Two States of Water Converge to One State below 215 K.

Anomalies of water have been explained by the two-state water model. In the model, water becomes one state upon supercooling. However, water crystallizes completely below 235 K ("no man's land"). The structural origin of the anomalous of the water is hidden in the "no man's land". To understand the properties of water, the spectroscopic experiment in "Norman's land" is inevitable. Hence, we proposed a new soft-confinement method for standard nuclear magnetic resonance spectroscopy to explore the "no man's land". We found the singularity temperature (215 K) at ambient pressure. Water exists in one state below 215 K. Above 215 K, the two states of water are supercritical states of the liquid-liquid critical point. The current study provides a perspective to determine the liquid-liquid critical point of water existing in a high-pressure condition.

Copolymer of Phenylene and Thiophene toward a Visible-Light-Driven Photocatalytic Oxygen Reduction to Hydrogen Peroxide.

π-Conjugated polymers including polythiophenes are emerging as promising electrode materials for (photo)electrochemical reactions, such as water reduction to H2 production and oxygen (O2) reduction to hydrogen peroxide (H2O2) production. In the current work, a copolymer of phenylene and thiophene is designed, where the phenylene ring lowers the highest occupied molecular orbital level of the polymer of visible-light-harvesting thiophene entities and works as a robust catalytic site for the O2 reduction to H2O2 production. The very high onset potential of the copolymer for O2 reduction (+1.53 V vs RHE, pH 12) allows a H2O2 production setup with a traditional water-oxidation catalyst, manganese oxide (MnO x ), as the anode. MnO x is deposited on one face of a conducting plate, and visible-light illumination of the copolymer layer formed on the other face aids steady O2 reduction to H2O2 with no bias assistance and a complete photocatalytic conversion rate of 14 000 mg (H2O2) gphotocat -1 h-1 or ≈0.2 mg (H2O2) cm-2 h-1.

Nonpolar Water Clusters: Proton Nuclear Magnetic Resonance Spectroscopic Evidence for Transformation from Polar Water to Nonpolar Water Clusters in Liquid State.

The hydrophilic/hydrophobic interactions of water are important in biological and chemical self-assembly phenomena. Water clusters in hydrophobic environments exhibit a unique morphology. Their process of formation and nonpolar properties have been extensively studied, but no direct experimental evidence has been available until now. This study provides spectroscopic evidence for the transformation of water to nonpolar configuration via clustering. Although individual water molecules form hydrogen bonds with the hydroxyl protons of n-hexanol when codissolved in a nonpolar solvent (toluene-d8), the water clusters are comprised solely of hydrogen bonds between water molecules and do not form hydrogen bonds with the hydroxyl protons of n-hexanol. This behavior indicates that the water clusters are nonpolar rather than polar. This study reports the first example of nonpolar water configuration produced via a liquid-state clustering. This property is a common and important interfacial phenomenon of water in chemistry, biology, materials science, geology, and meteorology.

Supercooled Low-Entropy Water Clusters.

The properties of low-entropy water clusters and small bulk water domains in a hydrophobic solvent over a wide temperature range (235-333 K), including supercooling temperatures, were investigated. 1H nuclear magnetic resonance spectroscopy showed singularity temperatures at ∼300, 250, 235, and 225 K. We proposed a model to understand these singularity temperatures in which the low-entropy water cluster is a locally favored tetrahedral structure (LFTS) and the small bulk water domain contains a mixture of disordered normal-liquid structure (DNLS) and LFTS. The model showed that the LFTS and DNLS populations change with applied temperature. Above ∼300 K, all local water structures become a DNLS. The population of LFTS increases with cooling and becomes dominant below ∼250 K. At ∼225 K, all local water structures converge to LFTS. The phase-transition rate of the low-entropy water clusters and small bulk water domains increases significantly at ∼235 K. The phase transition of the low-entropy water clusters showed primary ice nucleation. Low-entropy water clusters in a hydrophobic solvent are a unique water morphology and a probe material for water investigations.

Long-lived water clusters in hydrophobic solvents investigated by standard NMR techniques.

Unusual physical characteristics of water can be easier explained and understood if properties of water clusters are revealed. Experimental investigation of water clusters has been reported by highly specialized equipment and/or harsh experimental conditions and has not determined the properties and the formation processes. In the current work, we used standard 1H-NMR as a versatile and facile tool to quantitatively investigate water clusters in the liquid phase under ambient conditions. This approach allows collection of data regarding the formation, long lifetime, stability, and physical properties of water clusters, as a cubic octamer in the liquid phase.

Plasma Modification and Synthesis of Membrane Materials-A Mechanistic Review.

Although commercial membranes are well established materials for water desalination and wastewater treatment, modification on commercial membranes is still necessary to deliver high-performance with enhanced flux and/or selectivity and fouling resistance. A modification method with plasma techniques has been extensively applied for high-performance membrane production. The paper presents a mechanistic review on the impact of plasma gas and polymerization, at either low pressure or atmospheric pressure on the material properties and performance of the modified membranes. At first, plasma conditions at low-pressure such as plasma power, gas or monomer flow rate, reactor pressure, and treatment duration which affect the chemical structure, surface hydrophilicity, morphology, as well as performance of the membranes have been discussed. The underlying mechanisms of plasma gas and polymerization have been highlighted. Thereafter, the recent research in plasma techniques toward membrane modification at atmospheric environment has been critically evaluated. The research focuses of future plasma-related membrane modification, and fabrication studies have been predicted to closely relate with the implementation of the atmospheric-pressure processes at the large-scale.

Decoupling order and conductivity in doped conducting polymers.

Herein it is demonstrated that the high level of interchain ordering of pEDOT is not necessary for the polymer to have efficient charge transport. Resistance and order are compared during the manufacturing process, where the polymerisation step and ordering step are decoupled as separate stages of the processing. GIWAXS experiments measuring interchain order are correlated to resistivity measurements at multiple stages of the manufacturing process on single films, and it is shown that for an individual film, where percolation is achieved, having a long range ordered system offers no reduction in resistance compared to having a highly disordered state of the same film. For this system, once the chains of pEDOT are formed, it is experimentally demonstrated that for percolation to be achieved, a remarkably low 4.5% volume fraction pEDOT is required. The apparent lack of necessity for significant interchain ordering allows for a meaningful measurement of development of the charge transport during the chemical polymerisation process.

In vivo comparison of the charge densities required to evoke motor responses using novel annular penetrating microelectrodes.

Electrodes for cortical stimulation need to deliver current to neural tissue effectively and safely. We have developed electrodes with a novel annular geometry for use in cortical visual prostheses. Here, we explore a critical question on the ideal annulus height to ensure electrical stimulation will be safe and effective. We implanted single electrodes into the motor cortex of anesthetized rats and measured the current required to evoke a motor response to stimulation, and the charge injection capacity (CIC) of the electrodes. We compared platinum iridium (PtIr) electrodes with different annulus heights, with and without a coating of porous titanium nitride (TiN). Threshold charge densities to evoke a motor response ranged from 12 to 36 µC.cm(-2).ph(-1). Electrodes with larger geometric surface areas (GSAs) required higher currents to evoke responses, but lower charge densities. The addition of a porous TiN coating did not significantly influence the current required to evoke a motor response. The CIC of both electrode types was significantly reduced in vivo compared with in vitro measurements. The measured CIC was 72 and 18 µC.cm(-2).ph(-1) for electrodes with and without a TiN coating, respectively. These results support the use of PtIr annular electrodes with annulus heights greater than 100 µm (GSA of 38, 000 µm(2)). However, if the electrodes are coated with porous TiN the annulus height can be reduced to 40 µm (GSA of 16,000 µm(2)).

In vivo comparison of the charge densities required to evoke motor responses using novel annular penetrating microelectrodes.

Electrodes for cortical stimulation need to deliver current to neural tissue effectively and safely. We have developed electrodes with a novel annular geometry for use in cortical visual prostheses. Here, we explore a critical question on the ideal annulus height to ensure electrical stimulation will be safe and effective. We implanted single electrodes into the motor cortex of anesthetized rats and measured the current required to evoke a motor response to stimulation, and the charge injection capacity (CIC) of the electrodes. We compared platinum iridium (PtIr) electrodes with different annulus heights, with and without a coating of porous titanium nitride (TiN). Threshold charge densities to evoke a motor response ranged from 12 to 36 µC.cm(-2).ph(-1). Electrodes with larger geometric surface areas (GSAs) required higher currents to evoke responses, but lower charge densities. The addition of a porous TiN coating did not significantly influence the current required to evoke a motor response. The CIC of both electrode types was significantly reduced in vivo compared with in vitro measurements. The measured CIC was 72 and 18 µC.cm(-2).ph(-1) for electrodes with and without a TiN coating, respectively. These results support the use of PtIr annular electrodes with annulus heights greater than 100 µm (GSA of 38, 000 µm(2)). However, if the electrodes are coated with porous TiN the annulus height can be reduced to 40 µm (GSA of 16,000 µm(2)).

Amine Enrichment of Thin-Film Composite Membranes via Low Pressure Plasma Polymerization for Antimicrobial Adhesion.

Thin-film composite membranes, primarily based on poly(amide) (PA) semipermeable materials, are nowadays the dominant technology used in pressure driven water desalination systems. Despite offering superior water permeation and salt selectivity, their surface properties, such as their charge and roughness, cannot be extensively tuned due to the intrinsic fabrication process of the membranes by interfacial polymerization. The alteration of these properties would lead to a better control of the materials surface zeta potential, which is critical to finely tune selectivity and enhance the membrane materials stability when exposed to complex industrial waste streams. Low pressure plasma was employed to introduce amine functionalities onto the PA surface of commercially available thin-film composite (TFC) membranes. Morphological changes after plasma polymerization were analyzed by SEM and AFM, and average surface roughness decreased by 29%. Amine enrichment provided isoelectric point changes from pH 3.7 to 5.2 for 5 to 15 min of plasma polymerization time. Synchrotron FTIR mappings of the amine-modified surface indicated the addition of a discrete 60 nm film to the PA layer. Furthermore, metal affinity was confirmed by the enhanced binding of silver to the modified surface, supported by an increased antimicrobial functionality with demonstrable elimination of E. coli growth. Essential salt rejection was shown minimally compromised for faster polymerization processes. Plasma polymerization is therefore a viable route to producing functional amine enriched thin-film composite PA membrane surfaces.

Adsorption of cationic polyacrylamide at the cellulose-liquid interface: a neutron reflectometry study.

The layer thickness and density of high molecular weight cationic polyacrylamide (CPAM) adsorbed at the cellulose-water interface was quantified by neutron reflectometry. The thickness of a full monolayer of CPAM of constant molecular weight (13 MD) but different charge densities, adsorbed with or without NaCl (10(-3) M), was studied. Thin cellulose films (40±7 Å) of roughness <10 Å were produced by spin coating a cellulose acetate-acetone solution and regenerating by alkaline hydrolysis. Film smoothness was greatly improved by controlling the concentration of cellulose acetate (0.13 wt%) and the hydrolysis time in sodium methoxide. The adsorption thickness of CPAM (40% charge 13 MD) at the solid-D2O interface was 43±4 Å on cellulose and 13±2 Å on silicon, an order of magnitude smaller than the CPAM radius of gyration. At constant molecular weight, the thickness of the CPAM layer adsorbed on cellulose increases with polymer charge density (10±1 Å at 5%). Addition of 10(-3) M NaCl decreased the thickness of CPAM layer already adsorbed on cellulose. However, the adsorption layer on cellulose of a CPAM solution equilibrated in 10(-3) M NaCl is much thicker (89±11 Å for 40% CPAM). For high molecular weight CPAMs adsorbed from solution under constant conditions, the adsorption layer can be varied by 1 order of magnitude via control of the variables affecting electrostatic intra- and inter-polymer chain interactions.

A conductive stretchable PEDOT-elastomer hybrid with versatile processing and properties.

Herein we describe the use of vapour phase polymerisation (VPP) to form an elastomeric conducting hybrid, via the combination of poly(3,4-ethylene dioxythiophene) (PEDOT) and poly(glycerol sabecate) (PGS). The extent of PGS curing inversely affected the degree of PEDOT penetration in the material. At longer cure times, samples exhibited a negligible strain-resistance relationship. However, by reducing cure times and allowing greater penetration of PEDOT into PGS, more stable properties were observed over repeated deformation. The isolation of the PEDOT towards the surface allowed the use of laser engraving to pattern conducting tracks with ease. Such a benefit points to its potential for uninvolved, rapid manufacture of electrode arrays for biomedical devices or to allow precision cell interaction in tissue engineering.

Miniaturisation and simplification of solid-state proton activity sensors for non-aqueous media and ionic liquids.

This work is the further development of the previous pH (effective) sensor work where a biologically derived proton-active redox centre - riboflavin (RFN) - was entrapped into a vapour phase polymerised poly(3,4-ethylenedioxythiophene) film and ferrocene (Fc) dissolved in the sample solution was used as an internal reference redox couple. Here, we report a disposable solid state pH (effective) sensor where we successfully incorporated both RFN and Fc into a single solid state electrode. The electrodes were then used for pH (effective) sensing where water is not required. The system was further miniaturised and simplified from a 3 electrode to a 2 electrode setup with the working electrode area being as small as 0.09 mm(2). The sensors show the ability to measure pH (effective) in both aqueous and non-aqueous media including ionic liquids (ILs) regardless of their hydrophobicity. This is an important step towards the ability to customise ILs or non-aqueous media with suitable proton activity (PA) for various applications e.g. customised ILs for biotechnological applications such as protein preservation and customised media for PA dependent reactions such as catalytic reactions.

Exploring zinc coordination in novel zinc battery electrolytes.

The coordination of zinc ions by tetraglyme has been investigated here to support the development of novel electrolytes for rechargeable zinc batteries. Zn(2+) reduction is electrochemically reversible from tetraglyme. The spectroscopic data, molar conductivity and thermal behavior as a function of zinc composition, between mole ratios [80 : 20] and [50 : 50] [tetraglyme : zinc chloride], all suggest that strong interactions take place between chloro-zinc complexes and tetraglyme. Varying the concentration of zinc chloride produces a range of zinc-chloro species (ZnClx)(2-x) in solution, which hinder full interaction between the zinc ion and tetraglyme. Both the [70 : 30] and [50 : 50] mixtures are promising electrolyte candidates for reversible zinc batteries, such as the zinc-air device.

Engineering hydrophilic conducting composites with enhanced ion mobility.

Ion mobility has a direct influence on the performance of conducting polymers in a number of applications as it dictates the operational speed of the devices. We report here the enhanced ion mobility of poly(3,4-ethylene dioxythiophene) after incorporation of gelatin. The gelatin-rich domains were seen to provide an ion pathway through the composites.

Alcohol vapour detection at the three phase interface using enzyme-conducting polymer composites.

Immobilisation of enzymes on a breathable electrode can be useful for various applications where the three-phase interface between gas or chemical vapour, electrolyte and electrode is crucial for the reaction. In this paper, we report the further development of the breathable electrode concept by immobilisation of alcohol dehydrogenase into vapour-phase polymerised poly(3,4-ethylene dioxythiophene) that has been coated onto a breathable membrane. Typical alcohol sensing, whereby the coenzyme ß-Nicotinamide adenine dinucleotide (NADH) is employed as a redox-mediator, was successfully used as a model reaction for the oxidation of ethanol. This indicates that the ethanol vapour from the backside of the membrane has access to the active enzyme embedded in the electrode. The detecting range of the sensor is suitable for the detection of ethanol in fruit juices and for the baseline breath ethanol concentration of drunken driving. After continuous operation for 4.5h the system only showed a 20% decrease in the current output. The electrodes maintained 62% in current output after being refrigerated for 76 days. This work is continuing the progress of the immobilisation of specific enzymes for certain electrochemical reactions whereby the three-phase interface has to be maintained and/or the simultaneous separation of gas from liquid is required.

PdNi hollow nanoparticles for improved electrocatalytic oxygen reduction in alkaline environments.

Palladium-nickel (PdNi) hollow nanoparticles were synthesized via a modified galvanic replacement method using Ni nanoparticles as sacrificial templates in an aqueous medium. X-ray diffraction and transmission electron microscopy show that the as-synthesized nanoparticles are alloyed nanostructures and have hollow interiors with an average particle size of 30 nm and shell thickness of 5 nm. Compared with the commercially available Pt/C or Pd/C catalysts, the synthesized PdNi/C has superior electrocatalytic performance towards the oxygen reduction reaction, which makes it a promising electrocatalyst for alkaline anion exchange membrane fuel cells and alkali-based air-batteries. The electrocatalyst is finally examined in a H2/O2 alkaline anion exchange membrane fuel cell; the results show that such electrocatalysts could work in a real fuel cell application as a more efficient catalyst than state-of-the-art commercially available Pt/C.

Unexpected interaction between PEDOT and phosphonium ionic liquids.

In-situ-polymerized films of poly(3,4-ethylenedioxythiophene) (PEDOT) are known to be relatively ordered materials and maintain this order under changing chemical and electrochemical conditions. It is therefore surprising that certain ionic liquids (ILs) were found to interact with PEDOT and thereby to a large extent disrupt the ordered structure. The current work demonstrates the expansion of the interlayer distance (d100) of PEDOT and the composite of PEDOT with poly(ethyleneglycol) (PEDOT(PTS):PEG) in the presence of IL mixtures containing triisobutylmethylphosphonium tosylate (P1444PTS) and water. In presence of the mixtures, the PEDOT(PTS):PEG film expands up to ~100% while the PEDOT(PTS) film expanded ~50%. The expansion did not increase the electrical resistance but increased the absorption in the π-π* range, which can be explained by increased shielding of the PEDOT chains by the IL. The incorporation of P1444PTS increased the capacitance by 350%, compared to the theoretical capacitance of PEDOT(PTS), due to the formation of additional double-layer capacitance.

Chelating ionic liquids for reversible zinc electrochemistry.

Advanced, high energy-density, metal-air rechargeable batteries, such as zinc-air, are of intense international interest due to their important role in energy storage applications such as electric and hybrid vehicles, and to their ability to deal with the intermittency of renewable energy sources such as solar and wind. Ionic liquids offer a number of ideal thermal and physical properties as potential electrolytes in such large-scale energy storage applications. We describe here the synthesis and characterisation of a family of novel "chelating" ILs designed to chelate and solubilize the zinc ions to create electrolytes for this type of battery. These are based on quaternary alkoxy alkyl ammonium cations of varying oligo-ether side chains and anions such as p-toluene sulfonate, bis(trifluoromethylsulfonyl)amide and dicyanoamides. This work shows that increasing the ether chain length in the cation from two to four oxygens can increase the ionic conductivity and reduce the melting point from 67 °C to 15 °C for the tosylate system. Changing the anion also plays a significant role in the nature of the zinc deposition electrochemistry. We show that zinc can be reversibly deposited from [N(222(20201))][NTf2] and [N(222(202020201))][NTf2] beginning at -1.4 V and -1.7 V vs. SHE, respectively, but not in the case of tosylate based ILs. This indicates that the [NTf2] is a weaker coordinating anion with the zinc cation, compared to the tosylate anion, allowing the coordination of the ether chain to dominate the behavior of the deposition and stripping of zinc ions.

A solid-state pH sensor for nonaqueous media including ionic liquids.

We describe a solid state electrode structure based on a biologically derived proton-active redox center, riboflavin (RFN). The redox reaction of RFN is a pH-dependent process that requires no water. The electrode was fabricated using our previously described 'stuffing' method to entrap RFN into vapor phase polymerized poly(3,4-ethylenedioxythiophene). The electrode is shown to be capable of measuring the proton activity in the form of an effective pH over a range of different water contents including nonaqueous systems and ionic liquids (ILs). This demonstrates that the entrapment of the redox center facilitates direct electron communication with the polymer. This work provides a miniaturizable system to determine pH (effective) in nonaqueous systems as well as in ionic liquids. The ability to measure pH (effective) is an important step toward the ability to customize ILs with suitable pH (effective) for catalytic reactions and biotechnology applications such as protein preservation.