechanisms at the allophane-water interface.

We investigated arsenate (As(V)) reactivity and surface speciation on amorphous aluminosilicate mineral (synthetic allophane) surfaces using batch adsorption experiments, powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The adsorption isotherm experiments indicated that As(V) uptake increased with increasing [As-(V)]0 from 50 to 1000 microM (i.e., Langmuir type adsorption isotherm) and that the total As adsorption slightly decreased with increasing NaCl concentrations from 0.01 to 0.1 M. Arsenate adsorption was initially (0-10 h) rapid followed by a slow continuum uptake, and the adsorption processes reached the steady state after 720 h. X-ray absorption spectroscopic analyses suggest that As(V) predominantly forms bidentate binuclear surface species on aluminum octahedral structures, and these species are stable up to 11 months. Solubility calculations and powder XRD analyses indicate no evidence of crystalline Al-As(V) precipitates in the experimental systems. Overall, macroscopic and spectroscopic evidence suggest that the As(V) adsorption mechanisms at the allophane-water interface are attributable to ligand exchange reactions between As-(V) and surface-coordinated water molecules and hydroxyl and silicate ions. The research findings imply that dissolved tetrahedral oxyanions (e.g., H2PO42- and H2AsO4(2-)) are readily retained on amorphous aluminosilicate minerals in aquifer and soils at near neutral pH. The inner-sphere adsorption mechanisms might be important in controlling dissolved arsenate and phosphate in amorphous aluminosilicate-rich low-temperature geochemical environments.

Adsorption↗
PubMed2006

Molecular motion of tethered molecules in bulk and surface-functionalized materials: a comparative study of confinement.

Achieving high degrees of molecular confinement in materials is a difficult synthetic challenge that is critical for understanding supramolecular chemistry on solid surfaces and control of host-guest complexation for selective adsorption and heterogeneous catalysis. In this Article, using 2H MAS NMR spectroscopy of tethered carbamates as a molecular probe, we systematically investigate the degree of steric confinement within three types of materials: two-dimensional silica surface, bulk amorphous microporous silica, and bulk amorphous mesoporous silica. The resulting NMR spectra are described with a simple two-site hopping model for motion and prove that the bulk silica network severely limits the molecular mobility of the immobilized carbamate at room temperature to the same degree as surface-functionalized materials at low-temperatures (approximately 210 K). Raising the temperature of the bulk materials to 413 K still demonstrates the effect of confinement, as manifested in significantly longer characteristic times for the immobilized carbamate relative to surface-functionalized materials at room temperature. The environment surrounding the carbonyl functionality of the immobilized carbamate is investigated using FT-IR spectroscopy, which shows the carbonyl stretching band to be equally shifted for all materials to lower wavenumbers relative to its noninteracting value in carbon tetrachloride solvent. These results suggest that electrostatic interactions between the carbonyl of the immobilized carbamate and silica surface may play an important role in confining the immobilized carbamate and nucleating the formation of a pore wall close to the immobilized carbamate during bulk materials synthesis.

Journal Article↗
PubMed2006

Resolving radial composition gradients in polarized confocal raman spectra of individual 3C-SiC nanowires.

Silicon carbide nanowires are being actively pursued as components for nanoelectromechanical sensors, nanocatalytic elements, and nano-optical circuits able to operate in harsh environment, high temperature, and high power applications. The effect of geometric confinement and polarization anisotropy in confocal Raman spectroscopy has been employed to detect axial and radial composition information in individual nanowires. Polarization anisotropy causes a significant increase in signal from the surface layer (relative to bulk), and combined with the increased surface-to-volume ratio at the nanoscale, it allows for the direct characterization of bulk and surface defects.

Journal Article↗
PubMed2005

The peculiar kinetics of the reaction between acetylene and the cyclopentadienyl radical.

The cyclopentadienyl radical (cC(5)H(5)) is a fascinating molecule characterized by several peculiar properties, such as its high internal symmetry and resonance enhanced stability. This makes cC(5)H(5) one of the most abundant radicals present in high temperature gaseous environments, such as flames. Therefore it is generally considered an interesting candidate as the starting point of reaction pathways leading to the formation of polycyclic aromatic hydrocarbons (PAH) and soot in combustion processes. However, known reaction pathways are not able to explain some recent experimental findings concerning the rapid conversion of cC(5)H(5) into C(7)H(7) and C(9)H(8) in the presence of acetylene. In this work, we used ab initio calculations and quantum Rice-Ramsperger-Kassel (QRRK) theory to investigate the cC(5)H(5) + C(2)H(2) reaction kinetics. We found that cC(5)H(5) can add acetylene to form, through a fast and not previously known reaction, the heptatrienyl radical (cC(7)H(7)), which, in many ways, can be considered the superior homologue of cC(5)H(5). The calculated reaction kinetic constant is (2.2 x 10(11))exp(-6440/T(K)) cm(3) mol(-1) s(-1) and is in good agreement with experimental data, while that of the inverse process is (4.2 x 10(16))T(-1) exp(-30 850/T(K)) s(-1). In a successive reaction, cC(7)H(7) can add a second acetylene molecule to form indene, cC(9)H(8), and H. The forward and backward kinetic constants are (6.6 x 10(11))exp(-10 080/T(K)) and (4.2 x 10(14))exp(-27 300/T(K)) cm(3) mol(-1) s(-1), respectively. These two successive reactions, leading from a single C5 cycle to a bicyclic C5-C6 species, represent a new PAH growth mechanism, characterized by a C5-C7 ring enlargement reaction.

Journal Article↗
PubMed1999

Recording the photopic electroretinogram from conscious adult Yucatan micropigs.

The micropig is viewed by many as one of the best animal models of human system physiology. The purpose of this study was to develop a simple, rapid and reliable method to record clinical electroretinograms from conscious adult Yucatan micropigs. Photopic ERGs were recorded from 18 conscious animals following a 3-h period of preadaptation to a moderate photopic environment. Rectal temperature and blood pressure were monitored throughout the experiment. In order to test the reproducibility of our procedure, the same protocol was repeated (n=6 micropigs) on three different recording sessions each separated by a 48-h period. Our results indicate that the recording of reproducible ERGs, in the conscious Yucatan micropig, is feasible provided that an adequate experimental approach is used. We believe that our method will enable investigators to perform retinal physiology experiments using an approach which is compatible with that used in a human clinical setup thus facilitating the transposition of experimental data from animal to human.

Adaptation, Ocular↗
PubMed1978

Huddling by rat pups: multisensory control of contact behavior.

Huddling, or clumping behavior, begins in the litter situation and persists throughout the adult life of the rat (Rattus norvegicus). In pups, as in adults, the behavior provides a metabolically important means of reducing heat loss. The sensory stimuli that elicit, direct, and maintain huddling in developing rat pups (5-20 days of age) were studied in a standardized testing situation by using long-term time-lapse video observations. All pups huddled with a single, immobile sibling. A loop of warm tubing also elicited huddline. However, it appears that other, nonthermal cues can elicit huddling, since a dead, ambient-temperature pup was a sufficient stimulus for the behavior. Disruption of normal olfactory input by intranasal infusion of zinc sulfate interfered with the maintenance of contact. In addition, two kinds of tactile stimulus, vertical contours and furry "comfort" cues, as well as photic responses appeared to participate in the mediation of huddling. Huddling in the altricial rat is under multisensory control, although the number of cues used by pups for huddling appears to increase with age.

Age Factors↗
PubMed1981

The ontogeny of feeding in rats: V. Influence of texture, home odor, and sibling presence on ingestive behavior.

Terry-cloth texture, home odor, and the presence of siblings modulate the ingestive behavior of infant rats. Unlike warmth, which affects ingestion in pups until at least 15 days of age, the relative importance of these other cues varies with the age of the pup. At 3 days, ingestion is dependent on warmth but is not influenced by the other cues. At 6 days, texture and home odor enhance ingestive behavior (intake, activity, mouthing, and probing), but the presence of siblings has no effect. Home odor or terry-cloth texture did not alter the ingestive behavior of 12-day-olds, but the presence of siblings enhanced milk intake. Thus, during development, the external sensory controls for ingestion become progressively more complex. Warmth serves as a primary permissive cue for ingestion in developing pups, but as pups grow older, other types of cues (such as odor, texture, or social stimuli) also gain significance.

Aging↗
PubMed1981

Persistent parainfluenza virus shedding during isolation at the South Pole.

Persistent parainfluenza virus shedding in healthy young adults occurred throughout the 8 1/2-month winter isolation period at Amundsen-Scott South Pole Station during 1978. Two episodes of respiratory illness were observed after 10 and 29 weeks of complete social isolation. Throat swabs collected both routinely, and during each outbreak of respiratory illness, were directly inoculated into cell cultures. Parainfluenza virus types 1 and 3 were recovered from both symptomatic and asymptomatic subjects throughout the winter. No other viruses were obtained by these efforts. The presence of parainfluenza virus in these subjects long after the accepted incubation period for viral upper respiratory illness, and when the introduction of new virus to this community was impossible, suggests its persistence in man.

Animals↗
PubMedDate not supplied

Thermal stability and transition studies with a hybrid warming device for neonates.

OBJECTIVE: The use of both warmer beds and incubators is common in neonatal intensive care units (NICU), and transferring between these two warming devices is a routine and necessary event. This study was designed to evaluate the efficacy of a new hybrid-warming device, the Versalet, in transitioning a preterm animal from a warmer bed to an incubator mode and back. STUDY DESIGN: Nine premature lambs were randomized, following delivery, to receive thermal support from a conventional warming bed and an incubator (control group), or from the Versalet (study group) in the warmer bed and incubator modes. Core and various surface temperatures, as well as physiological parameters were measured first during warming in the radiant warmer bed mode, Versalet or Resuscitaire and then during transition to the incubator mode, Versalet or Isolette, and then back to the warmer bed mode. RESULTS: The animals remained stable during all the transitions. Despite careful planning, adverse events occurred in the control group during transfers. There were no significant differences in the temperature or physiologic profiles during any of the transitions in either group. CONCLUSION: Compared with the standard warming technique used in NICUs (separate warmer bed and incubator), the Versalet provides similar thermal and cardiovascular stability without adverse events during transition to different modes of warming. The degree to which this device would contribute to ease of management and improved outcomes in humans needs to be evaluated in a clinical trial.

Animals↗
PubMed2006

Chronic fluoxetine treatment attenuates stressor-induced changes in temperature, heart rate, and neuronal activation in the olfactory bulbectomized rat.

The olfactory bulbectomized (OB) rat is a well-characterized animal model that exhibits a number of behavioral and neurochemical changes that have relevance to clinical depression. Hyperactivity in the open field is the most widely used parameter assessed in this model and is reversed following chronic, but not acute, antidepressant treatment. This study investigated OB-induced alterations in heart rate, body temperature, and neuronal activation following open-field exposure and the impact of chronic treatment with fluoxetine on these parameters. Upon placement in the open field, OB rats exhibited a characteristic hyperactivity response. Heart rate and body temperature were increased in sham-operated rats following open-field exposure, a predictable response to stress, which was significantly reduced in OB rats. Moreover bulbectomy reduced open field-induced cFOS expression in the basal nucleus of the stria terminalis while concurrently increasing expression in the hippocampus, amygdala, paraventricular nucleus of the thalamus, and dorsal raphe nucleus. Chronic fluoxetine treatment (10 mg/kg subcutaneous once daily for 5 weeks) attenuated all of these OB-associated changes. In conclusion, OB rats exhibit alterations in behavior, body temperature, heart rate, and neuronal activation in response to open-field exposure, which are reversed following chronic fluoxetine administration. These results identify stress-sensitive regions within the brain which are altered following bulbectomy and which may underlie the abnormal behavioral and physiological changes observed in this rodent model of depression.

Animals↗
PubMed2006

VUV spectroscopy and photo-processing of astrochemical ices: an experimental study.

In order to understand much of the chemistry that underpins astronomical phenomena (e.g. star and planet formation) it is essential to probe the physico-chemistry of ice surfaces under astronomical conditions. The physical properties and chemical reactivity of such icy surfaces depends upon its morphology. Thus it is necessary to explore how the morphology of astrochemical ices is influenced by their local environment (e.g. temperature and pressure) and the mechanisms by which they are processed. In this paper we report the results of a series of experiments to explore the morphology of a variety of molecular ices using VUV spectroscopy. Spectral signatures are found that may allow the morphology of such ices to be identified.

Journal Article↗
PubMed2004

Exceptionally diverse morphotypes and genomes of crenarchaeal hyperthermophilic viruses.

The remarkable diversity of the morphologies of viruses found in terrestrial hydrothermal environments with temperatures >80 degrees C is unprecedented for aquatic ecosystems. The best-studied viruses from these habitats have been assigned to novel viral families: Fuselloviridae, Lipothrixviridae and Rudiviridae. They all have double-stranded DNA genomes and infect hyperthermophilic crenarchaea of the orders Sulfolobales and Thermoproteales. Representatives of the different viral families share a few homologous ORFs (open reading frames). However, about 90% of all ORFs in the seven sequenced genomes show no significant matches to sequences in public databases. This suggests that these hyperthermophilic viruses have exceptional biochemical solutions for biological functions. Specific features of genome organization, as well as strategies for DNA replication, suggest that phylogenetic relationships exist between crenarchaeal rudiviruses and the large eukaryal DNA viruses: poxviruses, the African swine fever virus and Chlorella viruses. Sequence patterns at the ends of the linear genome of the lipothrixvirus AFV1 are reminiscent of the telomeric ends of linear eukaryal chromosomes and suggest that a primitive telomeric mechanism operates in this virus.

African Swine Fever Virus↗