Calcium and zinc ion release from polyalkenoate cements formed from zinc oxide/apatite mixtures

Calcium and zinc ion release from hydroxyapatite-zinc oxide-poly(acrylic acid) (HAZnO-PAA) composite cements into deionised water was investigated as a function of HA content, PAA concentration, PAA molecular weight and maturation time. At any given maturation time, zinc ion release was constant until the HA content was at the maximum loading (60 wt%) resulting in the cement matrix breaking up, allowing exacerbated ion release. The calcium ion release increased with increased HA content in the composite until the maximum loading where the release drops off. Up to this point, the release of both ionic species was proportional to square root time for the initial 24 hour period, indicating that the release is diffusion controlled. In agreement with related data from conventional Glass Polyalkenoate Cements (GPCs), it is the concentration of the PAA, not the molecular weight, that influences ion release from these materials. However, unlike GPCs, the release of the active ions results in a pH rise in the deionised water, more conventionally seen with Bioglass and related bioactive glasses. It is this pH rise, caused by the ion exchange of Zn(2+) and Ca(2+) for H(+) from the water, leaving an excess of OH(-), that should result in a favourable bioactive response both in vitro and in-vivo.     

Metal ion release from metal implants

Metal ion release from metallic materials, e.g. stainless steel, cobalt–chromium alloy, titanium, and titanium alloys, implanted into human body was reviewed in this paper. Surface oxide films on metallic materials play an important role as an inhibitor of ion release and they change with the release in vivo. Low concentration of dissolved oxygen, inorganic ions, proteins, and cells may accelerate the metal ion release. The regeneration time of the surface oxide film after disruption also governs the amount of released ion. In addition, preferential release of specific elements during wear and fretting of metallic materials occurs. The behavior of metal ion release into biofluid is governed by the electrochemical rule. Released metal ions do not always combine with biomolecules to appear toxicity because active ion immediately combine with a water molecule or an anion near the ion to form an oxide, hydroxide, or inorganic salt. Thus, there is only a small chance that the ion will combine with biomolecules to cause cytotoxicity, allergy, and other biological influences.     

高氯酸盐离子新电极的建立

通过变性化学硅胶1,4-二氮杂双环[2,2,2]辛烷、环氧聚合物和碳混合,建立了高氯酸盐阴离子的电位响应。     

Nanostructured zinc oxide film for urea sensor

Nanostructured zinc oxide (Nano-ZnO) film has been electrochemically deposited onto indium-tin-oxide (ITO) coated glass plate to co-immobilized urease (Urs) and glutamate dehydrogenase (GLDH) for urea detection. The observed reflection planes corresponding to wurtzite ZnO nanoparticles (~25 nm) in XRD diffraction pattern and UV-visible absorption band at 338 nm reveal the formation of Nano-ZnO. Urs-GLDH/Nano-ZnO/ITO bioelectrode shows high sensitivity for urea detection within 10-80 mg/dL and limit of detection as 13.5 mg/dL with regression coefficient as 0.994 and Michaelis-Menten constant (K_m, 6.1 mg/dL) indicating good affinity of Urs-GLDH to urea.     

Improved zinc oxide film for gas sensor applications

Zinc oxide (ZnO) is a versatile material for different commercial applications such as transparent electrodes, piezoelectric devices, varistors, SAW devices etc because of its high piezoelectric coupling, greater stability of its hexagonal phase and its pyroelectric property. In fact, ZnO is a potential material for gas sensor applications. Good quality ZnO films were deposited on glass and quartz substrates by a novel CVD technique using zinc acetate as the starting solution. X-ray diffraction confirmed the crystallinity of the zinc oxide film and SEM study revealed uniform deposition of fine grains. Undoped ZnO films were used for detection of dimethylamine (DMA) and H₂ at different temperatures by recording the change in resistivity of the film in presence of the test gases. The response was faster and the sensitivity was higher compared to the earlier reported ZnO based sensors developed in our laboratory. The main objective of this work was to study the selectivity of the ZnO film for a particular gas in presence of the others. The operating temperature was found to play a key role in the selectivity of such sensors.     

Azamacrocycle activated quantum dot for zinc ion detection

A new fluorescent nanosensor family for Zn (2+) determination is reported based on azamacrocycle derivatization of CdSe/ZnS core/shell quantum dot nanoparticles. They are the first zinc ion sensors using QD nanoparticles in a host-guest and receptor-fluorophore system. Three azamacrocycles are demonstrated as receptors: TACN (1,4,7-triazacyclononane), cyclen (1,4,7,10-tetraazacyclododecane), and cyclam (1,4,8,11-tetraazacyclotetradecane). Azamacrocycles conjugated to QDs via an amide link interact directly with one of the photoinduced QD charge carriers, probably transferring the hole in the QD to the azamacrocycle, thereby disrupting the radiative recombination process. When zinc ion enters the aza-crown, the lone pair electrons of the nitrogen atom become involved in the coordination and the energy level is no longer available for the hole-transfer mechanism, switching on the QD emission and a dramatic increase of the fluorescence intensity results, allowing the detection of low concentrations of zinc ions. Using this operating principle, three zinc ion sensors based on CdSe-ZnS core-shell QD nanoparticles showed a very good linearity in the range 5-500 microM, with detection limits lower than 2.4 microM and RSDs approximately 3% ( n = 10). In addition, the versatility of the sensors was demonstrated, since different sizes (and colors) of QDs can be employed and will respond to zinc in a similar way. In a study of interferences, the zinc-sensitive QDs showed good selectivity in comparison with other physiologically important cations and other transition metals tested. The results from fetal calf serum and samples mimicking physiological conditions suggested very good applicability in the determination of zinc ion in physiological samples.     

Removal of zinc ion from water by sorption onto iron-based nanoadsorbent

Batch and column experiments were conducted to investigate zinc removal from dilute aqueous solution (i.e. effluent) by sorption onto synthetic nanocrystalline akaganéite. Due to favorite characteristics, this material was shown to be a promising inorganic adsorbent prepared in the laboratory, following a new method of synthesis-previously published. The effects of adsorbent amount, zinc concentration, solution pH value, ionic strength and temperature variation on the treatment process were mainly investigated during this study. Typical adsorption models were determined searching the mechanism of sorption while the bed depth-service time model was applied to column (with granular material) experiments.     

锌离子电容器正极材料研究进展

作为新型储能设备,水系锌离子电容器具有高功率密度、大能量密度、长循环寿命和高安全性等优异性能,在民用电子设备和军用电气化武器装备领域具有极高的应用前景,有望成为代替锂离子电池的新一代储能方案。本文系统梳理了活性炭正极材料、碳纳米管正极材料、石墨烯正极材料和生物质碳正极材料等碳基正极材料的储锌能力,总结了MXene正极材料在锌离子电容器领域的研究进展,归纳了过渡金属氧化物正极材料的锌离子储存性能,指出开发高容量、耐高压、耐低温正极材料的必要性与紧迫性。     

A fiber-optic fluorescence sensor for lithium ion in acetonitrile

A novel fiber-optic fluorescence sensor based on a controlled-release reagent for the determination of lithium ion in organic solvents is proposed. The fluorogenic indicator 2-(2-hydroxyphenyl)benzoxazole is contained in a mini-polyethylene tube as the reagent reservoir and is brought into contact with the analyte solution by diffusion across a poly(vinyl chloride) (PVC) membrane to form a strongly fluorescent complex at the membrane/solution interface. The fluorescence signals produced are measured via two joined optical fibers positioned closely to the backside of the PVC membrane for light illumination and collection. The sensor is useful for measuring Li+ at concentrations in acetonitrile ranging from 1.0 x 10(-6) to 1.0 x 10(-2) M with a detection limit of 3.0 x 10(-7) M. The steady-state response can be reached within seconds, and the signal changes are fully reversible. The sensor shows minimal interference effects from other alkali metal and alkaline earth metal cations and has good stability and durability when stored in acetonitrile solutions.     

一种基于脱氧核酶的铅离子电致化学发光传感器

本文设计了一种基于脱氧核酶(DNAzyme)检测Pb2+的电致化学发光(Electrocheluminescent,ECL)传感器。将对Pb2+特异性识别的DNAzyme通过金-巯键固定于金电极表面,并与标记有二氧化硅包埋的钌联吡啶(Ru-SNPs)的底物DNA链发生杂交,形成双链DNA(ds-DNA)传感器。Pb2+不存在时,由于Ru-SNPs靠近电极表面,产生强的ECL信号。当Pb2+存在时,DNAzyme催化底物链断裂,Ru-SNPs远离电极表面,导致ECL信号下降。实验结果表明ECL强度与Pb2+浓度在0.2-1.0 nmol/L范围内呈良好的线性关系,检测限可达0.04 nmol/L,其他二价金属离子对其基本无干扰。     

Asymmetric ion track nanopores for sensor technology. Reconstruction of pore profile from conductometric measurements

We reconstruct the profile of asymmetric ion track nanopores from an algorithm developed for conductometric measurements of symmetric nanopores. The validity of the reconstruction is supported by FESEM observations. Our analysis reveals that asymmetric pores fabricated by one-sided etching are funnel-like and not conical. The analysis provides the constriction diameter and the pore profile as a function of etching time. The reconstruction of the pore profile defines the starting conditions of asymmetric nanopores at breakthrough. The deviation from the conical shape is most pronounced at the pore tip. This critical zone dominates transport properties relevant to ion conductance, selectivity, current rectification, resistive pulse sensing and biosensors. The classical cone approximation used until now underestimates the tip diameter by a factor of two. As transport processes in nanopores depend in a highly nonlinear way on the constriction diameter the presented reconstruction must be taken into account when studying ionic and molecular transport processes in asymmetric pores.     

PEGylated zinc oxide nanoparticles induce apoptosis in pancreatic cancer cells through reactive oxygen species

In this study, the authors have successfully prepared the polyethylene glycol (PEG)‐coated zinc oxide nanoparticles (ZNPs) and studied its effect in pancreatic cancer cells. The authors have observed a nanosized particle with spherical shape. In this study, the authors have demonstrated the cytotoxic effect of ZNP and PZNP in PANC1 cells. To be specific, PZNP was more cytotoxic compared to that of ZNP in PANC1 cancer cells. The authors have further showed that apoptosis is the main mode of cytotoxic activity. It is worth noting that PEGylation of ZNP did not decrease the cell killing activity of zinc particles, whereas it further increases its anticancer effect in the pancreatic cancer cells. The authors have observed a significant upregulation of proapoptotic BAX while expression of antiapoptotic Bcl‐2 was significantly downregulated indicating the potent anticancer effect of zinc nanoparticles. Overall, PEGylation of ZNP could be an effective strategy to improve the stability, while at the same time, its anticancer activity could be enhanced for better therapeutic response.Inspec keywords: biomedical materials, drug delivery systems, tumours, toxicology, nanoparticles, cellular biophysics, drugs, nanomedicine, cancer, nanofabrication, zinc compounds, II‐VI semiconductorsOther keywords: pancreatic cancer cells, reactive oxygen species, polyethylene glycol‐coated zinc oxide nanoparticles, cytotoxic effect, cytotoxic activity, PEGylation, anticancer effect, PEGylated zinc oxide nanoparticle induce apoptosis, proapoptotic BAX upregulation, ZnO     

The antibacterial effects of zinc ion migration from zinc-based glass polyalkenoate cements

Zinc-based glass polyalkenoate cements have been synthesised and their potential use in orthopaedic applications investigated. Zinc ions were released from the materials in a rapid burst over the first 24 h after synthesis, with the release rate falling below detectable levels after 7 days. Cement-implanted bone samples were prepared and the released zinc was shown, using energy dispersive X-ray analysis, to penetrate from the cement into the adjacent bone by up to 40 μm. Finally, the cements exhibited antibacterial activity against Streptococcus mutans and Actinomyces viscosus that reflected the pattern of zinc release, with the inhibition of growth greatest shortly after cement synthesis and little or no inhibition measureable after 30 days.     

Quartz crystal microbalance sensor using ionophore for ammonium ion detection

Ionophore-based quartz crystal microbalance (QCM) ammonium ion sensors with a detection limit for ammonium ion concentrations as low as 2.2 microM were fabricated. Ionophores are molecules, which selectively bind a particular ion. In this study, one of the known ionophores for ammonium, nonactin, was used to detect ammonium ions for environmental in-situ monitoring of aquarium water for the first time. To fabricate the sensing films, poly(vinyl chloride) was used as the matrix for the immobilization of nonactin. Furthermore, the anionic additive, tetrakis (4-chlorophenyl) borate potassium salt and the plasticizer dioctyl sebacate were used to enhance the sensor properties. The sensor allowed detecting ammonium ions not only in static solution, but also in flowing water. The sensor showed a nearly linear response with the increase of the ammonium ion concentration. The QCM resonance frequency increased with the increase of ammonium ion concentration, suggesting a decreasing weight of the sensing film. The detailed response mechanism could not be verified yet. However, from the results obtained when using a different plasticizer, nitrophenyl octyl ether, it is considered that this effect is caused by the release of water molecules. Consequently, the newly fabricated sensor detects ammonium ions by discharge of water. It shows high selectivity over potassium and sodium ions. We conclude that the newly fabricated sensor can be applied for detecting ammonium ions in aquarium water, since it allows measuring low ammonium ion concentrations. This sensor will be usable for water quality monitoring and controlling.     

Controlling ion release from bioactive glass foam scaffolds with antibacterial properties

Bioactive glass scaffolds have been produced, which meet many of the criteria for an ideal scaffold for bone tissue engineering applications, by foaming sol-gel derived bioactive glasses. The scaffolds have a hierarchical pore structure that is very similar to that of cancellous bone. The degradation products of bioactive glasses have been found to stimulate the genes in osteoblasts. This effect has been found to be dose dependent. The addition of silver ions to bioactive glasses has also been investigated to produce glasses with bactericidal properties. This paper discusses how changes in the hierarchical pore structure affect the dissolution of the glass and therefore its bioactivity and rate of ion delivery and demonstrates that silver containing bioactive glass foam scaffolds can be synthesised. It was found that the rate of release of Si and Ca ions was more rapid for pore structures with a larger modal pore diameter, although the effect of tailoring the textural porosity on the rate of ion release was more pronounced. Bioactive glass scaffolds, containing 2 mol% silver, released silver ions at a rate that was similar to that which has previously been found to be bactericidal but not high enough to be cytotoxic to bone cells.     

Low energy ion trapping and gas release from nickel single crystals

A study has been made of the thermal release of helium implanted into randomly oriented nickel single crystals at 1 keV. The effects of dose, dose rate and implant temperature on post-bombardment gas evolution rate spectra have been investigated. On the basis of the spectra obtained a model for low energy helium trapping is suggested which is consistent with previously observed dose dependent trapping probability and explains the almost total inhibition of gas trapping observed at implant temperatures in excess of 450°C. The model is also used to explain the observed evolution rate maxima associated with release from small gas bubbles formed during annealing. The ultimate formation of the suggested gas bubbles has been shown to be strongly dependent on incident dose and co-incident with enhanced gas trapping.     

Fluorescence-based transient state monitoring for biomolecular spectroscopy and imaging

To increase read-out speed, sensitivity or specificity, an often applied strategy in fluorescence-based biomolecular spectroscopy and imaging is to simultaneously record two or more of the fluorescence parameters: intensity, lifetime, polarization or wavelength. This review highlights how additional, to-date largely unexploited, information can be extracted by monitoring long-lived, photo-induced transient states of organic dyes and their dynamics. Two major approaches are presented, where the transient state information is obtained either from fluorescence fluctuation analysis or by recording the time-averaged fluorescence response to a time-modulated excitation. The two approaches combine the detection sensitivity of the fluorescence signal with the environmental sensitivity of the long-lived transient states. For both techniques, proof-of-principle experiments are reviewed, and advantages, limitations and possible applications for biomolecular cellular biology studies are discussed.     

Piezoelectric quartz crystal microbalance sensor for trace aqueous cyanide ion determination

Using selective reaction chemistry, our present research has developed an online, real-time sensor capable of monitoring toxic cyanide at both drinking water standard and environmental regulatory concentrations. Through the use of a flow cell, aqueous samples containing cyanide are reacted with a gold electrode of a piezoelectric crystal to indirectly sense cyanide concentration by the dissolution of metallic gold. The quartz crystal is an AT-cut wafer sandwiched between two neoprene O-rings within the liquid flow cell. The presence of cyanide in solution results in the selective formation of a soluble dicyano-gold complex according to the Elsner reaction: 4Au + 8CN- + 2H2O + O2 <=> 4Au(CN)2- + 4OH-. The resulting loss of gold from the electrode is detected by the piezoelectric crystal as a resonant frequency change. Since free cyanide is a weak acid (pKa = 9.3), available protons compete for cyanide ligands. Therefore, increased sample pH provides higher sensitivity. The detection limits at pH 12 are 16.1 and 2.7 ppb for analysis times of 10 min and 1 h, respectively. The incorporation of the flow cell improves both analyte sensitivity and instrument precision, with an average signal intensity drift of only 5% over a 2-h analysis. The calibrations show excellent linearity over a variety of cyanide concentrations ranging from low ppb to hundreds of ppm. This detection method offers the advantage of selectively detecting cyanides posing a biohazard while avoiding detection of stable metal cyanides. This aspect of the system is based on competitive exchange of available metals and gold with cyanide ligands. Stable metal cyanide complexes possess a higher formation constant than cyanoaurate. This detection system has been configured into a flow injection analysis array for simple adaptation to automation. Anions commonly found in natural waters have been examined for interference effects. Additionally, the sensor is free from interference by aqueous cyanide analogues including thiocyanate. The developed detection system provides rapid cyanide determinations with little sample preparation or instrument supervision.     

Chemically deposited zinc oxide thin film gas sensor

Zinc oxide (ZnO) thin films were prepared by a low cost chemical deposition technique using sodium zincate bath. Structural characterizations by X-ray diffraction technique (XRD) and scanning electron microscopy (SEM) indicate the formation of ZnO films, containing 0.05–0.50 m size crystallites, with preferred c-axis orientation. The electrical conductance of the ZnO films became stable and reproducible in the 300–450 K temperature range after repeated thermal cyclings in air. Palladium sensitised ZnO films were exposed to toxic and combustible gases e.g., hydrogen (H₂), liquid petroleum gas (LPG), methane (CH₄) and hydrogen sulphide (H₂S) at a minimum operating temperature of 150 °C; which was well below the normal operating temperature range of 200–400 °C, typically reported in literature for ceramic gas sensors. The response of the ZnO thin film sensors at 150 °C, was found to be significant, even for parts per million level concentrations of CH₄ (50 ppm) and H₂S (15 ppm).     

Fluorescence-based peptide labeling and fractionation strategies for analysis of cysteine-containing peptides

This study demonstrates that 1,5-I-AEDANS (5-({2-[(iodoacetyl)amino]ethyl}amino)naphthalene-1-sulfonic acid) can be used as a versatile fluorescence-based peptide quantification tool and provides readily interpretable tandem mass spectra for de novo peptide sequencing. Two AEDANS-cysteinyl-peptide fractionation strategies were evaluated. One AEDANS-cysteinyl-peptide fractionation strategy employs immobilized metal affinity chromatography (IMAC) to recover AEDANS-labeled peptides and reduce the complexity of peptide mixtures. In an alternate solid-phase approach, 1,5-I-AEDANS was coupled to an o-nitrobenzyl-based photocleavable resin to produce a resin that can label and isolate thiols and cysteine-containing peptides with a modified-AEDANS label (mAEDANS: 5-((4-amino-4-oxobutanoyl){2-[(iodoacetyl)amino]ethyl}amino)naphthalene-1-sulfonic acid). This fractionation protocol enriches cysteine-containing peptides more specifically than the IMAC strategy. Using micro-LC-ESI-MS with an on-line fluorescence detector and a Q-TOF mass spectrometer, we generated fluorescence-based elution profiles and corresponding positive ion mass spectra of AEDANS-labeled peptides. This study demonstrates that AEDANS-peptides produce positive ion ESI-MS mass spectra with detection limits comparable to those of the unlabeled peptide. Collision-induced dissociation (CID) of fluorescent AEDANS-peptides revealed readily interpretable product ion spectra with the label intact. Similar to the AEDANS-labeled peptide, an mAEDANS-labeled thiol is fluorescent and CID of a mAEDANS-labeled peptide also reveals an interpretable product ion spectrum with the label intact.