Optical nanosensor design with uniform pore geometry and large particle morphology

Appropriate design of nanosensors for optically selective, sensitive sensing systems is needed for naked-eye detection of pollutants for environmental cleanup of toxic heavy-metal ions. Mesostructured materials with two- or three-dimensional (2D or 3D) geometries and large particle morphologies show promise as probe carriers, and can therefore be used to reproducibly fabricate uniformly packed nanosensors. This is the first report on the effects of significant key properties of the mesostructured carriers, such as morphology, geometry, and pore shape, on the functionality of optical nanosensor designs. Such mesostructured sensors with superior physical characteristics can be used as components in sensing systems with excellent stability and sensitivity, and with rapid detection response. The nanosensor design can enhance the selectivity even at low concentrations of the pollutant target ions (nanomolar level). Among the nanosensors developed here, the large pore-surface grains of highly ordered 3D monoliths (HOM) exhibited a high adsorption capability of the Pyrogallol Red probe and high accessibility to analyte ion transport, leading to possible naked-eye detection of Sb(III) ions at concentrations as low as 10(-9) mol dm(-3) and at a wide detection range of 0.5 ppb to 3 ppm. A key finding in our study was that our mesostructured nanosensor designs retained highly efficient sensitivity without a significant increase in kinetic hindrance, despite the slight decrease of the specific activity of the electron acceptor/donor strength of the probe functional group after several regeneration/reuse cycles. The results, in general, indicate that large-scale reversibility of optical nanosensors is feasible in such metal-ion sensing systems.     

Functionalized hexagonal mesoporous silica monoliths with hydrophobic azo-chromophore for enhanced Co(II) ion monitoring

We introduce here new optical strips for the colorimetric monitoring of Co(II) ions in an aqueous solution. The optical nanosensors were designed by direct immobilizing azo-chromophore with long hydrophobic tails onto hexagonal mesoporous silica monoliths (HOM-2). Although, azo-dye probe was used as signaling reporter for selective detection of the Co(II) analyte up to 10⁻⁶ mol/dm³ in solution, the tailoring of the Co(II) ion-sensing functionality was successfully manipulated up to 10⁻⁹ mol/dm³ with the incorporation of azo-chromophore into hexagonal mesoporous silica monoliths (HOM-2), which led to small, easy-to-use optical sensor strips. However, our simple design of colorimetric sensors is based on a physical adsorption of chemically responsive dyes onto HOM materials followed by stronger dye-analyte interactions in aqueous sensing systems. No elution of the probe molecules was evident with the addition of Co(II) analyte ions during the sensing process. The binding of Co(II) ions with probes led to the color change of nanosensors corresponding to the formation of the metal-chelate [Co(II)-Probe] ⁿ⁺ complexes. Results indicated that hexagonal nanosensors offer one-step and simple sensing procedures for both quantification and visual detection of Co(II) ions without the need for sophisticated instruments. However, the solid HOM-2 materials immobilized by the these indicator dyes, in principle, could be used as preconcentrators to yield high adsorption capacity and preconcentration efficiency, leading to simultaneously visual inspection and simple detection over a wide, adjustable range of Co(II) ions even at trace levels. For Co(II) ion selectivity assays, negligible changes in either the developed color or the reflectance intensities of the [Co-Probe] ⁿ⁺ complex were observed, despite the addition of competitive cations. Moreover, the hexagonal nanosensors are reversible and have the efficient potential to serve for multiple analyses. Hexagonal optical strips for the colorimetric monitoring of Co(II) ions in an aqueous solution was successfully fabricated. This strip enabled to create ion-sensitive responses with revisable, selective and sensitive recognitions of a wide range of detectable Co(II) ions down to sub-nanomolar (∼15×10⁻⁹ M) in rapid sensing responses (in the order of minutes) This special Festschrift for Professor Jaroniec.     

Speciation analysis of inorganic Sb(III) and Sb(V) ions by using mini column filled with Amberlite XAD-8 resin

The speciation of inorganic Sb(III) and Sb(V) ions in aqueous solution was studied. The adsorption behavior of Sb(III) and Sb(V) ions were investigated as iodo and ammonium pyrollidine dithiocarbamate (APDC) complexes on a column filled with Amberlite XAD-8 resin. Sb(III) and Sb(V) ions were recovered quantitatively and simultaneously from a solution containing 0.8 M NaI and 0.2 M H₂SO₄ by the XAD-8 column. Sb(III) ions were also adsorbed quantitatively as an APDC complex, but the recovery of the Sb(V)-APDC complex was found to be <10% at pH 5. According to these data, the concentrations of total antimony as Sb(III)+Sb(V) ions and Sb(III) ion were determined with XAD-8/NaI+H₂SO₄ and XAD-8/APDC systems, respectively. The Sb(V) ion concentration was calculated by subtracting the Sb(III) concentration found with XAD-8/APDC system from the total antimony concentration found with XAD-8/NaI+H₂SO₄ system. The developed method was applied to determine Sb(III) and Sb(V) ions in samples of artificial seawater and wastewater.     

A colorimetric and fluorometric dual-model assay for mercury ion by a molecule

The synthesis and sensing characteristics of a new class of colorimetric and fluorometric dual-modal probe for mercury ion are outlined. Judicious placement of two dithia-dioxa-aza macrocycles on the BODIPY chromophore generates this interesting molecule. A highly Hg2+-selective fluorescence enhancing property (>7-fold) in conjunction with a visible colorimetric change from purple to red-pink can be observed, leading to potential fabrication of both "naked-eye" and ratiometric fluorescent detection of Hg2+.     

Novel synthesis of graphene foils in mesostructured silica between hexagonal and lamellar phases

The mesostructured silica template between hexagonal and lamellar phases derived from self-assembled tetraethyl-ortho-silicate (TEOS) with uniform adsorption of iron-group metal ions provides an ideal environment for growing highly crystalline graphene foils at a low temperature.     

An electrochemical peptide-based Ara h 2 antibody sensor fabricated on a nickel(II)-nitriloacetic acid self-assembled monolayer using a His-tagged peptide

We report, for the first time, the use of a Ni(II)-nitriloacetic acid (NTA) self-assembled monolayer (SAM) in the fabrication of an electrochemical peptide-based (E-PB) sensor for detection of anti-Ara h 2 antibodies. We compared the performance of the sensor fabricated on a Ni(II)-NTA SAM using a His-tagged peptide with the sensor fabricated using the conventional approach via direct immobilization of a thiolated peptide. While both sensors responded only to the correct antibody in the presence of random antibodies, we observed differences between the sensors. Specifically, the detection limit of the His-tagged sensor was 1 pM, significantly lower than the 200 pM detection limit of the conventional thiolated sensor. More importantly, unlike our previously developed E-PB sensors, both sensors are regenerable and reusable. The thiolated sensor can be readily regenerated using guanidine hydrochloride; whereas the His-tagged sensor can be regenerated by direct displacement of the His-tagged probes using Ni(II) ions. Overall, our results show that both approaches are well-suited for E-PB sensor fabrication; more importantly, specific sensor properties such as detection limit and dynamic range can be tuned by simply using a different probe immobilization method.     

Colorimetric detection of Cu[II] cation and acetate, benzoate, and cyanide anions by cooperative receptor binding in new alpha,alpha'-bis-substituted donor-acceptor ferrocene sensors

New ferrocene derivatives bearing two donor-acceptor systems are capable of selectively sensing cations and anions by cooperative binding of the two alpha,alpha'-groups bonded to the ferrocene nucleus, thus permitting the naked-eye selective colorimetric detection of copper[II] cation and acetate, benzoate, or cyanide anions, which are ions of toxicological and biological relevance.     

Determination of antibilharzial antimony compounds by direct current, differential pulse, square-wave and alternating current anodic stripping voltammetry

A simple, rapid and sensitive method has been developed for the determination of Sb(III) in five antimonial antibilharzial drugs using anodic stripping voltammetry. The method is based on the reduction of Sb(III) on the HMDE, followed by a selected mode of oxidative sweep, i.e. direct current, differential pulse, square-wave or first harmonic alternating current sweep, using 2 mol/L HCl as a supporting electrolyte. Voltammograms for various sample concentrations in the range 3–47 ppb Sb(III) were recorded and the respective calibration graphs constructed. To overcome the expected effect of adsorption of surface active organic compounds on the mercury drop, the standard addition technique of Sb₂O₃ solution was applied to calculate the recoveries of all the tested antimonials. The method gave reproducible results within 2% and the limit of detection for all measurement modes was 3 ppb. SW and AC modes seem to achieve lower detection limits than the other two modes. The four modes proved to be of equal accuracy and precision.     

(Sn,Sb)O2-x基纳米结构厚膜材料气敏特性及机理

对采用水热合成技术所形成的纳米(Sn,Sb)O2 x晶粒结构、厚膜材料的气敏特性及其机理进行了研究,并采用XRD、TEM手段对纳米尺度的（Sn、Sb)O2 x晶粒的结构与表面效应及晶粒形态进行了表征.结果表明,当掺杂Sb5＋的浓度（摩尔分数xSb5＋)为（2.9～5.8)×10－6时,（Sn、Sb)O2 x纳米晶粒表面的电子缺陷浓度增大,增强了对气体的吸附能力,从而提高了对可燃性气体的灵敏度.同时可使晶粒保持短柱状的形态特征,对其灵敏度有一定的控制作用.     

Silica-based optical chemosensors for detection and removal of metal ions

Because some metal ions are highly toxic even at trace level, a constant demand of developing methods for monitoring and removing these metal ions is extremely urgent. Silica-based optical chemosensors are supposed as good alternatives to classical instrumental methods for detecting and adsorbing metal ions, due to their effect and lower price. Silica nanoparticles, silica gel and mesoporous silica are used as supporting platforms to fabricate optical chemosensors. They have certain properties containing high porosity and expectant adsorption capacity. Chromogenic-type and fluorogenic-type optical probes, such as azobenzene, naphthalimide and rhodamine, are grafted to the surface of silica-based materials by sol–gel reaction, the limit of detection, response time and selective properties of optical sensors are improved sequentially. In this paper, the articles of silica-based optical chemosensors are retrospected since 2008, describing silica-based optical sensors used for sensing metal ions. The sensing mechanism, optical phenomenon, detection limit, adsorption capacity and application are also reviewed.     

Determination of antibilharzial antimony compounds by direct current, differential pulse, square-wave and alternating current anodic stripping voltammetry

A simple, rapid and sensitive method has been developed for the determination of Sb(III) in five antimonial antibilharzial drugs using anodic stripping voltammetry. The method is based on the reduction of Sb(III) on the HMDE, followed by a selected mode of oxidative sweep, i.e. direct current, differential pulse, square-wave or first harmonic alternating current sweep, using 2 mol/L HCl as a supporting electrolyte. Voltammograms for various sample concentrations in the range 3–47 ppb Sb(III) were recorded and the respective calibration graphs constructed. To overcome the expected effect of adsorption of surface active organic compounds on the mercury drop, the standard addition technique of Sb₂O₃ solution was applied to calculate the recoveries of all the tested antimonials. The method gave reproducible results within 2% and the limit of detection for all measurement modes was 3 ppb. SW and AC modes seem to achieve lower detection limits than the other two modes. The four modes proved to be of equal accuracy and precision. Received: 9 October 1996 / Revised: 5 December 1996 / Accepted: 12 December 1996     

Critical review of bio/nano sensors for arsenic detection

Detection of arsenic is a long-standing challenge in environmental analytical chemistry. In recent years, using biomolecules and nanomaterials for sensing arsenic has been growingly reported. In this article, this field is critically reviewed based on some recent fundamental understandings including interactions between arsenic and gold, thiol, and DNA aptamers. First, taking advantage of the adsorption of As(III) on noble metal surfaces such as silver and gold, sensors were developed based on surface enhanced Raman spectroscopy, electrochemistry and colorimetry. In addition, by functionalizing metal nanoparticles with thiol containing molecules, As(III) induced aggregation of the particles based on As(III)/thiol interactions. As(V) interacts with metal oxides strongly and competitive sensors were developed by displacing pre-adsorbed DNA oligonucleotides. A DNA aptamer was selected for As(III) and many sensors were reported based on this aptamer, although careful binding measurements indicated that the sequence has no affinity towards As(III). Overall, bio/nano systems are promising for the detection of arsenic. Future work on fundamental studies, searching for more specific arsenic binding materials and aptamers, incorporation of sensors into portable devices, and more systematic test of sensors in real samples could be interesting and useful research topics.     

Synthesis and characterization of ordered hexagonal and cubic mesoporous tin oxides via mixed-surfactant templates route

Ordered hexagonal and cubic mesoporous tin oxides were synthesized for the first time in the presence of mixed cationic and neutral surfactants (a mixture of cetyltrimethylammonium bromide cationic surfactant and dodecylamine neutral surfactant) with different alkali and simple inorganic precursors at room temperature. In the synthesis systems, the dodecylamine neutral surfactant may function as a polar organic cosolvent and cosurfactant. The formation of the tin oxide mesostructured material was proposed to be due to the presence of hydrogen-bonding interactions between the supramolecular template and inorganic precursors Sn4+ and OH-, which were assumed to self-assemble around the cationic surfactant molecules. The materials are characterized by X-ray powder diffraction, transmission electron microscopy, thermogravimetric analysis, and N2 adsorption/desorption isotherm. The surface areas of materials evaluated from the N2 sorption isotherms are about 248 m(2)/g for hexagonal mesoporous tin oxide (SnH) and 281 m(2)/g for cubic mesoporous tin oxide (Sn-C) for calcination at 350 degrees C.     

A colorimetric probe for the selective naked-eye detection of Pb(II) ions in aqueous media

A new colorimetric molecular probe based on a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dye selectively binds Pb(II) ions in aqueous solutions, allowing for highly sensitive naked-eye detection.     

Nafion‐modified Carbon Based Sensor for Soil Potassium Detection

In the present investigation, we report a voltammetric sensor based on Nafion modified screen printed carbon ink functionalized with 4‐aminobenzo‐18‐crown‐6 ether for the detection of soil potassium. The potassium is one of the major nutrient elements required by the plants and is critical for the crop productivity. The selective and sensitive assay is based on recording change in current signal of a positively charged redox probe, hexammineruthenium(III)chloride in the absence and presence of K⁺ ion in solution. The sensing interface is highly stable and reproducible for detection of K⁺ ion a under a wide range of concentration 1 to 500 ppm. The detection sensitivity over a wide concentration range was achieved by altering the concentration of redox species. Mechanistically, the recognition properties of 4‐aminobenzo‐18‐Crown‐6 covalently bound to the Nafion on carbon surface was found to be selective for potassium ion over sodium, ammonium and calcium ion. Potassium recognition through host‐guest binding of crown ether derivative and proposed simplicity of fabrication protocol makes the systems highly promising for real‐time applications in soil analysis.     

Smart nano-architectures as potential sensing tools for detecting heavy metal ions in aqueous matrices

The discharge of heavy metal ions into water resources as a result of human activities has become a global issue. Contamination with heavy metal ions poses a major threat to the environment and human health. Therefore, there is a dire need to probe the presence of heavy metal ions in a more selective, facile, quick, cost-effective and sensitive way. Conventional sensors are being utilized to sense heavy metal ions; however, various challenges and limitations like interference, overlapping of oxidation potential, selectivity and sensitivity are associated with them that limit their in-field applicability. Hence, nanomaterial based chemical sensors have emerged as an alternative substitute and are extensively employed for the detection of heavy metal ions as a potent analytical tool. The incorporation of nanomaterials in sensors increases their sensitivity, selectivity, portability, on-site detection capability and device performance. Nanomaterial based electrodes exhibit enhanced performance because surface of electrode at nano-scale level offers high catalytic potential, large active surface area and high conductivity. Therefore, this review addresses the recent progress on chemical sensors based on different nanomaterials such as carbon nanotubes (CNTs), metal nanoparticles, graphene, carbon quantum dots and nanocomposites for sensing heavy metals ions using different sensing approaches. Furthermore, various types of optical sensors such as fluorescence, luminescence and colorimetry sensors have been presented in detail.     

Solid-phase extraction of antimony using chemically modified SiO2-PAN nanoparticles

A new analytical method using 1-(2-pyridylazo)-2-naphthol (PAN)-modified SiO2 nanoparticles as solid-phase extractant has been developed for the preconcentration of trace amounts of Sb(III) in different water samples. Conditions of the analysis such as preconcentration factor, effect of pH, sample volume, shaking time, elution conditions, and effects of interfering ions for the recovery of the analyte were investigated. The adsorption capacity of nanometer SiO2-PAN was found to be 186.25 micromol/g at optimum pH and the LOD (3sigma) was 0.60 microg/L. The extractant showed rapid kinetic sorption. The adsorption equilibrium of Sb(III) on nanometer SiO2-PAN was achieved in 10 min. Adsorbed Sb(III) was easily eluted with 4 mL 2 M hydrochloric acid. The maximum preconcentration factor was 62.20. The method was applied for the determination of trace amounts of Sb(III) in various water samples (tap, mineral water, and industrial effluents).     

A Stable Porous Anionic Metal–Organic Framework for Luminescence Sensing of Ln3+ Ions and Detection of Nitrobenzene

A hexagonal channel‐based porous anionic metal–organic framework was successfully constructed. IFMC‐3 is stable in air and acidic/basic aqueous solutions at room temperature, and constitutes a selective luminescent sensing material for Ln³⁺ ions and a recyclable probe for the sensitive detection of nitrobenzene.     

Optimizing integrated optical chips for label-free (bio-)chemical sensing

Label-free sensing is an important method for many (bio-)chemical applications in fields such as biotechnology, medicine, pharma, ecology and food quality control. The broad range of applications includes liquid refractive index sensing, molecule detection, and the detection of particles or cells. Integrated optics based on the use of waveguide modes offers a great potential and flexibility to tailor the sensor properties to these applications. In this paper, the results of a numerical study are presented, showing that this flexibility is founded on the many degrees of freedom that can be used for the integrated optical chip design, in contrast to other technologies such as those based on surface plasmon resonance, for which the materials' properties limit the range of choices. The applications that are explicitly considered and discussed include (1) bulk refractometry, (2) thin-layer sensing, for example biosensors monitoring molecular adsorption processes occurring within some 10 nm of the chip's surface, (3) thick-layer sensing with processes involving molecules or ions to be monitored within a sensing matrix extending to some 100 nm from the chip's surface, for example hydrogel-based layers and chemo-optically sensitive membranes, and (4) particle sensing with particles or, for example, biological cells to be monitored within probe volumes extending to some 1,000 nm from the chip's surface. The peculiarities for the different types of applications will be discussed, and suitable modeling methods presented. Finally, the application-specific design guidelines supplied will enable the optimization of various types of integrated optical sensors, including interferometers and grating-based sensors.     

Sm3+ Potentiometric Membrane Sensor as a Probe for Determination of Some Pharmaceutics

The increase use of ion sensors in the fields of environmental, agricultural, and medical analysis is stimulating analytical chemists to develop new sensors for fast, accurate, reproducible, and selective determination of various ions. In this study a new samarium membrane sensor was constructed and for the first time, it was applied as a probe in indirect determination of hyoscine, homatropine, and tramadol drugs in their pharmaceutical formulation. The proposed membrane sensor was constructed based on a membrane containing 2% sodium tetraphenyl borate (NaTPB) as an anionic additive, 63% dibutyl phthalate (DBP) as solvent mediator, 5% ionophore, and 30% poly(vinyl chloride) (PVC). The proposed Sm(III) electrode exhibits a Nernstian response of 19.35±0.2 mV per decade of samarium concentration, and has a lower detection limit of 1.0×10^?7 M. The linear range of the sensors was 1.0×10^?7–1.0×10^?1 M. It works well in the pH range of 3.0–8.0.