Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

Novel immobilization of a quaternary ammonium moiety on keratin fibers for medical applications.

This paper introduces a new approach for immobilizing a quaternary ammonium moiety on a keratinous substrate for enhanced medical applications. The method involves the generation of thiols by controlled reduction of cystine disulfide bonds in the keratin, followed by reaction with [2-(acryloyloxy)ethyl]trimethylammonium chloride through thiol-ene click chemistry. The modified substrate was characterized with Raman and infrared spectroscopy, and assessed for its antibacterial efficacy and other performance changes. The results have demonstrated that the quaternary ammonium moiety has been effectively attached onto the keratin structure, and the resultant keratin substrate exhibits a multifunctional effect including antibacterial and antistatic properties, improved liquid moisture management property, improved dyeability and a non-leaching characteristic of the treated substrate.

Evolution of the electrochemical capacitance of transition metal oxynitrides with time: the effect of ageing and passivation

A number of transition metal nitrides and oxynitrides, which are actively investigated today as electrode materials in a wide range of energy conversion and storage devices, possess an oxide layer on the surface. Upon exposure to ambient air, properties of this layer progressively change in the process known as "ageing". Since a number of electrochemical processes involve the surface or sub-surface layers of the active electrode compounds only, ageing could have a significant effect on the overall performance of energy conversion and storage devices. In this work, the influence of the ageing of tungsten and molybdenum oxynitrides on their electrochemical properties in supercapacitors is explored for the first time. Samples are synthesised by the temperature-programmed reduction in NH3 and are treated with different gases prior to exposure to air in order to evaluate the role of passivation in the ageing process. After the synthesis, products are subjected to controlled ageing and are characterised by low temperature nitrogen adsorption, X-ray photoelectron spectroscopy and transmission electron microscopy. Capacitive properties of the compounds are evaluated by performing cyclic voltammetry and galvanostatic charge and discharge measurements in the 1 M H2SO4 electrolyte. © 2014 the Partner Organisations.

Redox sulfur chemistry of the copper chaperone Atox1 is regulated by the enzyme glutaredoxin 1, the reduction potential of the glutathione couple GSSG/2GSH and the availability of Cu(I)

Glutaredoxins have been characterised as enzymes regulating the redox status of protein thiols via cofactors GSSG/GSH. However, such a function has not been demonstrated with physiologically relevant protein substrates in in vitro experiments. Their active sites frequently feature a Cys-xx-Cys motif that is predicted not to bind metal ions. Such motifs are also present in copper-transporting proteins such as Atox1, a human cytosolic copper metallo-chaperone. In this work, we present the first demonstration that: (i) human glutaredoxin 1 (hGrx1) efficiently catalyses interchange of the dithiol and disulfide forms of the Cys(12)-xx-Cys(15) fragment in Atox1 but does not act upon the isolated single residue Cys(41); (ii) the direction of catalysis is regulated by the GSSG/2GSH ratio and the availability of Cu(I); (iii) the active site Cys(23)-xx-Cys(26) in hGrx1 can bind Cu(I) tightly with femtomolar affinity (K(D) = 10(-15.5) M) and possesses a reduction potential of E(o)' = -118 mV at pH 7.0. In contrast, the Cys(12)-xx-Cys(15) motif in Atox1 has a higher affinity for Cu(I) (K(D) = 10(-17.4) M) and a more negative potential (E(o)' = -188 mV). These differences may be attributed primarily to the very low pKa of Cys23 in hGrx1 and allow rationalisation of conclusion (ii) above: hGrx1 may catalyse the oxidation of Atox1(dithiol) by GSSG, but not the complementary reduction of the oxidised Atox1(disulfide) by GSH unless Cu(aq)(+) is present at a concentration that allows binding of Cu(I) to reduced Atox1 but not to hGrx1. In fact, in the latter case, the catalytic preferences are reversed. Both Cys residues in the active site of hGrx1 are essential for the high affinity Cu(I) binding but the single Cys(23) residue only is required for the redox catalytic function. The molecular properties of both Atox1 and hGrx1 are consistent with a correlation between copper homeostasis and redox sulfur chemistry, as suggested by recent cell experiments. These proteins appear to have evolved the features necessary to fill multiple roles in redox regulation, Cu(I) buffering and Cu(I) transport.

Study and exploration on inorganic nanomaterials as additive in lubricant application.

 In this thesis, the application of planetary ball milling for the efficient production of nanomaterials is systematically studied. Three inorganic materials: calcium carbonate (CaCO3), molybdenum disulphide (MoS2) and hexagonal-boron nitride (h-BN) are chosen as model systems.

Functionalized mesoporous silica nanoparticles with redox-responsive short-chain gatekeepers for agrochemical delivery.

The controlled release of salicylic acid (SA), a key phytohormone, was mediated by using a novel decanethiol gatekeeper system grafted onto mesoporous silica nanoparticles (MSNs). The decanethiol was conjugated only to the external surfaces of the MSNs through glutathione (GSH)-cleavable disulfide linkages and the introduction of a process to assemble gatekeepers only on the outer surface so that the mesopore area can be maintained for high cargo loading. Raman and nitrogen sorption isotherm analyses confirmed the successful linkage of decanethiol to the surface of MSNs. The in vitro release of SA from decanethiol gated MSNs indicated that the release rate of SA in an environment with a certain amount of GSH was significantly higher than that without GSH. More importantly, in planta experiments showed the release of SA from decanethiol gated MSNs by GSH induced sustained expression of the plant defense gene PR-1 up to 7 days after introduction, while free SA caused an early peak in PR-1 expression which steadily decreased after 3 days. This study demonstrates the redox-responsive release of a phytohormone in vitro and also indicates the potential use of MSNs in planta as a controlled agrochemical delivery system.

Graphene/tri-block copolymer composites prepared via RAFT polymerizations for dual controlled drug delivery via pH stimulation and biodegradation

A novel tri-block copolymer poly(oxopentanoate ethyl methacrylate)-block-poly(pyridyl disulfide ethyl acrylate)-block-poly(ethylene glycol acrylate) [poly(OEMA-b-PDEA-b-PEGA)], retaining active keto groups and pyridyl disulfide (PDS) side functionalities, was synthesized as a drug delivery vehicle using reversible addition-fragmentation chain transfer (RAFT) polymerization method. One mimic drug pyridine-2-thione (PT) was introduced into the monomer, PDEA for copolymerization. The other mimic drug O-benzylhydroxylamine (BHA) was conjugated with tri-block copolymer via efficient oxime coupling chemistry, followed by the attachment onto graphene via π-π stacking interaction to obtain a graphene/tri-block copolymer composite. 1H NMR, UV-vis absorption spectroscopy, fluorescence spectroscopy, gel permeation chromatography (GPC), atomic force microscope (AFM) and transmission electron microscope (TEM) were used to verify the successful step-wise preparation of the tri-block copolymer and drug loaded composite. In vitro release behaviors of BHA and PT from graphene/tri-block copolymer composite via dual drug release mechanisms were investigated. BHA can be released under acid environment, while PT will be released in the presence of reducing agents, such as dithiothreitol (DTT) or glutathione (GSH). It can be envisioned that this novel composite could be exploited as a novel intracellular drug delivery system via dual release mechanisms.

Cisplatin-induced formation of biocompatible and biodegradable polypeptide-based vesicles for targeted anticancer drug delivery

Novel cisplatin (CDDP)-loaded, polypeptide-based vesicles for the targeted delivery of cisplatin to cancer cells have been prepared. These vesicles were formed from biocompatible and biodegradable maleimide-poly(ethylene oxide)114-b-poly(L-glutamic acid)12 (Mal-PEG114-b-PLG12) block copolymers upon conjugation with the drug itself. CDDP conjugation forms a short, rigid, cross-linked, drug-loaded, hydrophobic block in the copolymer, and subsequently induces self-assembly into hollow vesicle structures with average hydrodynamic diameters (Dh) of ∼ 270 nm. CDDP conjugation is critical to the formation of the vesicles. The reactive maleimide-PEG moieties that form the corona and inner layer of the vesicles were protected via formation of a reversible Diels-Alder (DA) adduct throughout the block copolymer synthesis so as to maintain their integrity. Drug release studies demonstrated a low and sustained drug release profile in systemic conditions (pH = 7.4, [Cl(-)] = 140 mM) with a higher "burst-like" release rate being observed under late endosomal/lysosomal conditions (pH = 5.2, [Cl(-)] = 35 mM). Further, the peripheral maleimide functionalities on the vesicle corona were conjugated to thiol-functionalized folic acid (FA) (via in situ reduction of a novel bis-FA disulfide, FA-SS-FA) to form an active targeting drug delivery system. These targeting vesicles exhibited significantly higher cellular binding/uptake into and dose-dependent cytotoxicity toward cancer cells (HeLa) compared to noncancerous cells (NIH-3T3), which show high and low folic acid receptor (FR) expression, respectively. This work thus demonstrates a novel approach to polypeptide-based vesicle assembly and a promising strategy for targeted, effective CDDP anticancer drug delivery.

Preparation and adsorption of phosphorus by new heteropolyacid salt–lanthanum oxide composites

In this article, we reported a new method in which molybdenum heteropolyacid salt was selected to mix with lanthanum oxide and bentonite, respectively, and the dipping method was used to prepare the new composites of heteropolyacid salt–lanthanum oxide, heteropolyacid salt–bentonite, and heteropolyacid salt–lanthanum oxide–bentonite. We observed that the composites have a better removal effect for phosphorus by control of the ratio and calcination temperature. The effect of quantity, adsorption time, phosphorus wastewater concentration, and pH value of composites on phosphorus adsorption was studied. We also found that the removal rate of phosphorus by the composite of heteropolyacid salt–lanthanum oxides increases up to 99.1% under the condition of 1:1 mass ratio and 500°C of calcination temperature. IR and XRD studies suggest that molybdenum heteropolyacid salt has been loaded to lanthanum oxide carrier successfully and heteropolyacid salt keeps the original Keggin structure. Heteropolyacid salt–lanthanum oxide has a good adsorption effect on phosphorus under the condition of 0.15 g of the composite, 90 min of adsorption time, phosphorus concentration of 50 mg L−1, and pH value of 3. The adsorption of phosphorus corresponds with the Langmuir isotherm model and Lagergren first-order kinetics equation. Therefore, the composite has excellent absorption ability and was competent in removing phosphorus with a low concentration from aqueous solution. It could be a great potential adsorbent for the removal of phosphorus in lakes, rivers, and reservoirs.

A preliminary study on machinability of super austenitic stainless steel

Stainless steel is the most widely used alloys of steel. The reputed variety of stainless steel having customised material properties as per the design requirements is Duplex Stainless Steel and Austenitic Stainless Steel. The Austenite Stainless Steel alloy has been developed further to be Super Austenitic Stainless Steel (SASS) by increasing the percentage of the alloying elements to form the half or more than the half of the material composition. SASS (Grade-AL-6XN) is an alloy steel containing high percentages of nickel (24%), molybdenum (6%) and chromium (21%). The chemical elements offer high degrees of corrosion resistance, toughness and stability in a large range of hostile environments like petroleum, marine and food processing industries. SASS is often used as a commercially viable substitute to high cost non-ferrous or non-metallic metals. The ability to machine steel effectively and efficiently is of utmost importance in the current competitive market. This paper is an attempt to evaluate the machinability of SASS which has been a classified material so far with very limited research conducted on it. Understanding the machinability of this alloy would assist in the effective forming of this material by metal cutting. The novelty of research associated with this is paper is reasonable taking into consideration the unknowns involved in machining SASS. The experimental design consists of conducting eight milling trials at combination of two different feed rates, 0.1 and 0.15 mm/tooth; cutting speeds, 100 and 150 m/min; Depth of Cut (DoC), 2 and 3 mm and coolant on for all the trials. The cutting tool has two inserts and therefore has two cutting edges. The trial sample is mounted on a dynamometer (type 9257B) to measure the cutting forces during the trials. The cutting force data obtained is later analyzed using DynaWare supplied by Kistler. The machined sample is subjected to surface roughness (Ra) measurement using a 3D optical surface profilometer (Alicona Infinite Focus). A comprehensive metallography process consisting of mounting, polishing and etching was conducted on a before and after machined sample in order to make a comparative analysis of the microstructural changes due to machining. The microstructural images were capture using a digital microscope. The microhardness test were conducted on a Vickers scale (Hv) using a Vickers microhardness tester. Initial bulk hardness testing conducted on the material show that the alloy is having a hardness of 83.4 HRb. This study expects an increase in hardness mostly due to work hardening may be due to phase transformation. The results obtained from the cutting trials are analyzed in order to judge the machinability of the material. Some of the criteria used for machinability evaluation are cutting force analysis, surface texture analysis, metallographic analysis and microhardness analysis. The methodology followed in each aspect of the investigation is similar to and inspired by similar research conducted on other materials. However, the novelty of this research is the investigation of various aspects of machinability and drawing comparisons between each other while attempting to justify each result obtained to the microstructural changes observed which influence the behaviour of the alloy. Due to the limited scope of the paper, machinability criteria such as chip morphology, Metal Removal Rate (MRR) and tool wear are not included in this paper. All aspects are then compared and the optimum machining parameters are justified with a scope for future investigations