Fundamental and practical aspects in the design of nanoscaled SnO2 gas sensors: a status report

Gas sensors based on semiconducting materials have become of great interest to both sensor users and researchers. In this context, a huge number of publications have appeared in the literature which deal with metal oxide gas sensors, in general, and with the prototype material SnO₂, in particular. The amount of data published grows continuously and has led to a situation in which even experts in this field tend to lose an overview. The present review describes the reasons for this complexity and outlines unifying concepts to understand the huge amount of published, mostly empirical data. This leads to a comprehension of gas-sensing phenomena in both the application and research domains. Received: 7 December 1998 / Revised: 6 May 1999 / Accepted: 19 May 1999     

Utility of Acetylenedicarboxylate in Organic Synthesis

Although, recent reviews demonstrated intensively on the reactivity of dimethyl acetylenedicarboxylate (DMAD) in organic synthesis, its reactions have still get importance addition in that field. Moreover, and due to the huge amount of published literatures dealing with the reactions of DMAD, we are trying to give more focus on the important missed reactions in addition to give more light to updated publications. DMAD is an organic compound with the formula (C₆H₆O₄), and it is a diester in which the ester groups are conjugated with a triple bond. As such, DMAD is highly electrophilic and a widely employed as a dienophile in cycloaddition reactions, like the Diels–Alder reaction. Many organic compounds specially the heterocyclic ones were prepared via its reactions.     

Low temperature fluorescence studies of the deactivation of the bend—stretch manifold of CO2

Laser fluorescence has been used to measure rate constants for the vibrational of the bend—stretch manifold of CO₂ between 300 and 170 K. The technique employed a pulsed chemical CO laser to produce vibrationally excited CO. This was used in a collisional pumping scheme designed to deposit an excess of vibrational energy in the bend—stretch manifold of CO₂. The deactivation of this vibrational manifold has been studied using the following collisional partners: CO₂, Ar, Xe, N₂ and H₂. Our results are compared with the limited amount of other low temperature data which have been published and with data obtained using a shock tube in the temperature range of about 1000 to 400 K. The present low temperature and the published high temperature results extrapolate together smoothly and clearly show the large deviations from Landau—Teller behaviour which occur at low temperatures.     

Determining scaling in known phase diagrams of nonionic microemulsions to aid constructing unknown

Microemulsions based on nonionic surfactants of the ethylene oxide alkyl ether type C_mE_n, have been studied thoroughly for around 30 years. Thanks to the considerable amount of published data available on these systems, it is possible to observe trends to make predictions of phase diagrams not yet determined. Strey and Kahlweit, and subsequently Sottmann and Strey, with coworkers have studied and published phase diagrams for systems with a fixed ratio of oil to water, varying the surfactant, the so-called Kahlweit fish-cut diagrams. Some properties of the phase diagrams can be scaled to become general and not system dependent. Here are shown two examples of scaling data from phase diagrams and the use of trends to determine phase diagrams, both inside and outside a dataset. The trends of microemulsions with fixed ratio of surfactant to oil, the so-called Lund-cut diagrams, are also investigated. The trends are used to determine a new phase diagram and this is compared with previously unpublished experimental data on C₁₂E₅-Octadecane-Water system. The scalings and trends make it possible to get good estimations of many of the important properties of the phase diagrams, both temperatures and surfactant concentrations of interest, by investigating one sample in the 3-phase region of the balanced fish-cut diagram.     

Overview on the recently developed thiazolyl heterocycles as useful therapeutic agents

Thiazoles are important heterocyclic compounds which have many biological activities and different applications such as useful ligands, in optical sensors, etc. A literature survey shows that there are different routes to thiazoles. One of the most frequently used synthetic approaches consists of a reaction between α-halocarbonyl compounds with a CSNH₂ moiety. In this mini-review we have classified the contents based on the reagent or material providing the sulfur atom of the thiazole ring. Also, among many articles which have been devoted to thiazole syntheses here we presented some synthetic approaches published from 2012 to 2014.     

The phosphorescence nanocomposite thin film with rich oxygen vacancy: Towards sensitive oxygen sensor

Organic room temperature phosphorescent (ORTP) materials provide an exciting research direction for phosphorescent oxygen (O₂) sensors due to their high sensitivity and rapid response to O₂. However, most pure ORTP materials are tightly-packed aromatic compound crystals in a face-to-face manner, which largely prohibits effective O₂ diffusion for sensing. Thus, how to solve this contradiction still faces huge challenges. Here, the use of organic phosphorescent indicator carbon dots (CDs), inorganic matrix layered double hydroxides (LDHs) and polymers (PVA) successfully prepared an ultra-long RTP composite film whose phosphorescence decay intensity is linearly related to O₂ concentration. More importantly, the use of the abundant O₂ defects (Vo) on the surface of the inorganic matrix LDHs to adsorb O₂, which further accelerates the phosphorescence quenching of the thin film and improves the O₂ response. This strategy will provide the possibility to develop high-sensitivity phosphorescent O₂ sensors from a new perspective.     

Self‐Assembled Discrete Molecules for Sensing Nitroaromatics

Efficient sensing of trace amount nitroaromatic (NAC) explosives has become a major research focus in recent time due to concerns over national security as well as their role as environment pollutants. NO₂‐containing electron‐deficient aromatic compounds, such as picric acid (PA), trinitrotoluene (TNT), and dinitrotoluene (DNT), are the common constituents of many commercially available chemical explosives. In this article, we have summarized our recent developments on the rational design of electron‐rich self‐assembled discrete molecular sensors and their efficacy in sensing nitroaromatics both in solution as well as in vapor phase. Several π‐electron‐rich fluorescent metallacycles (squares, rectangles, and tweezers/pincers) and metallacages (trigonal and tetragonal prisms) have been synthesized by means of metal–ligand coordination‐bonding interactions, with enough internal space to accommodate electron‐deficient nitroaromatics at the molecular level by multiple supramolecular interactions. Such interactions subsequently result in the detectable fluorescence quenching of sensors even in the presence of trace quantities of nitroaromatics. The fascinating sensing characteristics of molecular architectures discussed in this article may enable future development of improved sensors for nitroaromatic explosives.     

Influence of spacer in the formation of nanorings by templateless electropolymerization

In this original work, we want to control the shape of the resulting porous structures by templateless electropolymerization, by adjusting the spacer (flexible alkyl chains or rigid aromatic groups) between thieno[3,4-b]thiophene and carbazole used as the monomer and the substituent, respectively. A huge change is especially observed from ribbon-like structures to nanorings as the alkyl spacer increases. The presence of a significant amount of water is necessary for the formation of these porous structures because it allows releasing a high amount of gas bubbles. The size and number of nanorings are dependent on both the alkyl spacer and electrochemical parameters such as the number of deposition scans. These surfaces could be used in the future in various potential applications such as in water harvesting, oil/water separation membranes, optical devices, sensors or photocatalysis.     

Kinetics of crystallization processes in some glass ceramic products

The paper presents the kinetic study of the crystallization processes which take place in basalt glasses containing variable amount of nucleation agent (CaF₂, 310%). The activation energies have been calculated using Kissinger's equation and verified with the Ozawa-Flynn-Wall equation. In this order, the DTA curves have been registered with different heating rates, between 4 and 20 degrees/min. A correlation equation between the activation energy and the amount of nucleation agent (% of CaF₂) was established. By X-ray diffraction it was proved that the crystalline phase formed in the crystallization process represents a pyroxenic solid solution, Ca(Mg,Fe)SiO₃. This revised version was published online in July 2006 with corrections to the Cover Date.     

Nanostructured metal particlemodified electrodes for electrocatalytic and sensor applications

Nanotechnology has become one of the most exciting frontier fields in analytical chemistry. The huge interest in nanomaterials, for example in chemical sensors and catalysis, is driven by their many desirable properties. Although metal is a poor catalyst in bulk form, nanometre-sized particles can exhibit excellent catalytic activity due to their relative high surface area-to-volume ratio and their interface-dominated properties, which significantly differ from those of the bulk material. The integration of metal nanoparticles into thin film of permselective membrane is particularly important for various applications, for example in biological sensing and in electrocatalysis. We have already established different techniques to design permselective membrane-coated chemically modified electrodes with incorporated redox molecules for electrocatalytic, electrochromic and sensor applications. Recently, we have prepared nanostructured platinum and copper (represented M_nano, M = Pt and Cu) modified GC/Nafion electrodes (GC/Nf/M_nano) and characterized by using AFM, XPS, XRD and electrochemical techniques. The nanostructured M_nano modified electrodes were utilized for efficient electrocatalytic selective oxidation of neurotransmitter molecules in the presence of interfering species such as ascorbic acid (AA) and uric acid (UA). It has been also shown that the modified electrodes could be used as sensors for the detection of submicromolar concentrations of biomolecules with practical applications to real samples such as blood plasma and dopamine hydrochloride injection solution. The GC/Cu_nano electrode has been used for catalytic reduction of oxygen.     

Plasticizer and catalyst co-functionalized PEDOT:PSS enables stretchable electrochemical sensing of living cells

Recently, stretchable electrochemical sensors have stood out as a powerful tool for the detection of soft cells and tissues, since they could perfectly comply with the deformation of living organisms and synchronously monitor mechanically evoked biomolecule release. However, existing strategies for the fabrication of stretchable electrochemical sensors still face with huge challenges due to scarce electrode materials, demanding processing techniques and great complexity in further functionalization. Herein, we report a novel and facile strategy for one-step preparation of stretchable electrochemical biosensors by doping ionic liquid and catalyst into a conductive polymer (poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate), PEDOT:PSS). Bis(trifluoromethane) sulfonimide lithium salt as a small-molecule plasticizer can significantly improve the stretchability and conductivity of the PEDOT:PSS film, and cobalt phthalocyanine as an electrocatalyst endows the film with excellent electrochemical sensing performance. Moreover, the functionalized PEDOT:PSS retained good cell biocompatibility with two extra dopants. These satisfactory properties allowed the real-time monitoring of stretch-induced transient hydrogen peroxide release from cells. This work presents a versatile strategy to fabricate conductive polymer-based stretchable electrodes with easy processing and excellent performance, which benefits the in-depth exploration of sophisticated life activities by electrochemical sensing.

A facile strategy for constructing stretchable sensors with excellent mechanical, electrochemical and biocompatible performance is developed, and in situ inducing and monitoring of stretch-evoked H₂O₂ release from cells has been successfully achieved.     

Semiconductor Sensors Based on SnO<Subscript>2</Subscript> with Pt Additives and their Catalytic Activity in Oxidation of Methane

We have studied the effect of small additives of Pt on the methane sensitivity of semiconductor adsorption sensors based on SnO₂ (doped with Sb₂O₅) and on the catalytic activity of sensor materials of the same composition in oxidation of methane. We have shown that as the amount of Pt increases, the catalytic activity increases and the sensitivity of the sensors passes through a maximum. The results obtained are explained taking into account the spillover phenomenon.__________Translated from Teoreticheskaya i Eksperimental’naya Khimiya, Vol. 41, No. 3, pp. 176–179, May–June, 2005.     

Evaluation of antibody immobilization technqiues for fiber optic-based fluoroimmunosensing

Fiber optic chemical sensors have been developed that employ immunochemicals to perform fluoroimmunoassays. A regenerable fiber optic sensor was developed with a capillary delivery system to perform repetitive assays using antibodies immobilized to beads, “immunobeads”. The sensitivity of these sensors is directly proportional to the amount of antibody present. For the immunobeads, the amount immobilized (loaded) and the ability of the immobilized antibody to maintain antibody recognition (activity) are two criteria which will affect the sensitivity of the sensors. Four reagents, [1,1′-carbonyldiimidazole (CDI), Protein A, glycidoxypropyltrimethoxysilane (GOPS) and 2-fluoro-1-methylpyridium toluene-4-sulfonate (FMP)], were evaluated using these two criteria. Two antibody—antigen systems were employed to investigate the four procedures. The first combination is a polyclonal rabbit anti-human IgG with a F(ab)^′₂ fragment human IgG as the antigen. The second combination is a monoclonal mouse anti-benzo[a]pyrene tetraol (BPT) IgG with BPT as the hapten. In the case of the BPT, CDI demonstrated superior performance, combining high loading and high retention of antibody activity. In the case of the large antigen, CDI again immobilized the most antibody but suffered activity losses of about 40%. The large amount of inactive antibody may make this procedure less attractive than the Protein A beads, which maintained the activity of the anti-human IgG but exhibited less loading than the CDI. However, in terms of active antibody there are similar amounts. FMP yielded similar results to CDI for the large antigen case but the sample preparation is more labor intensive. GOPS yielded losses of up to 70% of the antibody activity, which makes it unattractive as a reagent. The two systems tested give an indication of antibody—antigen interactions but may not be representative of all cases. The ideal immobilization reagent and conditions will probably change from system to system.     

Detection Mechanism of Metallized Carbon Epoxy Oxidase Enzyme Based Sensors

The coenzyme FAD has been identified to play an important role in the detection mechanism of oxidase enzyme based biosensors. Incorporating FAD into the carbon composite improved sensitivity to H₂O₂ consequently increasing sensitivity to the respective analyte. The amount of active enzyme also increased thus enhancing the overall performance of the sensors. Polycarboxybetaine (PCB) has been used as a biocompatible membrane coating. The PCB coated sensors gave reproducible calibrations in protein solutions, which has been shown to be a valid protocol for testing biocompatibility. The importance of reporting selectivity in a manner which indicates the “fitness of purpose” of biosensors has been discussed.     

Concentrated solutions of polydisperse rodlike polymers in the isotropic and lyotropic liquid-crystalline phases. I. The effects of molecular length distribution on phase behavior

The earlier calculations of Moscicki and Williams of the phase behavior of rodlike macromolecules in solution incorporating a Gaussian distribution of rod lengths have been extended to include, in addition to a “basic” Gaussian distribution, a small amount of high-molecular-weight species which are characterized by a δ-function or “box-function” distribution. It is shown that C^*_p, the concentration of polymer at which the biphasic material (isotropic plus anisotropic phase) first appears may be substantially lowered in comparison with that for the system comprising only the basic distribution. The volume fraction Φ_A of anisotropic phase, the compositions of the two phases, and the distribution of species between the phases are calculated for a range of polymer concentration which spans the isotropic, biphasic, and anisotropic phase and, among several features obtained, it is shown that the high-molecular-weight species are essentially responsible for the initial formation of anisotropic phase in the biphasic system. The results of the calculations have important implications for the interpretation of published dielectric relaxation data for polyalkylisocyanates in solution at high concentration and for published shear-flow viscosity data for polyalkylisocyanates and poly(p-benzamide) in solution at high concentration and these are discussed in some detail.     

Recent advances in the development of electrochemical hydrogen peroxide carbon nanotube–based (bio)sensors

The relevance of H₂O₂ as biomarker for different neurodegenerative diseases and cancer has been one of the most significant incentives for the development of new (bio)sensors that allow a more sensitive, selective, fast, and stable quantification of H₂O₂. In this regard, the association of carbon nanotubes with hemoproteins, nanoparticles, and other nanostructures and different electrochemical transducers has offered new avenues for the construction of innovative H₂O₂ bioanalytical platforms. This short review highlights the most relevant contributions in the field of electrochemical (bio)sensors for H₂O₂ based on carbon nanotubes published in the period 2016–2018.     

Incorporation of extra amino acids in peptide recognition probe to improve specificity and selectivity of an electrochemical peptide-based sensor

We investigated the effect of incorporating extra amino acids (AA) at the n-terminus of the thiolated and methylene blue-modified peptide probe on both specificity and selectivity of an electrochemical peptide-based (E-PB) HIV sensor. The addition of a flexible (SG)₃ hexapeptide is, in particular, useful in improving sensor selectivity, whereas the addition of a highly hydrophilic (EK)₃ hexapeptide has shown to be effective in enhancing sensor specificity. Overall, both E-PB sensors fabricated using peptide probes with the added AA (SG-EAA and EK-EAA) showed better specificity and selectivity, especially when compared to the sensor fabricated using a peptide probe without the extra AA (EAA). For example, the selectivity factor recorded in the 50% saliva was ∼2.5 for the EAA sensor, whereas the selectivity factor was 7.8 for both the SG-EAA and EK-EAA sensors. Other sensor properties such as the limit of detection and dynamic range were minimally affected by the addition of the six AA sequence. The limit of detection was 0.5 nM for the EAA sensor and 1 nM for both SG-EAA and EK-EAA sensors. The saturation target concentration was ∼200 nM for all three sensors. Unlike previously reported E-PB HIV sensors, the peptide probe functions as both the recognition element and antifouling passivating agent; this modification eliminates the need to include an additional antifouling diluent, which simplifies the sensor design and fabrication protocol.     

Lead-free bilayer heterometallic halide perovskite with reversible phase transition and photoluminescence properties

The layered heterometallic halide perovskites, as a newly explored material, have attracted great scientific attention. As one of the representatives of perovskite, lead-free or lead-substituted perovskite materials are widely applied in photovoltaic, sensors, catalysis, detectors and other fields. Therefore, it is urgent to carry out more systematic exploration and expand applicable preresearch, so as to make more interesting discoveries in this new hot spot. As an interesting candidate, heterometallic compounds will introduce more structural adjustability and novel physical properties, which is the main feature to be selected as the research hotspot. Here, we reported a lead-free bilayer heterometallic Ruddlesden-Popper (RP) type perovskite, [(MACH)₂CsAgBiBr₇] (MACH = cyclohexanemethylamine), which possesses a reversible phase transition at 379.6 K/ 375.1 K during heating-cooling cycle. Besides, it exhibits reddish-brown light emission under 365 nm, meanwhile, CIE chromaticity coordinate is (0.32, 0.45) on the yellow side and correlated color temperature is about 6000 K. Moreover, both the experimental data and theoretical calculation results suggest that [(MACH)₂CsAgBiBr₇] shows indirect semiconducting characteristics. In summary, this work will inspire the design of lead-free heterometallic perovskite materials for the application of sensors and light-emitting diodes (LEDs) fields.     

Synthesis of LaFeO<Subscript>3</Subscript> catalytic materials and their sensing properties

LaFeO₃ is a p-type semiconductor catalytic material of perovskite structure (ABO₃). Its magnetic and photocatalytic properties have been widely investigated, but the gas sensing properties are seldom reported, especially for toxic and noxious gases of NO₂ and CO. The nanocomposites of LaFeO₃ and LaFe_1−x Mg _x O₃ (x = 0.02, 0.04, 0.06) were prepared by various methods of the wet chemical process and their exact composition, crystal structures, grain sizes, specific surfaces, morphology and the electronic interaction between components were characterized by EDX, XRD, BET, SEM and XPS analysis. The sensors based on these nanocomposites have been fabricated to examine the sensing responses to gases, and the results show that these sensors exhibited high response to both oxidizing gas (NO₂) and reducing gas (CO), and the response was greatly enhanced by the surface modification of MgO. The additive method, amount of additives, and their effects on the LaFeO₃ structure and gas response have been analyzed and discussed by temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopic (XPS) analysis.     

Design Rules for Nanogap‐Based Hydrogen Gas Sensors

Nanoscale gaps, which enable many research applications in fields such as chemical sensors, single‐electron transistors, and molecular switching devices, have been extensively investigated over the past decade and have witnessed the evolution of related technologies. Importantly, nanoscale gaps employed in hydrogen‐gas (H₂) sensors have been used to reversibly detect H₂ in an On–Off manner, and function as platforms for enhancing sensing performance. Herein, we review recent advances in nanogap design for H₂ sensors and deal with various strategies to create these gaps, including fracture generation by H₂ exposure, deposition onto prestructured patterns, island formation on a surface, artificial manipulation methods, methods using hybrid materials, and recent approaches using elastomeric substrates. Furthermore, this review discusses a new nanogap design that advances sensing capabilities in order to meet the diverse needs of academia and industry.