Increase in the reduction potential of uranyl upon interaction with graphene oxide surfaces.

Coordination of uranyl (U(vi)) with carboxylate groups on functionalized graphene oxide (GO) surfaces has been shown to alter the reduction potential of the sorbed uranium ion. A quantitative measure of the reduction potential and qualitative estimation of sorption/desorption processes were conducted using cyclic voltammetry, and the proposed coordination environment was determined using the surface sensitive attenuated total reflection mode of infrared spectroscopy (ATR-FTIR). GO is a nanostructured material possessing a large amount of oxygen-containing functional groups both on basal planes and at the edges, which can form strong surface complexes with radionuclides. The presence of these functional groups on the surface of GO allows efficient immobilization of uranium due to sorption of uranyl (UO22+) to carboxylate, hydroxide, or sulfonate functional groups and the potential for enhanced reduction of U(vi) to more strongly sorbing and insoluble U(iv). Herein, binding of U(vi) to carboxylate groups on the GO surface is proposed as the primary sorption mechanism based on the FTIR study. Furthermore, the coordination of uranium with the surface increases the reduction potential of the U(vi)/U(iv) redox couple as compared to the case of the aqueous U(vi)/U(iv) species. This is consistent with the alteration of the electronic structure of the sorbed ion, which can be determined in our case due to the use of a GO-coated working electrode. Thus, GO-coated glassy carbon electrodes and other semi-conducting electrodes with high ion sorption capacities may provide a means of examining the oxidation/reduction potentials of sorbed ions.

Modulation of the Electrostatic and Quantum Capacitances of Few Layered Graphenes through Plasma Processing.

It is shown that charged defect generation, through argon ion-based plasma processing, in few layer graphene, could substantially enhance the electrical capacitance for electrochemical energy storage. Detailed consideration of the constituent space charge and quantum capacitances were used to delineate a new length scale, correlated to electrically active defects contributing to the capacitance, and was found to be smaller than a structural correlation length determined through Raman spectroscopy. The study offers insights into an industrially viable method (i.e., plasma processing) for modifying and enhancing the energy density of graphene-based electrochemical capacitors.

Phonon anharmonicity in binary chalcogenides for efficient energy harvesting.

Thermoelectric (TE) materials have received much attention due to their ability to harvest waste heat energy. TE materials must exhibit a low thermal conductivity (κ) and a high power factor (PF) for efficient conversion. Both factors define the figure of merit (ZT) of the TE material, which can be increased by suppressing κ without degrading the PF. Recently, binary chalcogenides such as SnSe, GeTe, and PbTe have emerged as attractive candidates for thermoelectric energy generation at moderately high temperatures. These materials possess simple crystal structures with low κ in their pristine forms, which can be further lowered through doping and other approaches. Here, we review the recent advances in the temperature-dependent behavior of phonons and their influence on the thermal transport properties of chalcogenide-based TE materials. Because phonon anharmonicity is one of the fundamental contributing factors for low thermal conductivity in SnSe, Sb-doped GeTe, and related chalcogenides, we discuss complementary experimental approaches such as temperature-dependent Raman spectroscopy, inelastic neutron scattering, and calorimetry to measure anharmonicity. We further show how data gathered using multiple techniques helps us understand and engineer better TE materials. Finally, we discuss the rise of machine learning-aided efforts to discover, design, and synthesize TE materials of the future.

Binary III-V semiconductor core optical fiber.

For the first time to the best of our knowledge a glass-clad optical fiber comprising a crystalline binary III-V semiconductor core has been fabricated. More specifically, a phosphate glass-clad fiber containing an indium antimonide (InSb) core was drawn using a molten core approach. The core was found to be highly crystalline with some oxygen and phosphorus diffusing in from the cladding glass. While optical transmission measurements were unable to be made, most likely due to free carrier absorption associated with the conductivity of the core, this work constitutes a proof-of-concept that optical fibers comprising semiconductor cores of higher crystallographic complexity than previously realized can be drawn using conventional fiber fabrication techniques. Such binary semiconductors may open the door to future fiber-based nonlinear devices.

Silicon optical fiber.

Described herein are initial experimental details and properties of a silicon core, silica glass-clad optical fiber fabricated using conventional optical fiber draw methods. Such semiconductor core fibers have potential to greatly influence the fields of nonlinear fiber optics, infrared and THz power delivery. More specifically, x-ray diffraction and Raman spectroscopy showed the core to be highly crystalline silicon. The measured propagation losses were 4.3 dB/m at 2.936 microm, which likely are caused by either microcracks in the core arising from the large thermal expansion mismatch with the cladding or to SiO(2) precipitates formed from oxygen dissolved in the silicon melt. Suggestions for enhancing the performance of these semiconductor core fibers are provided. Here we show that lengths of an optical fiber containing a highly crystalline semiconducting core can be produced using scalable fiber fabrication techniques.

Influence of dopants on the impermeability of graphene.

Graphene has attracted much attention as an impermeable membrane and a protective coating against oxidation. While many theoretical studies have shown that defect-free graphene is impermeable, in reality graphene inevitably has defects in the form of grain boundaries and vacancies. Here, we study the effects of N-dopants on the impermeability of few-layered graphene (FLG) grown on copper using chemical vapor deposition. The grain boundaries in FLG have minimal impact on their permeability to oxygen as they do not provide a continuous channel for gas transport due to high tortuosity. However, we experimentally show that the N-dopants in FLG display multiple configurations that create structural imperfections to selectively allow gas molecules to permeate. We used a comprehensive array of tools including Raman spectroscopy, X-ray photoelectron spectroscopy, optically stimulated electron emission measurements, and density functional theory of N-doped graphene on copper to elucidate the effects of dopant configuration on the impermeability of graphene. Our results clearly show that oxygen can permeate through graphene with non-graphitic nitrogen dopants that create pores in graphene and oxidize the underlying Cu substrate while graphitic nitrogen dopants do not show any changes compared to the pristine form. Furthermore, we observed that the work function of graphene can be tuned effectively by changing the dopant configuration.

A GH receptor antisense oligonucleotide inhibits hepatic GH receptor expression, IGF-I production and body weight gain in normal mice.

Diabetic retinopathy and acromegaly are diseases associated with excess action of GH and its effector IGF-I, and there is a need for improved therapies. We have designed an optimised 2'-O-(2-methoxyethyl)-modified phosphorothioate oligodeoxynucleotide, ATL 227446, and demonstrated its ability to suppress GH receptor mRNA in vitro. Subcutaneous injections of ATL 227446 reduced GH receptor mRNA levels, GH binding activity and serum IGF-I levels in mice after seven days of dosing. The reduction in serum IGF-I could be sustained for over ten weeks of dosing at therapeutically relevant levels, during which there was also a significant decrease in body weight gain in antisense-treated mice relative to saline and mismatch control-treated mice. The findings indicate that administration of an antisense oligonucleotide to the GH receptor may be applicable to human diseases in which suppression of GH action provides therapeutic benefit.

Electrochemical organization of monolayer protected gold nanoclusters on single-walled carbon nanotubes: significantly enhanced double layer capacitance.

This paper reports a novel electrochemical route for anchoring monolayer protected gold nanoclusters (size 8 +/- 0.2 nm) on single-walled carbon nanotube bundles, resulting in the formation of hybrid materials. Monolayer protected gold nanoclusters prepared by modified Brust synthesis route were organized on SWNT bundles by cycling the potential in dichloromethane between -1 to +1 V at a scan rate of 50 mV/s. Monolayer protected nanoclusters in electrolyte solutions possess ionic space charge around them (double layer charging), making them suitable for organization on nanotube bundles, by tuning the electrostatic interactions. More significantly, analysis of the double layer capacitance of these hybrid materials shows almost ten times increase in capacitance compared to that of bare SWNT bundles. We believe that these hybrid materials are potentially useful in nanoelectronics.

Asymmetric distribution of a fluorescent sterol in synaptic plasma membranes: effects of chronic ethanol consumption.

Ethanol-induced structural changes in membranes have in some studies been attributed to an increase in total membrane cholesterol. Consistent changes in cholesterol content, however, have not been observed in membranes of ethanol consuming animals and alcoholic patients. This study examined the hypotheses that cholesterol was asymmetrically distributed in synaptic plasma membranes (SPM) and that chronic ethanol consumption alters the transbilayer distribution of cholesterol. Dehydroergosterol, a fluorescent cholesterol analogue was used to examine sterol distribution and exchange in chronic ethanol-treated and pair-fed control groups. The cytofacial leaflet was found to have significantly more dehydroergosterol as compared to the exofacial leaflet. This asymmetric distribution was significantly reduced by chronic ethanol consumption as was sterol transport. Total cholesterol content did not differ between the two groups. Chronic ethanol consumption appeared to alter transbilayer sterol distribution as determined by the incorporation and distribution of dehydroergosterol in SPM. The changes in transbilayer sterol distribution are consistent with recent reports on the asymmetric effects of ethanol in vitro ((1988) Biochim. Biophys. Acta 946, 85-94) and in vivo ((1989) J. Neurochem. 52, 1925-1930) on membrane leaflet structure. The results of this study also underscore the importance of examining membrane lipid domains in addition to the total content of different lipids.

Specific requirement of lysophosphatidylcholine for palmitoyl-CoA synthetase of chicken intestine.

The presence of palmitoyl-CoA synthetase (EC 6.2.1.3) in the brush border-free particulate fraction of chicken intestinal mucosa is demonstrated. The enzyme was dependent on the simultaneous presence of lysophosphatidylcholine and Triton X-100 as well as ATP, CoA and Mg2+ for maximal activity. Lysophosphatidylcholine could not be replaced by other lipids. Enzyme preparations solubilized by Triton X-100 or lysophosphatidylcholine were still dependent on the presence of detergents for maximal activity.

ZnO nanowires by pulsed laser vaporization: synthesis and properties.

We report a new pulsed-laser vaporization (PLV) technique to synthesize nanowires of single-crystal ZnO having a wurtzite structure by using colloidal gold nanoparticles as seeding catalysts. The average diameter of the nanowires is approximately 13 nm, with a very narrow range of 7 to 25 nm. The nanowires are straight for the most part, with the axes parallel to the [0001] growth direction. Raman and photoluminescence spectra from the nanowires and bulk ZnO are similar except for a approximately 510 nm band in the nanowires due to oxygen vacancies. The bulk-like vibrational and electronic properties of the nanowires is due to the diameter being larger than the threshold below which quantum confinement-induced effects are expected.

Molecular functionalization of carbon nanotubes and use as substrates for neuronal growth.

Carbon nanotubes are strong, flexible, conduct electrical current, and can be functionalized with different molecules, properties that may be useful in basic and applied neuroscience research. We report the first application of carbon nanotube technology to neuroscience research. Methods were developed for growing embryonic rat-brain neurons on multiwalled carbon nanotubes. On unmodified nanotubes, neurons extend only one or two neurites, which exhibit very few branches. In contrast, neurons grown on nanotubes coated with the bioactive molecule 4-hydroxynonenal elaborate multiple neurites, which exhibit extensive branching. These findings establish the feasability of using nanotubes as substrates for nerve cell growth and as probes of neuronal function at the nanometer scale.

Beneficial effects of S-adenosyl-L-methionine on blood-brain barrier breakdown and neuronal survival after transient cerebral ischemia in gerbils.

We have studied the beneficial effects of S-adenosyl-L-methionine (SAM) tosylate on blood-brain barrier (BBB) breakdown and neuronal survival after transient cerebral ischemia in gerbils. BBB breakdown experiments were performed in pentobarbital anesthetized gerbils subjected to 10 min of bilateral carotid artery occlusion and 6 h of reperfusion. For BBB breakdown measurements, SAM (120 mg/kg, i.p.) was administered to gerbils just after occlusion and thereafter every hour up to 5 h. Fluorometric measurements quantified the blood-brain permeability tracer, Evans blue (EB). SAM treatment significantly reduced the BBB breakdown as indicated by reduced levels of EB fluorescence. Neuronal count experiments were conducted in gerbils subjected to transient ischemia and 7 days of reperfusion. For neuronal count experiments SAM (15-120 mg/kg) was administered at 6 and 12 h after reperfusion, and twice each day thereafter for 7 days. SAM dose dependently protected the hippocampal CA1 neurons assessed by histopathological methods. SAM has a beneficial effect on the outcome of ischemic injury by reducing the BBB breakdown and neuronal death.

Effect of difluoromethylornithine treatment on regional ornithine decarboxylase activity and edema formation after experimental brain injury.

This study examined the effect of difluoromethylornithine (DFMO) on regional activities of ornithine decarboxylase (ODC) and edema formation in bilateral cerebral cortex and hippocampus after a unilateral controlled cortical-impact (CCI) injury in rats. To measure the activity of ODC, the brains of injured and control rats were frozen in situ at 30 min, 3, 6, and 24 h after CCI brain injury of moderate severity. The specific gravity, an indicator of edema formation, was examined in decapitated animals at corresponding time points. Brain injury induced significant increases of ODC in the ipsilateral hippocampus, adjacent and injury-site cortices, and in the contralateral cortex and hippocampus at 3 and 6 h after injury. No significant edema formation was found in any brain region at 30 min after injury. A significant edema formation was first found only in the injury-site cortex at 3 h after injury. At 6 and 24 h after injury, significant edema was found in all regions ipsilateral to the injury-site. At 24 h after injury, significant but less severe edema was also found in the contralateral cortex and hippocampus. DFMO, an irreversible inhibitor of ODC, abolished the increase in ODC in all regions. It also attenuated edema formation in the adjacent cortex and in the contralateral cortex and hippocampus. These findings indicate that polyamines may play a role in posttraumatic brain edema formation, particularly in important brain regions remote from the injury-site.

Kinetics and size of cholesterol lateral domains in synaptosomal membranes: modification by sphingomyelinase and effects on membrane enzyme activity.

Cholesterol domains and transport have been well-studied in non-neuronal membranes in contrast to neuronal membranes. The purpose of the experiments reported in this paper was to determine: (1) exchangeable and non-exchangeable cholesterol domains or pools were present in brain synaptosomal membranes; (2) effects of hydrolysis of sphingomyelin on cholesterol pools, that has previously been shown to alter membrane cholesterol in non-neuronal membranes and; (3) sphingomyelin hydrolysis and enzyme activity. Cholesterol pools were determined using cholesterol exchange between radiolabeled small unilamellar vesicles and mouse synaptosomes. Activity of Ca(2+)+Mg(2+)-ATPase and Na(+)+K(+)-ATPase were measured in synaptosomal membranes following treatment with sphingomyelinase. The size of the exchangeable pool of synaptosomal membrane cholesterol was approx 50% of total membrane cholesterol when measured at 37 degrees C. The t1/2 of cholesterol exchange at 37 degrees C in synaptosomes was approx 10 h. Lowering the incubation temperature to 25 degrees C, significantly reduced the size of the exchangeable pool and significantly increased the t1/2 of cholesterol exchange. Sphingomyelinase treatment of synaptosomes significantly slowed cholesterol exchange but did not modify the size of the exchangeable pool of cholesterol. Ca(2+)+Mg(2+)-ATPase activity was significantly inhibited by sphingomyelinase treatment as compared to Na(+)+K(+)-ATPase activity. Cholesterol domains were described in neuronal tissue and the size and kinetics of those pools were altered by temperature-induced changes in fluidity and hydrolysis of sphingomyelin. Sphingomyelinase-induced changes in Ca(2+)+Mg(2+)-ATPase activity were not affected by hydrolysis of sphingomyelin but appeared to be associated with a reduction in cytofacial phosphatidylinositol.

Glial glutamate transporter GLT-1 down-regulation precedes delayed neuronal death in gerbil hippocampus following transient global cerebral ischemia.

Glial (GLT-1 and GLAST) and neuronal (EAAC1) high-affinity transporters mediate the sodium dependent glutamate reuptake in mammalian brain. Their dysfunction leads to neuronal damage by allowing glutamate to remain in the synaptic cleft for a longer duration. The purpose of the present study is to understand their contribution to the ischemic delayed neuronal death seen in gerbil hippocampus following transient global cerebral ischemia. The protein levels of these three transporters were studied by immunoblotting as a function of reperfusion time (6 h to 7 days) following a 10 min occlusion of bilateral common carotid arteries in gerbils. In the vulnerable hippocampus, there was a significant decrease in the protein levels of GLT-1 (by 36-46%, P < 0.05; between 1 and 3 days of reperfusion) and EAAC1 (by 42-68%, P < 0.05; between 1 and 7 days of reperfusion). Histopathological evaluation showed no neuronal loss up to 2 days of reperfusion but an extensive neuronal loss (by approximately 84%, P < 0.01) at 7 days of reperfusion in the hippocampal CA1 region. The time frame of GLT-1 dysfunction (1-3 days of reperfusion) precedes the initiation of delayed neuronal death (2-3 days of reperfusion). This suggests GLT-1 dysfunction as a contributing factor for the hippocampal neuronal death following transient global cerebral ischemia. Furthermore, decreased EAAC1 levels may contribute to GABAergic dysfunction and excitatory/inhibitory imbalance following transient global ischemia.

Enhanced accumulation of free fatty acids in experimental focal cerebral ischemia.

Cerebral ischemia is well known to cause an increase in the level of free fatty acids (FFAs) in rodent species. Such FFA accumulations may signal regional lipid membrane damage and are postulated to participate in the pathogenesis of progressive infarction after cerebral ischemia. In this study we have examined the regional levels of FFAS in the cortices of cats after 8 h of middle cerebral artery occlusion. The levels of specific FFAs (palmitic, stearic, and oleic acids) were 1.5 and 2.0 times higher in the penumbral and dense ischemic regions, respectively, than those in the non-ischemic contralateral region. Although no significant differences were found between the penumbra and dense ischemic regions in the levels of arachidonic acid, the levels of docosahexaenoic acid in both of these regions were significantly higher than those in the contralateral region (P < 0.05). These results suggest that enhanced accumulation of FFAs are regionally distributed after focal ischemia and may contribute to neuronal damage after focal cerebral ischemia in non-rodent species.

Does CDP-choline modulate phospholipase activities after transient forebrain ischemia?

Ten min forebrain ischemia/1-day reperfusion resulted in significant decreases in total phosphatidylcholine (PtdCho), phosphatidylinositol (PtdIns), and cardiolipin in gerbil hippocampus. CDP-choline restored cardiolipin levels, arachidonic acid content of PtdCho, partially but significantly restored total PtdCho, and had no effect on PtdIns. These data suggest that CDP-choline prevented the activation of phospholipase A(2) (rather than inhibiting phospholipase A(2) activity) but did not affect activities of PtdCho-phospholipases C and/or D, or phosphoinositide-phospholipase C. CDP-choline also provided significant protection for hippocampal CA(1) neurons.

Fluorometric assay of nitrite and nitrate in brain tissue after traumatic brain injury and cerebral ischemia.

Nitric oxide synthase (NOS) is distributed within the brain, and nitric oxide (NO) is felt to be involved in the pathophysiology of deterioration after head injury and cerebral ischemia. This study determined the levels of the stable end products of NOS (NOx=nitrite+nitrate) after traumatic brain injury (TBI) and transient cerebral ischemia. A fluorometric assay using nitrate reductase and the NADPH regenerating system was used to quantitate NOx in ultrafiltered (10-kDa cutoff) cortical and hippocampal extracts after reduction of nitrate. In TBI rats, both the plasma and tissue showed a sharp increase in NOx levels 5 min after injury. Plasma NOx returned to control levels by 2 h after injury. Ipsilateral-cortex NOx levels returned to control levels approximately 6 h after injury and remained constant from 6-24 h. Contralateral-cortex returned near to control levels after 1 h. Hippocampus also followed a similar trend. In gerbils, there was a significant elevation in tissue NOx levels immediately after 10 min transient cerebral ischemia, which gradually returned to control levels over 24 h reperfusion. This striking burst of NO synthesis immediately after injury is clearly evident whether the injury is head trauma or ischemia, or whether the measurements were performed on tissue or plasma. It is unknown whether endothelial NOS, neuronal NOS, or both caused the elevation of the NO end products seen after the CNS insults.