Sol-gel derived potentiometric pH sensors

A potentiometric sol-gel derived (xerogel) pH sensor based on covalently attached amine groups is described. The sensor consists of a Ag/AgCl electrode coated with a hybrid aminosilane/alkylsilane xerogel film. Various combinations of aminosilanes and alkylsilanes are evaluated for their potentiometric response to pH. The optimal sensor design is composed of (aminoethylaminomethyl)phenethyltrimethoxysilane and methyltrimethoxysilane. This sensor exhibits near-Nerstian response (-55 mV.decade(-)(1)), responds rapidly (< or =3 s) to changes in pH, and has H(+) selectivity coefficients (log K(pot)(H)()+ (, )(j)()) of -13 and -11 for interfering j cations Na(+) and K(+), respectively. In vitro platelet adhesion tests indicate that the xerogel coatings are more blood compatible than conventional poly(vinyl chloride) and poly(urethane) ion-selective electrode coatings.     

释放一氧化氮聚合物研究进展

从制备、应用、一氧化氮的释放机制及影响一氧化氮释放的因素几个方面,综述了释放一氧化氮聚合物研究进展;分析了部分释放一氧化氮聚合物的优缺点。     

Xerogel optical sensor films for quantitative detection of nitroxyl

Xerogel sensing films were synthesized via sol-gel chemistry were used to fabricate optical nitroxyl (HNO) sensors [corrected] Selective detection of HNO in solution was achieved by monitoring the rates of manganese(III) meso-tetrakis(4-sulfonatophenyl) porphyrinate (MnIIITPPS) reductive nitrosylation in the anaerobic interior of aminoalkoxysilane-derived xerogel films. Nitroxyl permeability in sensor films deposited in round-bottom 96-well plates was enhanced via incorporation of trimethoxysilyl-terminated poly(amidoamine-organosilicon) dendrimers in the xerogel network. The selectivity of MnIIITPPS for HNO, the overall sensitivity, and the working dynamic range of the resulting sensors were characterized. The HNO-sensing microtiter plates were used to quantify pH-dependent HNO generation by the recently described HNO-donor sodium 1-(isopropylamino)diazene-1-ium-1,2-diolate (IPA/NO), and compare HNO production efficiency between IPA/NO and Angeli's salt, a traditional HNO-donor.     

Improving the thromboresistivity of chemical sensors via nitric oxide release: fabrication and in vivo evaluation of NO-releasing oxygen-sensing catheters

The development and in vivo analytical performance of a nitric oxide (NO)-releasing amperometric oxygen sensor with greatly enhanced thromboresistivity are reported. Gas permeable coatings formulated with cross-linked silicone rubber (SR) containing NO-generating compounds (diazeniumdiolates) are shown to release NO for extended periods of time (> 20 h) while reducing platelet adhesion and activation. Oxygen-sensing catheters prepared by dip-coating the NO-releasing films over the outer SR tubes of the implantable devices display similar analytical response properties in vitro (sensitivity, selectivity, response times) when compared to analogous sensors prepared without the NO release coatings. Superior analytical accuracy (relative to blood PO2 values measured in vitro) and greatly reduced thrombus formation on the outer surface of the sensors are observed in vivo (in canine model) with the NO release PO2 sensors compared to control sensors (without NO release) implanted simultaneously within the same animals. Based on these preliminary studies, the use of NO release polymers to fabricate catheter-style chemical sensors may be a potential solution to lingering biocompatibility and concomitant performance problems encountered when attempting to employ such devices for continuous intravascular measurements of blood gases and electrolytes.     

Sol-gel derived amperometric nitric oxide microsensor

An amperometric sol-gel derived nitric oxide microsensor is described. Several silicon-based xerogel membranes are evaluated to identify the optimum composition for maximizing NO permeability while providing sufficient selectivity for NO in the presence of common interfering species. Xerogel permeability and selectivity are further manipulated as a function of reaction/processing conditions. In addition, the effects of incorporating Nafion into the xerogel matrix on sensor performance and the stability of the ensuing xerogel/Nafion hybrid film are evaluated. The optimal permselective membrane is achieved by catalyzing polycondensation of the xerogel composed of methyltrimethoxysilane and (aminoethylaminomethyl)phenethyltrimethoxysilane and Nafion with NO gas. The resulting NO microsensor exhibits a sensitivity of 0.17 +/-0.02 pA/nM (from 25 to 800 nM, r = 0.9991), detection limit of 25 nM (S/N = 3), response time of 9 s (t(95%), a NO concentration change from 400 to 500 nM), selectivity (log K(NOj) amp) of -5.8, <-6, <-6, and <-6 for j = nitrite, ascorbic acid, uric acid, and acetaminophen, and a lifetime of 8 d (82% of initial sensitivity without serious deterioration in selectivity).     

Characterization of brown ferric oxide hydrate xerogel

Ferric chloride solution was neutralized using sodium hydroxide as the precipitant to the extent that the final pH of the suspension was 7. After thorough washing the precipitated gel was dried in air at 60° C for 24 h to yield brown ferric oxide hydrate xerogel. The xerogel was examined at room temperature using infrared (IR) spectroscopy, powder X-ray diffraction (XRD), electron optical measurements, magnetometry and Mössbauer resonance spectroscopy. It has been concluded that the structural, morphological and magnetic characteristics of the xerogel are identifiable with those of the protoferrihydrite phase.     

Nitric oxide-releasing electrospun polymer microfibers

The preparation of electrospun polymer microfibers with nitric oxide (NO)-release capabilities is described. Polymer solutions containing disodium 1-[2-(carboxylato)pyrrolidin-1-yl]diazen-1-ium-1,2-diolate (PROLI/NO), a low-molecular-weight NO donor, were electrospun to generate fibers ranging from 100-3000 nm in diameter capable of releasing NO upon immersion in aqueous solutions under physiological conditions (pH 7.4, 37 °C), with kinetics depending on polymer composition and fiber diameter. The NO release half-life for PROLI/NO-doped electrospun fibers was 2-200 times longer than that of PROLI/NO alone. The influence of polymer concentration, applied voltage, capillary diameter, solution conductivity, flow rate, and additives on fiber properties are reported and discussed with respect to potential applications.     

Nitric oxide-releasing sol-gel particle/polyurethane glucose biosensors

A hybrid sol-gel/polyurethane glucose biosensor that releases nitric oxide is developed and characterized. The biosensor consists of a platinum electrode coated with four polymeric membranes including the following: (1) sol-gel with immobilized glucose oxidase (GOx); (2) polyurethane to protect the enzyme; (3) NO donor-modified sol-gel particle-doped polyurethane; and (4) polyurethane. This configuration was developed due to the drastic reduction in sensitivity observed for NO donor-modified sol-gel film-based glucose sensors. For the hybrid sol-gel/polyurethane biosensor, sol-gel particles are first modified with the NO donor and then incorporated into a polyurethane layer that is coated onto the preimmobilized GOx electrode. In this manner, the GOx layer is not exposed to the harsh conditions necessary to impart NO release ability to the biosensor, and only a minimal decrease in sensitivity due to the NO release is observed. The glucose response of the NO-releasing glucose biosensor and its NO generation profiles are reported. In addition, the stability of the sol-gel particles in the supporting polyurethane membrane is discussed.     

Encapsulation of aromatic oxygen palladium phthalocyanine in silica xerogel and its optical limiting property

Metallophthalocyanines (MPc) exhibit, among many useful properties, the ability to protect sensors against short, intense pulse deleterious to efficient sensor operation. For the successful application of this optical limiting property, an important issue is the incorporation of MPc molecules in a matrix to fabricate a solid state system. We report here the study of different concentrations of aromatic oxygen palladium phthalocyanine (ArOPdPc) encapsulated in silica xerogel obtained by the sol–gel technique. The resulted composites were transparent and homogeneous with the required optical limiting properties. The trapping effect was confirmed by the characteristic absorption bands of ArOPcPd in the UV–Vis spectra. The optical limiting properties of the composites were measured at 532 nm with 8 ns pulses. The results showed that the composites had obviously optical limiting effect, owing to the existing of large amount of monomers and the introduction of palladium atom in the cavity of phthalocyanine ring.     

Profiling pH changes in the electrospray plume

Laser-induced fluorescence spectrometry is used to profile pH changes as droplets evaporate in an electrospray plume by measuring emission spectra of 2(or 4)-[10-(dimethylamino)-3-oxo-3H-benzo[c]xanthene-7-yl]-benzenedicarboxylic acid (carboxy SNARF-1), a pH-sensitive fluorescent dye. The observed pH changes depend on initial droplet pH and polarity. In some instances, small or negligible changes of pH are observed, consistent with expected buffering. The pH of initially acidic droplets decreases along the spray axis in both positive and negative ion modes, to an extent larger than expected from solvent evaporation. This phenomenon may be a manifestation of droplet cooling, droplet subdivision, or heterogeneous charge distribution within the spray plume or within individual ES droplets.     

Properties of xerogel layers for the detection of toluene in water

This paper presents results of experimental investigation of optical properties of xerogel layers applied on silica optical fibers and their sensitivity to toluene dissolved in water. Several types of layers, namely the layers prepared from sols based on tetraethoxysilane (TEOS), methyltriethoxysilane (MTES) and of a mixture of methyltriethoxysilane and phenyltriethoxysilane (MTES/PTES) were applied on the bare core of silica fibers by the dip-coating method. For comparison, thin layers of a polydimethylsiloxane (PDMS) polymer were also applied on the fibers from toluene solutions of the prepolymer.Properties of the layers were characterized by measuring angular distributions of optical power from the fiber and by time and spectral responses of the layers to toluene dissolved in water. The angular and time response characteristics were measured at 670 nm, the spectral changes were measured in a wavelength range of 1600–1800 nm. Inclined beams were used for fiber excitation in order to increase measurement accuracy.The experimental results obtained show that the MTES-based xerogel layer exhibits higher sensitivity to toluene dissolved in water than the PTES-based or TEOS-based one. With the MTES-based layers a detection limit of about 1 ppm (5 mg/l) was achieved. The spectral measurements provided experimental evidence of the presence of toluene in the layers.     

Real-time pH microscopy down to the molecular level by combined scanning electrochemical microscopy/single-molecule fluorescence spectroscopy

A new technique combining scanning electrochemical microscopy (SECM) and single-molecule fluorescence spectroscopy was developed to accomplish locally and temporally defined pH adjustments in buffer solutions and on surfaces monitored by fluorescence alteration of pH-sensitive fluorophores in real time. Local pH gradients were created by electrochemical generation of H(+) or OH(-) during redox reactions at ultramicro- or nanoelectrodes with radii from 5 microm to 35 nm. Ratiometric fluorescence measurements were performed with a confocal laser microscope using two detectors for different spectral regions. Time-resolved pH measurements were carried out with freely diffusing SNARF-1-dextran. For pH measurements on surfaces, total internal reflection fluorescence microscopy was used in combination with a CCD camera. The fluorophore SNAFL-succinimidyl ester was bound to amino-terminated octadecylsilane-coated coverslips. Local pH determinations could be accomplished with an accuracy of 0.2 unit. The measured pH profiles showed a strong dependence on the tip diameter, the buffer/mediator concentration ratio, and the tip-surface distance. As an application for bionanotechnology using SECM-induced pH changes on the molecular level, the proton-driven ATP synthesis by single membrane-bound F(0)F(1)-ATP synthases was investigated. ATP synthesis resulted in stepwise subunit rotation within the enzyme that was monitored by single-molecule fluorescence resonance energy transfer.     

Chemical and optical properties of dye-doped sol-gel films

Sol-gel silica coatings doped with an acid indicator were prepared and their behaviour vs pH in aqueous media were studied. Absorption spectroscopy was used to characterize the reversible optical response of doped films both in liquid and gaseous media. Several features such as: a) strong influence of acid concentration on films colour change, b) reversibility without fatigue all over the pH range, and c) spontaneous regain of initial basic absorption when coatings were sensitized under acid vapour; pointed out that dye molecules were incorporated in the surface of the silica films pores. On the other hand, coatings resistance vs alkaline attack showed that damage quickly proceeded if films surface were inhomogeneous, due to direct corrosion of the glass substrate.     

Replicated, high-aspect-ratio micro-optical components fabricated from inorganic solgel materials

A replication process for the fabrication of refractive microlenses from a purely inorganic solgel material based on tetraethoxysilane is presented. The geometrical dimensions and optical properties of the inorganic microlenses are characterized and compared with those of microlenses replicated in a hybrid xerogel containing organic additives. By a reduced solvent content in the sol composition, together with modifications in the replication process, it was possible to obtain inorganic xerogel lenses with exceptionally high sagittal height values of as much as 28 microm. Compared with the hybrid xerogel, the inorganic xerogel has the advantage of an absorption coefficient that is five times lower in the visible spectral range and exhibits optical transparency in the near-ultraviolet range for wavelengths down to 200 nm.     

Contact angle measurement on xerogel sensitive layer for optical fibre sensor

This paper deals with approach for the detection of chemical vapours based on refractive-index changes of a silica xerogel layer deposited as an optical cladding on the fibre core. The fibre is multimode fibre excited with an inclined collimated beam. The refractive-index changes are evaluated by means of changes of the output power at the end put of the fibre. The optical properties of the sensitive cladding (refractive index and absorption coefficient) can be obtained with modelisation program. The sensitivities of tetraethoxysilane (TEOS) and methyltriethoxysilane (MTEOS)-based xerogel layers to toluene and water are presented in the paper. The hydrophobicity of the two-xerogel layers and their surface-free energy has been determined with contact angle measurements. A correlation between optical detection results and contact angle measurements can be done.     

Tailored Synthesis of Nitric Oxide-Releasing Polyurethanes Using O-Protected Diazeniumdiolated Chain Extenders

Nitric oxide (NO) has been shown to exhibit significant anti-platelet activity and its release from polymer matrices has been already utilized to increase the biocompatibility of various blood-contacting devices. Herein, details of a new synthetic approach for preparing NO-releasing diazeniumdiolated polyurethanes (PU) are described. The method's utility is demonstrated by the incorporation of methoxymethyl- or sugar-protected pre-formed diazeniumdiolate moieties directly into chain extender diols which are then incorporated into the polyurethane backbone. This approach provides the ability to control the number of diazeniumdiolate groups incorporated into the polymer backbone, and hence the surface flux of NO that can ultimately be liberated from polymeric films prepared from the new PU materials. The method provides a means of covalently attaching diazeniumdiolate groups to polyurethanes in a form that resists dissociation of NO during processing but can be activated for spontaneous NO release via hydrolysis of the carbohydrate or methoxymethyl moieties under basic and acidic conditions, respectively.     

Aqueous deposition of calcium phosphates and silicate substituted calcium phosphates on magnesium alloys

Attempts were made to deposit homogeneous films of calcium phosphates (CaPs) on two magnesium alloy systems, AZ31 and Mg-4Y, through an aqueous phosphating bath method. The deposition of silicate substituted CaPs by this aqueous method was also explored as silicate substitution is believed to increase the bioactivity of CaPs. The effect of doped and undoped coatings on the in vitro degradation and bioactivity of both alloy systems was studied. FTIR and EDX confirmed the deposition of Ca, P, and Si on both alloys and the coatings appeared to consist primarily biphasic mixtures of hydroxyapatite and β-TCP. These largely inhomogeneous coatings, as observed by SEM, were not shown to have any significant effect on maintaining the physiological pH of the culture medium in comparison to the uncoated samples, as the pH remained approximately in the 8.4-8.7 range. Interestingly, despite similar pH profiles between the coated and uncoated samples, CaP coatings affected the degradation of both alloys. These doped and undoped calcium phosphate coatings were observed to decrease the degradation of AZ31 whereas they increased the degradation of Mg-4Y. In vitro studies on cell attachment using MC3T3-E1 mouse osteoblasts showed that between the uncoated alloys, Mg-4Y appeared to be the more biocompatible of the two. Silicate substituted CaP coatings were observed to increase the cell attachment on AZ31 compared to bare and undoped CaPs coated samples, but did not have as great of an effect on increasing cell attachment on Mg-4Y.     

等离子喷涂HA／Ti复合涂层研究

对等离子喷涂HA／Ti复合涂层进行模拟体液和体外细胞试验,以考察涂层的生物学性能．结果指出,涂层经模拟体液浸泡后,表面覆盖一层碳酸磷灰石(carbonate-apatite),这表明涂层具有良好的生物活性．粗糙的涂层表面易于形成碳酸磷灰石．模拟体液的浓度太小或pH值太大,均会导致碳酸磷灰石层不能在涂层表面形成．体外细胞试验显示,成骨细胞能在涂层表面紧密贴壁并正常生长,显示涂层具有优良的生物相容性．     

Fluorinated xerogel-derived microelectrodes for amperometric nitric oxide sensing

An amperometric fluorinated xerogel-derived nitric oxide (NO) microelectrode is described. A range of fluorine-modified xerogel polymers were synthesized via the cohydrolysis and condensation of alkylalkoxy- and fluoroalkoxysilanes. Such polymers were evaluated as NO sensor membranes to identify the optimum composition for maximizing NO permeability while providing sufficient selectivity for NO in the presence of common interfering species. By taking advantage of both the versatility of sol-gel chemistry and the "poly(tetrafluoroethylene)-like" high NO permselective properties of the xerogels, the performance of the fluorinated xerogel-derived sensors was excellent, surpassing all miniaturized NO sensors reported to date. In contrast to previous electrochemical NO sensor designs, xerogel-based NO microsensors were fabricated using a simple, reliable dip-coating procedure. An optimal permselective membrane was achieved by synthesizing xerogels of methyltrimethoxysilane (MTMOS) and 20% (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane (17FTMS, balance MTMOS) under acid-catalyzed conditions. The resulting NO microelectrode had a conical tip of approximately 20 microm in diameter and approximately 55 microm in length and exhibited sensitivities of 7.91 pA x nM (-1) from 0.2 to 3.0 nM (R (2) = 0.9947) and 7.60 nA x microM (-1) from 0.5 to 4.0 microM ( R (2) = 0.9999), detection limit of 83 pM (S/ N = 3), response time ( t 95%) of <3 s, and selectivity (log K NO, j (amp)) of -5.74, <-6, <-6, <-6, <-6, -5.84, and -1.33 for j = nitrite, ascorbic acid, uric acid, acetaminophen, dopamine, ammonia/ammonium, and carbon monoxide. In addition, the sensor proved functional up to 20 d, maintaining >or=90% of the sensor's initial sensitivity without serious deterioration in selectivity.     

Silica-chitosan hybrid coating on Ti for controlled release of growth factors

A hybrid material composed of a silica xerogel and chitosan was coated on Ti for the delivery of growth-factors. Fibroblast growth factor (FGF) and green fluorescence protein were incorporated into the coatings for hard tissue engineering. Silica was chosen as a coating material because of its high surface area as well as its good bioactivity. Chitosan provides mechanical stability and contributes to the control of the release rate of the growth factors. When the chitosan composition was 30% or more, the hybrid coating was stable physically and mechanically. The release of the growth-factors, observed in phosphate buffer solution at 37°C, was strongly dependent on the coating material. The hybrid coating containing FGF showed significantly improved osteoblast cell responses compared to the pure xerogel coating with FGF or the hybrid coating without FGF. These results indicate that the hybrid coating is potentially very useful in enhancing the bioactivity of metallic implants by delivering growth-factors in a controlled manner.