Size-controlled synthesis of monodispersed gold nanoparticles via carbon monoxide gas reduction

An in depth analysis of gold nanoparticle (AuNP) synthesis and size tuning, utilizing carbon monoxide (CO) gas as a reducing agent, is presented for the first time. The sizes of the AuNPs are tunable from ~4 to 100 nm by altering the concentration of HAuCl4 and inlet CO gas-injection flow rate. It is also found that speciation of aqueous HAuCl4, prior to reduction, influences the size, morphology, and properties of AuNPs when reduced with CO gas. Ensemble extinction spectra and TEM images provide clear evidence that CO reduction offers a high level of monodispersity with standard deviations as low as 3%. Upon synthesis, no excess reducing agent remains in solution eliminating the need for purification. The time necessary to synthesize AuNPs, using CO, is less than 2 min.     

Electrically conducting particle networks in polymer electrolyte as three-dimensional electrodes for hydrogenase electrocatalysis

Efficient H₂ oxidation and production by hydrogenase enzymes has attracted much interest because of the possibilities it raises for clean energy cycling without the need for precious metal catalysts. Although hydrogenases are extremely active electrocatalysts, high surface-area electrode structures will be necessary if the enzymes are to find application in energy technologies. Taking inspiration from fuel cell electrode assemblies, in which metal nanoparticles are commonly mounted on particulate carbon supports encased in polymer electrolyte, we show that high surface-area hydrogenase electrodes can be constructed from enzyme-loaded pyrolytic graphite particles in pH-neutralised Nafion. Pyrolytic graphite is the favoured surface for direct electrochemistry of many redox proteins, and on sanding, yields micron-dimension platelike particles. By modifying graphite platelets with hydrogenase before assembling the particles into a network, we ensure a high, uniform enzyme coverage. Incorporation of hydrogenases into high surface-area conducting network electrodes enhanced electrocatalytic H₂ oxidation currents by 30-times compared to values obtained for a planar hydrogenase electrode, while retaining efficient conductivity and H₂ mass transport through the network. This approach should make it possible to directly compare enzyme and precious metal electrocatalysis and to benchmark what opportunities are possible with selective enzyme catalysts.     

Study of microcellular foaming of polystyrene aided with 45 kHz of ultrasound waves energy

ABSTRACT

In the microcellular foam plastic processing, cellular formation stage was being an essential stage since the nucleation and growth of the cell take place within. Based on classical nucleation theory, diminution of the free energy for nucleation, exponentially lead to an increase in the nucleation rate. This can be done by increasing the super-saturation level which achieved by heating the gas-saturated polymer. Hence, the advance is taken out by utilizing the ultrasound wave simultaneously with heating for foaming Polystyrene-scCO₂, which, not only to keep the super-saturation degree but also reduce the nucleation barrier. In this work, foaming was conducted under 45 kHz of ultrasound and varying the foaming temperature after saturating polystyrene with scCO₂. The results demonstrate, that foaming under ultrasound, the expansion ratio attained up to 1.5 fold, increase along with the heating temperature. Higher cell densities obtained with ultrasound applied at 50°C, however only slight difference can be seen, which about 10¹⁰–10¹¹ cell/cm³. From the cell size distribution results, cell distributed around 0.5–3.5 µm, with or without ultrasound applied for 60 and 70°C, Meanwhile at 50°C of foaming, the lowest cell size obtained with the aid of ultrasound in the range of 0.3–2.4 µm.     

Catalytic CO Hydrogenation: Mechanism and Kinetics from Chemical Transients at Low and Atmospheric Pressures

The hydrogenation of CO over Co model catalysts was studied using relaxation-type methods operating in situ either at atmospheric pressures or under surface science conditions. Emphasis was laid on providing information on the surface composition and on how it changes with time under catalytic reaction conditions. Using pressure forcing in chemical transient kinetics (CTK), the build-up of the steady-state was studied at 503 K and atmospheric pressure to demonstrate that the active catalyst surface is not metallic but covered with carbon, oxygen and hydrogen in excess of a monolayer equivalent. Both build-up and backward transients suggest CO to act as the “monomer” which probably inserts into an O–H bond to form the primary surface complex necessary for hydrocarbon and oxygenate formation. Repetitive electric field pulses (pulsed field desorption mass spectrometry, PFDMS) at low pressures have allowed the CO dissociation kinetics on a nano-sized Co 3D crystal (“tip”) to be monitored in the millisecond time range. No evidence for the occurrence of the Boudouard reaction was obtained in either PFDMS or CTK. Adsorbed CH _x (x = 1–3) species were detected in small amounts demonstrating that CO dissociation is fast compared to carbon hydrogenation. Adsorbed Co-subcarbonyl species, Co(CO) _x were also detected by PFDMS and possibly mediate the necessary surface mobility during the initial restructuring of the catalyst. Surface carbon seems to inhibit Co-subcarbonyl formation.     

Investigation into the activity of heteropolyacids towards the oxygen reduction reaction on PEMFC cathodes

A total of 18 heteropolyacids (HPAs) were investigated to determine their activity as non-Pt oxygen reduction reaction (ORR) catalysts in polymer electrolyte membrane fuel cell cathodes (PEMFCs). Polarization curves, cyclic voltammetry and impedance spectroscopy determined that, of the HPAs tested, only molybdenum based HPAs are active for the ORR and that vanadium substitutions improved the activity. The reduction potentials of the HPAs in the fuel cell environment were determined by cyclic voltammetry. This showed that no activity is seen above 0.55 V, as the catalysts must first be reduced in situ by 4e⁻ before the HPA can reduce oxygen. The potential at which the HPA can be reduced has been determined to be the limiting factor when using these catalysts for ORR in PEMFCs. Power densities of 67 mW/cm² at 0.2 V were obtained using H₅PMo₁₀V₂O₄₀. Molybdenum based HPAs were covalently bonded to the carbon achieving mass loadings 3× that obtained through adsorption. Using this approach catalyst, performance was improved to 86 mW/cm² at 0.2 V. The increased loadings did not significantly increase the potentials at which the HPA becomes active for the ORR. We were able to show that MEA degradation, as measured by F⁻ emission rates, using these catalysts are reduced during accelerated testing protocols.     

Apoptosis-inducing high (.)NO concentrations are not sustained either in nascent or in developed cancers

Nitric oxide ((.)NO) induces apoptosis at high concentrations by S-nitrosating proteins such as glyceraldehyde-3-phosphate dehydrogenase. This literature analysis revealed that failure to sustain high (.)NO concentrations is common to all cancers. In cervical, gastric, colorectal, breast, and lung cancer, the cause of this failure is the inadequate expression of inducible nitric oxide synthase (iNOS), resulting from the inhibition of iNOS expression by TGF-beta1 at the mRNA level. In bladder, renal, and prostate cancer, the reason for the insufficient (.)NO levels is the depletion of arginine, resulting from arginase overexpression. Arginase competes with iNOS for arginine, catalyzing its hydrolysis to ornithine and urea. In gliomas and ovarian sarcomas, low (.)NO levels are caused by inhibition of iNOS by N-chlorotaurine, produced by infiltrating neutrophils. Stimulated neutrophils express myeloperoxidase, catalyzing H2O2 oxidation of Cl- to HOCl, which N-chlorinates taurine at its concentration of 19 mM in neutrophils. In squamous cell carcinomas of the skin, ovarian cancers, lymphomas, Hodgkin's disease, and breast cancers, low (.)NO concentrations arise from the inhibition of iNOS by N-bromotaurine, produced by eosinophil-peroxidase-expressing infiltrating eosinophils. Eosinophil peroxidase catalyzes the H2O2 oxidation of Br- to HOBr, which N-brominates taurine to N-bromotaurine at its concentration of 15 mM in eosinophils. In microvascularized tumors, the (.)NO concentration is further depleted; (.)NO is rapidly consumed by red blood cells (RBCs) through S-nitrosation of RBC glutathione and hemoglobin, and by oxidation to nitrate by RBC oxyhemoglobin. Angiogenesis-inhibiting antibodies are currently used to treat cancers; their mode of action is not, as previously thought, reduction of the tumor O2 or nutrient supply. They actually decrease the loss of (.)NO to RBCs.     

Azido and Diazarinyl Analogues of Bis‐Tyrphostin as Asymmetrical Inhibitors of Dynamin GTPase

Probing the dynamin binding site : Bis‐tyrphostin ( 1 , Bis‐T), is a potent inhibitor of the phospholipid‐stimulated GTPase activity of dynamin I. Analogues of Bis‐T have significant potential as a biological probes for the dissection of endocytic pathways. Bis‐T‐derived compounds were synthesised and evaluated for their ability to inhibit the GTPase activity of dynamin I. Two analogues ( 23 and 24 ) represent the first asymmetrically substituted Bis‐T analogues to retain dynamin inhibition.

     

Tuning the mechanical properties of UV coatings towards hard and flexible systems

The standard resins of radiation-curable coatings provide either hard or flexible coatings dependent on the type of chemistry used. Whereas aromatic epoxide acrylates usually give hard and brittle coatings, urethane acrylates are known for their flexibility. Since the radiation curable systems should not contain solvents, the desired low viscosity for the specific application is adjusted with reactive monomers. This normally prevents the use of flexible high-molecular-weight polymers. On the other hand, the viscosity of dispersions is determined by the solid content only and not by the molecular weight of the polymers used. Thus, waterbased UV-curable coatings are one strategy out of this dilemma in order to combine the flexibility of higher-molecular-weight polymers with the hardness of highly crosslinked acrylates. The mechanical data of conventional and waterbased UV coatings are discussed in dependency on glass transition temperature and elastically effective chain length between crosslinks.     

Polysiloxane‐Derived Ceramics Containing Nanowires with Catalytically Active Tips

By direct foaming of a Pt‐containing polysiloxane precursor, macroporous ceramics were generated by pyrolysis at 1400°C under nitrogen or argon. The growth of nanowires was induced via a vapor–liquid–solid mechanism in which the Pt particles acted as deposition site for the decomposition gases released upon pyrolyzing the preceramic polymer. SEM, HR‐SEM, TEM/EDX, and XRD investigations revealed that pyrolysis under argon atmosphere leads to short SiC nanowires of only a few micrometers length and under nitrogen atmosphere Si₃N₄ nanowires evolved, with length of several 10 μm. In both cases the tips of the nanowires mainly consisted of PtSi. In contrast to samples pyrolyzed at 600°C, the components after higher temperature pyrolysis showed moderate‐specific surface areas of 55–67 m²/g. In CO oxidation experiments, a good catalytic activity was found for the Pt silicide particles, suggesting that despite their relatively large size, their location at the tips of the nanowires affords them good reactivity.     

A buffered form of creatine does not promote greater changes in muscle creatine content, body composition, or training adaptations than creatine monohydrate

ABSTRACT: BACKGROUND: Creatine monohydrate (CrM) has been consistently reported to increase muscle creatine content and improve high-intensity exercise capacity. However, a number of different forms of creatine have been purported to be more efficacious than CrM. The purpose of this study was to determine if a buffered creatine monohydrate (KA) that has been purported to promote greater creatine retention and training adaptations with fewer side effects at lower doses is more efficacious than CrM supplementation in resistance-trained individuals. METHODS: In a double-blind manner, 36 resistance-trained participants (20.2 +/- 2 years, 181 +/- 7 cm, 82.1 +/- 12 kg, and 14.7 +/- 5% body fat) were randomly assigned to supplement their diet with CrM (Creapure(R) AlzChem AG, Trostberg, Germany) at normal loading (4 x 5 g/d for 7-days) and maintenance (5 g/d for 21-days) doses; KA (Kre-Alkalyn(R), All American Pharmaceutical, Billings, MT, USA) at manufacturer's recommended doses (KA-L, 1.5 g/d for 28-days); or, KA with equivalent loading (4 x 5 g/d for 7-days) and maintenance (5 g/d) doses of CrM (KA-H). Participants were asked to maintain their current training programs and record all workouts. Muscle biopsies from the vastus lateralis, fasting blood samples, body weight, DEXA determined body composition, and Wingate Anaerobic Capacity (WAC) tests were performed at 0, 7, and 28-days while 1RM strength tests were performed at 0 and 28-days. Data were analyzed by a repeated measures multivariate analysis of variance (MANOVA) and are presented as mean +/- SD changes from baseline after 7 and 28-days, respectively. RESULTS: Muscle free creatine content obtained in a subgroup of 25 participants increased in all groups over time (1.4 +/- 20.7 and 11.9 +/- 24.0 mmol/kg DW, p = 0.03) after 7 and 28-days, respectively, with no significant differences among groups (KA-L -7.9 +/- 22.3, 4.7 +/- 27.0; KA-H 1.0 +/- 12.8, 9.1 +/- 23.2; CrM 11.3 +/- 23.9, 22.3 +/- 21.0 mmol/kg DW, p = 0.46). However, while no overall group differences were observed (p = 0.14), pairwise comparison between the KA-L and CrM groups revealed that changes in muscle creatine content tended to be greater in the CrM group (KA-L -1.1 +/- 4.3, CrM 11.2 +/- 4.3 mmol/kg DW, p = 0.053 [mean +/- SEM]). Although some significant time effects were observed, no significant group x time interactions (p > 0.05) were observed in changes in body mass, fat free mass, fat mass, percent body fat, or total body water; bench press and leg press 1RM strength; WAC mean power, peak power, or total work; serum blood lipids, markers of catabolism and bone status, and serum electrolyte status; or, whole blood makers of lymphocytes and red cells. Serum creatinine levels increased in all groups (p < 0.001) with higher doses of creatine promoting greater increases in serum creatinine (p = 0.03) but the increases observed (0.1 -- 0.2 mg/dl) were well within normal values for active individuals (i.e., <1.28 +/- 0.2 mg/dl). Serum LDL was decreased to a greater degree following ingesting loading doses in the CrM group but returned to baseline during the maintenance phase. No side effects were reported. CONCLUSIONS: Neither manufacturers recommended doses of KA (1.5 g/d) or KA with equivalent loading (20 g/d for 7-days) and maintenance doses (5 g/d for 21-days) of CrM promoted greater changes in muscle creatine content, body composition, strength, or anaerobic capacity than CrM (20 g/d for 7-days, 5 g/d for 21-days). There was no evidence that supplementing the diet with a buffered form of creatine resulted in fewer side effects than CrM. These findings do not support claims that consuming a buffered form of creatine is a more efficacious and/or safer form of creatine to consume than creatine monohydrate.