A review of pH measurement at high temperatures

Measurement of pH in aqueous solutions at up to 300 degrees and 150-300 bar is reviewed. Potentiometric membrane electrodes are identified as the sensors giving the most immediate hope of being practical. Zirconia membranes work well above 200 degrees and in alkaline solution, whereas glass membranes are best up to 150 degrees and in acidic solutions. Both membranes are largely free from interferences. Metal-metal oxide electrodes offer poor prospects, deviating from the ideal Nernstian response at all temperatures and being susceptible to interference from many redox and complexing agents, but systems based on iridium oxide have some promise. The hydrogen electrode remains the standard for pH measurement, but its analytical application is limited by the need to know the hydrogen partial pressure. A practical solution to this problem has yet to be found, except in restricted and artificial circumstances. Palladium hydride electrodes may be useful up to about 200 degrees , but in hydrogen-saturated waters revert to being hydrogen electrodes in any case. Non-potentiometric pH measurements with semiconducting oxides have been shown to be possible, but there are many unanswered questions about possible interferences. Considerable extra instrumentation is required, compared with potentiometry. Fibre-optic sensors based on indicator dyes have been investigated at room temperature, and have the great merit of not requiring a reference electrode. They seem, however, prone to many interferences and have an inherently limited working range of approximately 2 pH. No measurements at high temperature have been reported. Improved reference electrodes for potentiometric systems are still needed, although there have been advances in the design of external pressure-compensated electrodes working at room temperature. The silver-silver chloride system is still the one most favoured. There has been little rigorous work on standard buffer solutions at above 100 degrees and none at above 200 degrees . Neutral and alkaline buffers are especially needed. The establishment of proper pH standards for high-temperature work would make the testing of sensors both speedier and more reliable. Doubtless because of the experimental difficulties involved, few measurements have actually been made at high temperature, and those in a rather restricted range of conditions. In particular, measurements in dilute, poorly buffered, solutions, which provide the most rigorous test of a system's capability, are completely lacking.     

Oxygen diffusion in poly(methyl methacrylate) at low temperatures

Oxygen diffusion in atactic poly(methyl methacrylate) has been studied by anthracene luminescence quenching in geminate pairs anthracene-oxygen at 77–130 K. Analysis of the experimental data shows that the luminescence quenching is well accounted for by a polychromatic model assuming a log-normal diffusion coefficients distribution due to inhomogeneity of polymer structure. Energy activation is equal to 30 ± 1 KJ/mol. All diffusion coefficients data in the range 77–300 K demonstrate a good linear Arrhenius law. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 127–131, 1998     

UV-curable low-surface-energy fluorinated poly(urethane-acrylate)s for biomedical applications

Novel UV-curable fluorinated poly(urethane-acrylate) (FPUA) oligomers have been synthesized from 1H,1H,12H,12H-perfluoro-1,12-dodecanediol (PFDDOL), either 1,6-hexamethylene diisocyanate (HDI) or 4,4′-diphenylmethane diisocyanate (MDI), and 2-hydroxyethyl methacrylate (HEMA) for end-capping with photo-crosslinkable methacrylate groups. The fluorine content and the nature of the isocyanate were investigated to determine their effects on the physical properties, surface properties, and blood compatibilities of the polymers. The introduction of hydrophobic fluorocarbon chains led to phase separation and a low total surface energy, which reduced the adhesion of blood platelets onto the materials. The HDI-type UV-curable, fluorinated poly(urethane-acrylate) exhibited a low-surface-energy and superior blood compatibility (as determined from RIPA values).     

Photocrosslinkable polyesters and poly(ester anhydride)s for biomedical applications

Crosslinking is a feasible way to prepare biodegradable polymers with potential in biomedical applications such as controlled release of active agents and tissue engineering. A synthesis route in which functional telechelic aliphatic polyester oligomers are used as precursors for the preparation of crosslinked polyesters and poly(ester anhydride)s is described. Mechanical properties, degradation characteristics and rate, and bioactivity can be modified widely by controlling the chemical composition and architecture of the crosslinkable oligomers. In tissue engineering, photocrosslinking allows to use crosslinkable oligomers in advanced manufacturing techniques like micromolding in capillaries, stereolithography and two-photon polymerization.     

A theory for environmental craze yielding of polymers at low temperatures

It has been recently discovered that polymers craze at low temperatures in the presence of nitrogen or argon. A quantitative theory has been developed which explains (1) the critical temperature above which the phenomenon disappears, (2) the critical stress for nucleating a craze, (3) the effect of strain rate on the yield point and size of crazes, (4) the drop in the load during craze yielding, and (5) the increase in strength of the polymer in N₂ or Ar at high strain rates so that the ultimate strength may exceed that in He or vacuum. The crazing action of the gases is described qualitatively at the molecular level.     

Sorption of oxygen by glassy poly(ethyl methacrylate) at low temperatures

The solubility of molecular oxygen in glassy poly(ethyl methacrylate) at 160–308 K and a gas pressure from 50 kPa to 1.7 MPa is studied. The kinetics of desorption of O₂ molecules from films in vacuum at 175 K is investigated at various initial gas concentrations in the glass. It is shown that the dependences of concentration of the dissolved oxygen on temperature and pressure may be described if the intermolecular cavities in the glass are regarded as sorption sites and if the presence of distributions over the energies of insertion of the molecules into these sites are assumed. The same values of sorption-site concentrations and insertionenergy dispersions make it possible to describe both the solubility of the gas and the dependence of the desorption kinetics of oxygen on its initial concentration in the glass. The concentration of sites does not change with temperature throughout the studied temperature range and amounts to ~3.5×10²⁷ m^–3. The function of the distribution over energies is likewise independent of temperature and the concentration of oxygen in the glass up to ~6.5×10²⁶ m^–3 (at 160 K). The dispersion of energies is ~3.9 kJ/mol. The temperature independence of the concentration of sites is explained by the fact that the sizes of cavities in the glass change very weakly at temperatures below the glass-transition temperature.     

Reduction and oxidation of SrCoO(2.5) thin films at low temperatures

Brownmillerite SrCoO(2.5) (010) thin films synthesized by pulsed laser deposition became amorphous when reduced at low temperatures by CaH(2), indicating that the infinite-layer structure with the square planar Co(2+)O(4) configuration is unstable. Ferromagnetic and conducting perovskite SrCoO(3) epitaxial thin films, on the other hand, were obtained topotactically at room temperature by oxidation with NaClO.     

Dioxygen binding of water-soluble iron(II) porphyrins in phosphate buffer at room temperature

Two water-soluble tris(2-aminoethylamine) (tren) capped iron porphyrins were synthesized. The stability of their dioxygen adducts was studied in phosphate buffer, leading to half-life times around 7 min for the oxygenated species.     

Efficient CO oxidation at low temperature on Au(111)

The rate of CO oxidation to CO2 depends strongly on the reaction temperature and characteristics of the oxygen overlayer on Au(111). The factors that contribute to the temperature dependence in the oxidation rate are (1) the residence time of CO on the surface, (2) the island size containing Au-O complexes, and (3) the local properties, including the degree of order of the oxygen layer. Three different types of oxygen--defined as chemisorbed oxygen, a surface oxide, and a bulk oxide--are identified and shown to have different reactivity. The relative populations of the various oxygen species depend on the preparation temperature and the oxygen coverage. The highest rate of CO oxidation was observed for an initial oxygen coverage of 0.5 monolayers that was deposited at 200 K where the density of chemisorbed oxygen is maximized. The rate decreases when two-dimensional islands of the surface oxide are populated and further decreases when three-dimensional bulk gold oxide forms. Our results are significant for designing catalytic processes that use Au for CO oxidation, because they suggest that the most efficient oxidation of CO occurs at low temperature--even below room temperature--as long as oxygen could be adsorbed on the surface.     

A new class of azobenzene chelators for Mg and Ca in buffer at physiological pH

A new class of azobenzene-based chelators, trans-3a and trans-3b (3a and 3b), were designed and synthesized in two steps. Both 3a and 3b were readily dissolved in a buffer solution at physiological pH. The values of the dissociation constant of 3a and 3b for Mg²⁺ and Ca²⁺ were determined by the Hills plot; K_d^Mg=1.12 mM and K_d^Ca=660 μM for 3a and K_d^Mg=158 μM and K_d^Ca=200 μM for 3b, respectively. On irradiation at 489 nm light, 3a isomerized to give cis-form, which underwent cis-to-trans thermal isomerization in darkness at room temperature. The change in the absorption spectrum of the irradiated solution of 3a in the presence of Mg²⁺, showing the cis-to-trans thermal isomerization, indicates that the affinity of cis-3a for Mg²⁺ is lower than that of 3a.     

Self-assembly of poly(ethylene glycol)-based block copolymers for biomedical applications

Nanostructure fabrication from block copolymers is discussed in this review paper. Particularly, novel approaches for the construction of functionalized poly(ethylene glycol) (PEG) layers on surfaces were focused to attain the specific adsorption of a target protein through PEG-conjugated ligands with a minimal non-specific adsorption of other proteins. Furthermore, surface organization of block copolymer micelles with cross-linking cores was described from the standpoint of preparation of a new functional surface-coating with a unique macromolecular architecture. The micelle-attached surface and the thin hydrogel layer made by layered micelles exhibited non-fouling properties and worked as a reservoir for hydrophobic reagents. These PEG-functionalized surface in brush form or in micelle form can be used in diverse fields of medicine and biology to construct high-performance medical devices including scaffolds for tissue engineering and matrices for drug delivery systems.     

Excitation energy transfer in branched dendritic macromolecules at low (4 k) temperatures

To understand the mode of energy transport in branched dendritic macromolecules, the optical excitation of a dendritic core (A-DSB) at low temperature (4.2 K) was investigated. Fluorescence depolarization measurements were utilized to probe the energy-transfer processes in the branching center at several different temperatures. We found that the anisotropy decay shows an interesting trend at low temperature where depolarization times decreased and the residual anisotropy value also decreased with decreasing temperature. The very fast anisotropy decay suggests a coherent mechanism of energy transport in these systems at low temperature. The contribution of inhomogeneous broadening is suggested as an important factor in the temperature dependence of the anisotropy decay and residual value. The change in inhomogeneous linewidth is responsible for this type of anisotropy behavior.     

A review on electrospun nanofibers for multiple biomedical applications

Electrospinning is a well-known technique since 1544 to fabricate nanofibers using different materials like polymers, metals oxides, proteins, and many more. In recent years, electrospinning has become the most popular technique for manufacturing nanofibers due to its ease of use and economic viability. Nanofibers have remarkable properties like high surface-to-volume ratio, variable pore size distribution (10–100 nm), high porosity, low density, and are suitable for surface functionalization. Therefore, electrospun nanofibers have been utilized for numerous applications in the pharmaceutical and biomedical field like tissue engineering, scaffolds, grafts, drug delivery, and so on. In this review article, we will be focusing on the versatility, current scenario, and future endeavors of electrospun nanofibers for various biomedical applications. This review discusses the properties of nanofibers, the background of the electrospinning technique, and its emergence in chronological order. It also covers the various types of electrospinning methods and their mechanism, further elaborating the factors affecting the properties of nanofibers, and applications in tissue engineering, drug delivery, nanofibers as biosensor, skin cancer treatment, and magnetic nanofibers.     

Bio-friendly synthesis of ZnO nanoparticles in aqueous solution at near-neutral pH and low temperature

ZnO nanoparticles are synthesized using a new bio-friendly method. The experimental conditions are very mild: aqueous solution at near-neutral pH and 37 degrees C. The as-obtained nanoparticles show the stable wurtzite structure without the need of annealing. The two reagents used are aqueous solutions of zinc nitrate and buffer tris(hydroxymethyl)aminomethane. This is a standard nontoxic buffer and inert to a wide variety of chemicals and biomolecules, therefore extremely satisfactory for biochemical reactions. Furthermore, this is a polydentade ligand which adsorbs strongly on one or more surfaces of ZnO inhibiting its crystal growth and yielding nearly spherical ZnO nanoparticles. Our objective is to use the crystallization method described here for further incorporation of biomolecules as additives in the reaction solution, aiming at the formation of ZnO with new physical properties.     

A low-energy-consumption electroactive valveless hydrogel micropump for long-term biomedical applications

Stimuli-responsive hydrogels have attracted considerable interest in the field of microfluidics due to their ability to transform electrical energy directly into mechanical work through swelling, bending, and other deformations. In particular, electroactive hydrogels hold great promise for biomedical micropumping applications such as implantable drug delivery systems. In such applications, energy consumption rate and durability are key properties. Here, we developed a valveless micropump system that utilizes a hydrogel as the main actuator, and tested its performance over 6 months of continuous operation. The proposed micropump system, powered by a single 1.5 V commercial battery, expended very little energy (less than 750 μWs per stroke) while pumping 0.9 wt% saline solution under a low voltage (less than 1 V), and remained fully functional after 6 months. CFD simulations were conducted to improve the microchannel geometry so as to minimize the backflow caused by the valveless mechanism of the system. Based on the simulation results, an asymmetric geometry and a stop post were introduced to enhance the pumping performance. To demonstrate the feasibility of the proposed system as a drug delivery pump, an anti-cancer drug (adriamycin) was perfused to human breast cancer cells (MCF-7) using the pump. The present study showed that the proposed system can operate continuously for long periods with low energy consumption, powered by a single 1.5 V battery, making it a promising candidate for an implantable drug delivery system.     

Plasticizer-assisted bonding of poly(methyl methacrylate) microfluidic chips at low temperature

As an important phthalate plasticizer, dibutyl phthalate (DBP) was employed to decrease the bonding temperature of poly(methyl methacrylate) (PMMA) microfluidic chips in this work based on the fact that it can lower the glass transition temperature of PMMA. The channel plates of the PMMA microchips were fabricated by the UV-initiated polymerization of prepolymerized methyl methacrylate between a silicon template and a PMMA plate. Prior to bonding, DBP solution in isopropanol was coated on PMMA covers. When isopropanol in the coating was allowed to evaporate in air, DBP was left on the PMMA covers. Subsequently, the DBP-coated covers were bonded to the PMMA channel plates at 90 °C for 10 min under pressure. The channels in the complete microchips had been examined by optical microscope and scanning electron microscope. The results indicated that high quality bonding was achieved below the glass transition temperature of PMMA (∼105 °C). The performance of the PMMA microfluidic chips sealed by plasticizer-assisted bonding has been demonstrated by separating and detecting ionic species by capillary electrophoresis in connection with contactless conductivity detection.     

Lipid,protein and poly(NIPAM) coated mesoporous silica nanoparticles for biomedical applications

In the past decade, mesoporous silica nanoparticles (MSNs) as nanocarriers have showed much potential in advanced nanomaterials due to their large surface area and pore volume. Especially, more and more MSNs based nanodevices have been designed as efficient drug delivery systems (DDSs) or biosensors. In this paper, lipid, protein and poly(NIPAM) coated MSNs are reviewed from the preparation, properties and their potential application. We also introduce the preparative methods including physical adsorption, covalent binding and self-assembly on the MSNs' surfaces. Furthermore, the interaction between the aimed cells and these molecular modified MSNs is discussed. We also demonstrate their typical applications, such as photodynamic therapy, bioimaging, controlled release and selective recognition in biomedical field.     

Phase behavior at low temperature of poly(tetrafluoroethylene) by temperature-modulated calorimetry

Temperature modulated differential calorimetry (TMDSC) is used to examine the crystal-crystal transitions of poly(tetrafluoroethylene). This study gives new information about the dynamic thermal behavior of such transitions. The involvement of reversible and irreversible processes during the phenomenon is observed, which are related to the order-disorder changes occurring during the transition.This study adds a new example to the response of TMDSC during first order transitions.