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1.  Poly(3-Methylthiophene) Thin Films Deposited Electrochemically on QCMs for the Sensing of Volatile Organic Compounds 
Poly(3-methylthiophene) (PMeT) thin films were electrochemically deposited on quartz crystal microbalance QCM transducers to investigate their volatile organic compound (VOC) sensing properties depending on ambient conditions. Twelve different VOCs including alcohols, ketones, chlorinated compounds, amines, and the organosphosphate dimethyl methylphosphonate (DMMP) were used as analytes. The responses of the chemical sensors against DMMP were the highest among the tested analytes; thus, fabricated chemical sensors based on PMeT can be evaluated as potential candidates for selectively detecting DMMP. Generally, detection limits in the low ppm range could be achieved. The gas sensing measurements were recorded at various humid air conditions to investigate the effects of the humidity on the gas sensing properties. The sensing performance of the chemical sensors was slightly reduced in the presence of humidity in ambient conditions. While a decrease in sensitivity was observed for humidity levels up to 50% r.h., the sensitivity was nearly unaffected for higher humidity levels and a reliable detection of the VOCs and DMMP was possible with detection limits in the low ppm range.
PMCID: PMC4850937  PMID: 27023539
chemical gas sensor; poly(3-methylthiophene); humid air; electrochemical deposition; QCM; VOCs; DMMP
2.  Study of a QCM Dimethyl Methylphosphonate Sensor Based on a ZnO-Modified Nanowire-Structured Manganese Dioxide Film 
Sensors (Basel, Switzerland)  2010;10(9):8275-8290.
Sensitive, selective and fast detection of chemical warfare agents is necessary for anti-terrorism purposes. In our search for functional materials sensitive to dimethyl methylphosphonate (DMMP), a simulant of sarin and other toxic organophosphorus compounds, we found that zinc oxide (ZnO) modification potentially enhances the absorption of DMMP on a manganese dioxide (MnO2) surface. The adsorption behavior of DMMP was evaluated through the detection of tiny organophosphonate compounds with quartz crystal microbalance (QCM) sensors coated with ZnO-modified MnO2 nanofibers and pure MnO2 nanofibers. Experimental results indicated that the QCM sensor coated with ZnO-modified nanostructured MnO2 film exhibited much higher sensitivity and better selectivity in comparison with the one coated with pure MnO2 nanofiber film. Therefore, the DMMP sensor developed with this composite nanostructured material should possess excellent selectivity and reasonable sensitivity towards the tiny gaseous DMMP species.
PMCID: PMC3231230  PMID: 22163653
quartz crystal microbalance; gas sensor; volatile organic vapor; DMMP; nanowire; manganese dioxide; zinc oxide
3.  Effects of Textural Properties on the Response of a SnO2-Based Gas Sensor for the Detection of Chemical Warfare Agents 
Sensors (Basel, Switzerland)  2011;11(7):6893-6904.
The sensing behavior of SnO2-based thick film gas sensors in a flow system in the presence of a very low concentration (ppb level) of chemical agent simulants such as acetonitrile, dipropylene glycol methyl ether (DPGME), dimethyl methylphosphonate (DMMP), and dichloromethane (DCM) was investigated. Commercial SnO2 [SnO2(C)] and nano-SnO2 prepared by the precipitation method [SnO2(P)] were used to prepare the SnO2 sensor in this study. In the case of DCM and acetonitrile, the SnO2(P) sensor showed higher sensor response as compared with the SnO2(C) sensors. In the case of DMMP and DPGME, however, the SnO2(C) sensor showed higher responses than those of the SnO2(P) sensors. In particular, the response of the SnO2(P) sensor increased as the calcination temperature increased from 400 °C to 800 °C. These results can be explained by the fact that the response of the SnO2-based gas sensor depends on the textural properties of tin oxide and the molecular size of the chemical agent simulant in the detection of the simulant gases (0.1–0.5 ppm).
PMCID: PMC3231691  PMID: 22163991
sensor; SnO2; sensor response; chemical agent simulant
4.  Designing Hollow Nano Gold Golf Balls 
ACS Applied Materials & Interfaces  2014;6(13):9937-9941.
Hollow/porous nanoparticles, including nanocarriers, nanoshells, and mesoporous materials have applications in catalysis, photonics, biosensing, and delivery of theranostic agents. Using a hierarchical template synthesis scheme, we have synthesized a nanocarrier mimicking a golf ball, consisting of (i) solid silica core with a pitted gold surface and (ii) a hollow/porous gold shell without silica. The template consisted of 100 nm polystyrene beads attached to a larger silica core. Selective gold plating of the core followed by removal of the polystyrene beads produced a golf ball-like nanostructure with 100 nm pits. Dissolution of the silica core produced a hollow/porous golf ball-like nanostructure.
PMCID: PMC4334244  PMID: 24937196
hollow; porous; nanocarrier; gold shell; template; hierarchical
5.  Hierarchical Thin Film Architectures for Enhanced Sensor Performance: Liquid Crystal-Mediated Electrochemical Synthesis of Nanostructured Imprinted Polymer Films for the Selective Recognition of Bupivacaine 
Biosensors  2014;4(2):90-110.
Nanostructured bupivacaine-selective molecularly imprinted 3-aminophenylboronic acid-p-phenylenediamine co-polymer (MIP) films have been prepared on gold-coated quartz (Au/quartz) resonators by electrochemical synthesis under cyclic voltammetric conditions in a liquid crystalline (LC) medium (triton X-100/water). Films prepared in water and in the absence of template were used for control studies. Infrared spectroscopic studies demonstrated comparable chemical compositions for LC and control polymer films. SEM studies revealed that the topologies of the molecularly imprinted polymer films prepared in the LC medium (LC-MIP) exhibit discernible 40 nm thick nano-fiber structures, quite unlike the polymers prepared in the absence of the LC-phase. The sensitivity of the LC-MIP in a quartz crystal microbalance (QCM) sensor platform was 67.6 ± 4.9 Hz/mM under flow injection analysis (FIA) conditions, which was ≈250% higher than for the sensor prepared using the aqueous medium. Detection was possible at 100 nM (30 ng/mL), and discrimination of bupivacaine from closely related structural analogs was readily achieved as reflected in the corresponding stability constants of the MIP-analyte complexes. The facile fabrication and significant enhancement in sensor sensitivity together highlight the potential of this LC-based imprinting strategy for fabrication of polymeric materials with hierarchical architectures, in particular for use in surface-dependent application areas, e.g., biomaterials or sensing.
PMCID: PMC4264373  PMID: 25587412
bupivacaine; electropolymerization; liquid crystal; molecularly imprinted polymer; nanostructured polymer films; piezoelectric sensor; quartz crystal microbalance
6.  The Different Sensitive Behaviors of a Hydrogen-Bond Acidic Polymer-Coated SAW Sensor for Chemical Warfare Agents and Their Simulants 
Sensors (Basel, Switzerland)  2015;15(8):18302-18314.
A linear hydrogen-bond acidic (HBA) linear functionalized polymer (PLF), was deposited onto a bare surface acoustic wave (SAW) device to fabricate a chemical sensor. Real-time responses of the sensor to a series of compounds including sarin (GB), dimethyl methylphosphonate (DMMP), mustard gas (HD), chloroethyl ethyl sulphide (2-CEES), 1,5-dichloropentane (DCP) and some organic solvents were studied. The results show that the sensor is highly sensitive to GB and DMMP, and has low sensitivity to HD and DCP, as expected. However, the sensor possesses an unexpected high sensitivity toward 2-CEES. This good sensing performance can’t be solely or mainly attributed to the dipole-dipole interaction since the sensor is not sensitive to some high polarity solvents. We believe the lone pair electrons around the sulphur atom of 2-CEES provide an electron-rich site, which facilitates the formation of hydrogen bonding between PLF and 2-CEES. On the contrary, the electron cloud on the sulphur atom of the HD molecule is offset or depleted by its two neighbouring strong electron-withdrawing groups, hence, hydrogen bonding can hardly be formed.
PMCID: PMC4570322  PMID: 26225975
hydrogen-bond acidic polymer; chemical sensor; SAW
7.  Gas sensing properties of conducting polymer/Au-loaded ZnO nanoparticle composite materials at room temperature 
Nanoscale Research Letters  2014;9(1):467.
In this work, a new poly (3-hexylthiophene):1.00 mol% Au-loaded zinc oxide nanoparticles (P3HT:Au/ZnO NPs) hybrid sensor is developed and systematically studied for ammonia sensing applications. The 1.00 mol% Au/ZnO NPs were synthesized by a one-step flame spray pyrolysis (FSP) process and mixed with P3HT at different mixing ratios (1:1, 2:1, 3:1, 4:1, and 1:2) before drop casting on an Al2O3 substrate with interdigitated gold electrodes to form thick film sensors. Particle characterizations by X-ray diffraction (XRD), nitrogen adsorption analysis, and high-resolution transmission electron microscopy (HR-TEM) showed highly crystalline ZnO nanoparticles (5 to 15 nm) loaded with ultrafine Au nanoparticles (1 to 2 nm). Film characterizations by XRD, field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX) spectroscopy, and atomic force microscopy (AFM) revealed the presence of P3HT/ZnO mixed phases and porous nanoparticle structures in the composite thick film. The gas sensing properties of P3HT:1.00 mol% Au/ZnO NPs composite sensors were studied for reducing and oxidizing gases (NH3, C2H5OH, CO, H2S, NO2, and H2O) at room temperature. It was found that the composite film with 4:1 of P3HT:1.00 mol% Au/ZnO NPs exhibited the best NH3 sensing performances with high response (approximately 32 to 1,000 ppm of NH3), fast response time (4.2 s), and high selectivity at room temperature. Plausible mechanisms explaining the enhanced NH3 response by composite films were discussed.
PMCID: PMC4159556  PMID: 25246871
P3HT; Au-loaded ZnO; Composite films; NH3 sensor; Flame spray pyrolysis
8.  Selective Surface Acoustic Wave-Based Organophosphorus Sensor Employing a Host-Guest Self-Assembly Monolayer of β-Cyclodextrin Derivative 
Sensors (Basel, Switzerland)  2015;15(8):17916-17925.
Self-assembly and molecular imprinting technologies are very attractive technologies for the development of artificial recognition systems and provide chemical recognition based on need and not happenstance. In this paper, we employed a β-cyclodextrin derivative surface acoustic wave (SAW) chemical sensor for detecting the chemical warfare agents (CWAs) sarin (O-Isoprophyl methylphosphonofluoridate, GB). Using sarin acid (isoprophyl hydrogen methylphosphonate) as an imprinting template, mono[6-deoxy-6-[(mercaptodecamethylene)thio]]-β-cyclodextrin was prepared by self-assembled method on one of the SAW oscillators. After templates’ removal, a sensitive and selective molecular imprinting (MIP) monolayer for GB was prepared. Electrochemical impedance spectroscopy and atomic force microscope (AFM) were used to characterize this film. Comparing the detection results to GB by MIP film and non-MIP film, the molecularly imprinting effect was also proved. The resulting SAW sensor could detect sarin as low as 0.10 mg/m3 at room temperature and the frequency shift was about 300 Hz. The response frequency increased linearly with increasing sarin concentration in the range of 0.7 mg/m3~3.0 mg/m3. When sarin was detected under different temperatures, the SAW sensor exhibited outstanding sensitivity and reliability.
PMCID: PMC4570299  PMID: 26213930
surface acoustic wave (SAW); β-cyclodextrin; self-assembly; molecular imprinting (MIP); detection
9.  Enhanced Dibutyl Phthalate Sensing Performance of a Quartz Crystal Microbalance Coated with Au-Decorated ZnO Porous Microspheres 
Sensors (Basel, Switzerland)  2015;15(9):21153-21168.
Noble metals addition on nanostructured metal oxides is an attractive way to enhance gas sensing properties. Herein, hierarchical zinc oxide (ZnO) porous microspheres decorated with cubic gold particles (Au particles) were synthesized using a facile hydrothermal method. The as-prepared Au-decorated ZnO was then utilized as the sensing film of a gas sensor based on a quartz crystal microbalance (QCM). This fabricated sensor was applied to detect dibutyl phthalate (DBP), which is a widely used plasticizer, and its coating load was optimized. When tested at room temperature, the sensor exhibited a high sensitivity of 38.10 Hz/ppb to DBP in a low concentration range from 2 ppb to 30 ppb and the calculated theoretical detection limit is below 1 ppb. It maintains good repeatability as well as long-term stability. Compared with the undecorated ZnO based QCM, the Au-decorated one achieved a 1.62-time enhancement in sensitivity to DBP, and the selectivity was also improved. According to the experimental results, Au-functionalized ZnO porous microspheres displayed superior sensing performance towards DBP, indicating its potential use in monitoring plasticizers in the gaseous state. Moreover, Au decoration of porous metal oxide nanostructures is proved to be an effective approach for enhancing the gas sensing properties and the corresponding mechanism was investigated.
PMCID: PMC4610551  PMID: 26343661
ZnO porous microspheres; Au-decorated; dibutyl phthalate; gas sensor; quartz crystal microbalance (QCM)
10.  Smart Nanocomposites of Cu-Hemin Metal-Organic Frameworks for Electrochemical Glucose Biosensing 
Scientific Reports  2016;6:36637.
Herein, a smart porous material, Cu-hemin metal-organic-frameworks (Cu-hemin MOFs), was synthesized via assembling of Cu2+ with hemin to load glucose oxidase (GOD) for electrochemical glucose biosensing for the first time. The formation of the Cu-hemin MOFs was verified by scanning electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, N2 adsorption/desorption isotherms, UV-vis absorption spectroscopy, fluorescence spectroscopy, thermal analysis and electrochemical techniques. The results indicated that the Cu-hemin MOFs showed a ball-flower-like hollow cage structure with a large specific surface area and a large number of mesopores. A large number of GOD molecules could be successfully loaded in the pores of Cu-hemin MOFs to keep their bioactivity just like in a solution. The GOD/Cu-hemin MOFs exhibited both good performance toward oxygen reduction reaction via Cu-hemin MOFs and catalytic oxidation of glucose via GOD, superior to other GOD/MOFs and GOD/nanomaterials. Accordingly, the performance of GOD/Cu-hemin MOFs-based electrochemical glucose sensor was enhanced greatly, showing a wide linear range from 9.10 μM to 36.0 mM and a low detection limit of 2.73 μM. Moreover, the sensor showed satisfactory results in detection of glucose in human serum. This work provides a practical design of new electrochemical sensing platform based on MOFs and biomolecules.
PMCID: PMC5095656  PMID: 27811998
11.  Sulfur/graphitic hollow carbon sphere nano-composite as a cathode material for high-power lithium-sulfur battery 
Nanoscale Research Letters  2013;8(1):343.
The intrinsic low conductivity of sulfur which leads to a low performance at a high current rate is one of the most limiting factors for the commercialization of lithium-sulfur battery. Here, we present an easy and convenient method to synthesize a mono-dispersed hollow carbon sphere with a thin graphitic wall which can be utilized as a support with a good electrical conductivity for the preparation of sulfur/carbon nano-composite cathode. The hollow carbon sphere was prepared from the pyrolysis of the homogenous mixture of the mono-dispersed spherical silica and Fe-phthalocyanine powder in elevated temperature. The composite cathode was manufactured by infiltrating sulfur melt into the inner side of the graphitic wall. The electrochemical cycling shows a capacity of 425 mAh g−1 at 3 C current rate which is more than five times larger than that for the sulfur/carbon black nano-composite prepared by simple ball milling.
PMCID: PMC3735411  PMID: 23914902
Lithium-sulfur battery; Hollow carbon sphere; Graphitic carbon; Nano-composite; Cathode
12.  A Novel Route for Preparation of Hollow Carbon Nanospheres Without Introducing Template 
Nanoscale Research Letters  2009;4(11):1365-1370.
A newly developed route for the synthesis of hollow carbon nanospheres without introducing template under hydrothermal conditions was reported. Hollow carbon nanospheres with the diameter of about 100 nm were synthesized using alginate as reagent only. Many instruments were applied to characterize the morphologies and structures of carbon hollow nanospheres, such as XRD, TEM, and Raman spectroscopy. The possible formation and growth mechanism of carbon hollow spheres were discussed on the basis of the investigation of reaction influence factors, such as temperature, time, and content. The findings would be useful for the synthesis of more materials with hollow structure and for the potential use in many aspects. The loading of SnO2 on the surface of carbon hollow spheres was processed, and its PL property was also characterized.
Electronic supplementary material
The online version of this article (doi:10.1007/s11671-009-9406-7) contains supplementary material, which is available to authorized users.
PMCID: PMC2894182  PMID: 20628463
Synthesis; Nanostructure; Carbon hollow nanospheres
13.  A Novel Route for Preparation of Hollow Carbon Nanospheres Without Introducing Template 
Nanoscale Research Letters  2009;4(11):1365-1370.
A newly developed route for the synthesis of hollow carbon nanospheres without introducing template under hydrothermal conditions was reported. Hollow carbon nanospheres with the diameter of about 100 nm were synthesized using alginate as reagent only. Many instruments were applied to characterize the morphologies and structures of carbon hollow nanospheres, such as XRD, TEM, and Raman spectroscopy. The possible formation and growth mechanism of carbon hollow spheres were discussed on the basis of the investigation of reaction influence factors, such as temperature, time, and content. The findings would be useful for the synthesis of more materials with hollow structure and for the potential use in many aspects. The loading of SnO2on the surface of carbon hollow spheres was processed, and its PL property was also characterized.
PMCID: PMC2894182  PMID: 20628463
Synthesis; Nanostructure; Carbon hollow nanospheres
14.  Dye–Sensitized Nanostructured Crystalline Mesoporous Tin-doped Indium Oxide Films with Tunable Thickness for Photoelectrochemical Applications 
A simple route towards nanostructured mesoporous Indium–Tin Oxide (templated nano–ITO) electrodes exhibiting both high conductivities and optimized bicontinuous pore–solid network is reported. The ITO films are first produced as an X–ray–amorphous, high surface area material, by adapting recently established template–directed sol–gel methods using Sn(IV) and In(III) salts. Carefully controlled temperature/atmosphere treatments convert the as–synthesized ITO films into nano-crystalline coatings with the cubic bixbyite structure. Specially, a multi-layered synthesis was successfully undertaken for tuning the film thickness. In order to evaluate the performances of templated nano–ITO as an electrode substrate for photoelectrochemical applications, photoelectrodes were prepared by covalent grafting of a redox–active dye, the complex [Ru(bpy)2(4,4′-(CH2PO3H2)2-bpy)]Cl2 1 (bpy=bipyridine). Surface coverage was shown to increase with the film thickness, from 0.7 × 10−9−2 (one layer, 45 nm) to 3.5 × 10−9−2 (ten layers, 470 nm), the latter value being ~ 100 times larger than that for commercially available planar ITO. In the presence of an electron mediator, photocurrents up to 50 μ−2 have been measured under visible light irradiation, demonstrating the potential of this new templated nano-ITO preparation for the construction of efficient photoelectrochemical devices.
PMCID: PMC3880857  PMID: 24404381
ITO; Mesoporous; Sol-gel Process; Multi-layered; Ruthenium dye; Photocurrents
15.  Wispy Prosthesis: A Novel Method in Denture Weight Reduction 
Stability and retention of the denture becomes at stake with the increase in weight of the denture prosthesis. As a consequence, different materials and methods have been introduced to overcome these issues but denture weight reduction still remains to be a cumbersome and strenuous procedure.
To introduce a novel technique for the fabrication of denture prosthesis where in the weight of the denture will not affect the retention and stability of the denture.
Materials and Methods
Four groups with a sample size of 10 each, were included where in one group was control and other three were study groups. The control group samples were made completely solid and the study group samples were packed with materials like bean balls, cellulose balls and polyacrylic fibers. The weight of all the samples of each study group was measured and compared with the control group. The observations were analyzed statistically by paired t-test.
It was observed that the bean balls group produced a weight reduction of 31.3%, cellulose balls group 27.4% and polyacrylic fibers group 24.5% when compared to that of the control group.
This novel technique will eliminate the problems that were associated in creating hollowness and at the same time will reduce the weight of the prosthesis and among all the study groups, bean balls group were found to reduce maximum weight of the prosthesis.
PMCID: PMC4866245  PMID: 27190947
Bean balls; Cellulose balls; Hollow; Obturator
16.  Investigation of phase composition and nanoscale microstructure of high-energy ball-milled MgCu sample 
Nanoscale Research Letters  2012;7(1):390.
The ball milling technique has been successfully applied to the synthesis of various materials such as equilibrium intermetallic phases, amorphous compounds, nanocrystalline materials, or metastable crystalline phases. However, how the phase composition and nanoscale microstructure evolute during ball milling in various materials is still controversial due to the complex mechanism of ball milling, especially in the field of solid-state amorphization caused by ball milling. In the present work, the phase evolution during the high-energy ball milling process of the Mg and Cu (atomic ratio is 1:1) mixed powder was investigated. It was found that Mg firstly reacts with Cu, forming the Mg2Cu alloy in the primary stage of ball milling. As the milling time increases, the diffracted peaks of Mg2Cu and Cu gradually disappear, and only a broad halo peak can be observed in the X-ray diffraction pattern of the final 18-h milled sample. As for this halo peak, lots of previous studies suggested that it originated from the amorphous phase formed during the ball milling. Here, a different opinion that this halo peak results from the very small size of crystals is proposed: As the ball milling time increases, the sizes of Mg2Cu and Cu crystals become smaller and smaller, so the diffracted peaks of Mg2Cu and Cu become broader and broader and result in their overlap between 39° and 45°, at last forming the amorphous-like halo peak. In order to determine the origin of this halo peak, microstructure observation and annealing experiment on the milled sample were carried out. In the transmission electron microscopy dark-field image of the milled sample, lots of very small nanocrystals (below 20 nm) identified as Mg2Cu and Cu were found. Moreover, in the differential scanning calorimetry curve of the milled sample during the annealing process, no obvious exothermic peak corresponding to the crystallization of amorphous phase is observed. All the above results confirm that the broad halo diffracted peak in the milled MgCu sample is attributed to the overlap of the broadened peaks of the very small Mg2Cu and Cu nanocrystalline phase, not the MgCu amorphous phase. The whole milling process of MgCu can be described as follows: Mg+Cu→Mg2Cu+Cu→Mg2Cunanocrystal+Cunanocrystal.
PMCID: PMC3462153  PMID: 22793264
17.  Carboxylic Acid-Functionalized Conducting-Polymer Nanotubes as Highly Sensitive Nerve-Agent Chemiresistors 
Scientific Reports  2016;6:33724.
Organophosphates are powerful inhibitors of acetylcholinesterase, which is critical to nerve function. Despite continuous research for detecting the highly toxic organophosphates, a new and improved methodology is still needed. Herein we demonstrate simple-to-fabricate chemiresistive gas sensors using conducting-polymer polypyrrole (PPy) nanotube transducers, which are chemically specific and capable of recognizing sub-ppb concentrations (ca. 0.5 ppb) of dimethyl methylphosphonate (DMMP), a simulant of nerve agent sarin. Interestingly, the introduction of carboxylic groups on the surface of PPy nanotube transistors resulted in enhanced sensitivity to DMMP via intermolecular hydrogen bonding. Furthermore, it was found that the sensitivity of the nanotube transducer depended on the degree of the carboxylic group introduced. Finally, a sensor array composed of 5 different transducers including the carboxylated nanotubes exhibited excellent selectivity to DMMP in 16 vapor species.
PMCID: PMC5030647  PMID: 27650635
18.  Ammonia gas sensors based on In2O3/PANI hetero-nanofibers operating at room temperature 
Indium nitrate/polyvinyl pyrrolidone (In(NO3)3/PVP) composite nanofibers were synthesized via electrospinning, and then hollow structure indium oxide (In2O3) nanofibers were obtained through calcination with PVP as template material. In situ polymerization was used to prepare indium oxide/polyaniline (In2O3/PANI) composite nanofibers with different mass ratios of In2O3 to aniline. The structure and morphology of In(NO3)3/PVP, In2O3/PANI composite nanofibers and pure PANI were investigated by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and current–voltage (I–V) measurements. The gas sensing properties of these materials towards NH3 vapor (100 to 1000 ppm) were measured at room temperature. The results revealed that the gas sensing abilities of In2O3/PANI composite nanofibers were better than pure PANI. In addition, the mass ratio of In2O3 to aniline and the p–n heterostructure between In2O3 and PANI influences the sensing performance of the In2O3/PANI composite nanofibers. In this paper, In2O3/PANI composite nanofibers with a mass ratio of 1:2 exhibited the highest response values, excellent selectivity, good repeatability and reversibility.
PMCID: PMC5082485  PMID: 27826505
ammonia (NH3); electrospinning; gas sensor; indium(III) oxide (In2O3); polyaniline (PANI)
19.  Potentiometric CO2 Sensor Using Li+ Ion Conducting Li3PO4 Thin Film Electrolyte 
Sensors (Basel, Switzerland)  2005;5(11):465-472.
Li+ ion conducting Li3PO4 thin film electrolytes with thickness 300nm, 650nm and 1.2μm were deposited on Al2O3 substrate at room temperature by thermal evaporation method. Reference and sensing electrodes were printed on Au interfaces by conventional screen printing technique. The overall dimension of the sensor was 3 × 3 mm and of electrodes were 1 × 1.5 mm each. The fabricated solid state potentiometric CO2 sensors of type: CO2, O2, Au, Li2TiO3-TiO2| Li3PO4 |Li2CO3, Au, CO2, O2 have been investigated for CO2 sensing properties. The electromotive force (emf) and Δemf/dec values of the sensors are dependent on the thickness of the electrolyte film. 1.2μm thickness deposited sensor has shown good sensing behavior than the sensors with less thickness. The Δemf values of the sensor are linearly increased up to 460°C operating temperature and became stable above 460°C. Between 460-500°C temperatures region the sensor has reached an equilibrium state and the experimentally obtained Δemf values are about 80% of the theoretically calculated values. A Nernst's slope of -61mV/decade has been obtained between 250 to 5000 ppm of CO2 concentration at 500°C temperature. The sensor is suitable for ease of mass production in view of its miniaturization and cost effectiveness after some further improvement.
PMCID: PMC3934518
Thin film; Thick film; Potentiometric CO2 sensor; Li+ ion electrolyte
20.  Mesoporous Non-stacked Graphene-receptor Sensor for Detecting Nerve Agents 
Scientific Reports  2016;6:33299.
A novel gas sensor consisting of porous, non-stacked reduced graphene oxide (NSrGO)-heaxfluorohydoroxypropanyl benzene (HFHPB) nanosheets was successfully fabricated, allowing the detection of dimethyl methyl phosphonate (DMMP), similar to sarin toxic gas. The HFHPB group was chemically grafted to the NSrGO via a diazotization reaction to produce NSrGO-HFHPB. The NSrGO-HFHPB 3D film has a mesoporous structure with a large pore volume and high surface area that can sensitively detect DMMP and concurrently selectively signal the DMMP through the chemically-attached HFHPB. The DMMP uptake of the mesoporous NSrGO-HFHPB was 240.03 Hz, 12 times greater than that of rGO-HFHPB (20.14 Hz). In addition, the response rate of NSrGO-HFHPB was faster than that of rGO-HFHPB, an approximately 3 times more rapid recovery due to the mesoporous structure of the NSrGO-HFHPB. The NSrGO-HFHPB sensor exhibited long-term stability due to the use of robust carbon and resulting high resistance to humidity.
PMCID: PMC5022036  PMID: 27624664
21.  Ion-shaping of embedded gold hollow nanoshells into vertically aligned prolate morphologies 
Scientific Reports  2016;6:21116.
Ion beam shaping is a novel technique with which one can shape nano-structures that are embedded in a matrix, while simultaneously imposing their orientation in space. In this work, we demonstrate that the ion-shaping technique can be implemented successfully to engineer the morphology of hollow metallic spherical particles embedded within a silica matrix. The outer diameter of these particles ranges between 20 and 60 nm and their shell thickness between 3 and 14 nm. Samples have been irradiated with 74 MeV Kr ions at room temperature and for increasing fluences up to 3.8 × 1014 cm−2. In parallel, the experimental results have been theoretically simulated by using a three-dimensional code based on the thermal-spike model. These calculations show that the particles undergo a partial melting during the ion impact, and that the amount of molten phase is maximal when the impact is off-center, hitting only one hemisphere of the hollow nano-particle. We suggest a deformation scenario which differs from the one that is generally proposed for solid nano-particles. Finally, these functional materials can be seen as building blocks for the fabrication of nanodevices with really three-dimensional architecture.
PMCID: PMC4756376  PMID: 26883992
22.  Molecular packing and magnetic properties of lithium naphthalocyanine crystals: hollow channels enabling permeability and paramagnetic sensitivity to molecular oxygen 
Journal of materials chemistry  2009;19(24):4138-4147.
The synthesis, structural framework, magnetic and oxygen-sensing properties of a lithium naphthalocyanine (LiNc) radical probe are presented. LiNc was synthesized in the form of a microcrystalline powder using a chemical method and characterized by electron paramagnetic resonance (EPR) spectroscopy, magnetic susceptibility, powder X-ray diffraction analysis, and mass spectrometry. X-Ray powder diffraction studies revealed a structural framework that possesses long, hollow channels running parallel to the packing direction. The channels measured approximately 5.0 × 5.4 Å2 in the two-dimensional plane perpendicular to the length of the channel, enabling diffusion of oxygen molecules (2.9 × 3.9 Å2) through the channel. The powdered LiNc exhibited a single, sharp EPR line under anoxic conditions, with a peak-to-peak linewidth of 630 mG at room temperature. The linewidth was sensitive to surrounding molecular oxygen, showing a linear increase in pO2 with an oxygen sensitivity of 31.2 mG per mmHg. The LiNc microcrystals can be further prepared as nano-sized crystals without the loss of its high oxygen-sensing properties. The thermal variation of the magnetic properties of LiNc, such as the EPR linewidth, EPR intensity and magnetic susceptibility revealed the existence of two different temperature regimes of magnetic coupling and hence differing columnar packing, both being one-dimensional antiferromagnetic chains but with differing magnitudes of exchange coupling constants. At a temperature of ∼50 K, LiNc crystals undergo a reversible phase transition. The high degree of oxygen-sensitivity of micro- and nano-sized crystals of LiNc, combined with excellent stability, should enable precise and accurate measurements of oxygen concentration in biological systems using EPR spectroscopy.
PMCID: PMC2756769  PMID: 19809598
23.  Visible photoassisted room-temperature oxidizing gas-sensing behavior of Sn2S3 semiconductor sheets through facile thermal annealing 
Well-crystallized Sn2S3 semiconductor thin films with a highly (111)-crystallographic orientation were grown using RF sputtering. The surface morphology of the Sn2S3 thin films exhibited a sheet-like feature. The Sn2S3 crystallites with a sheet-like surface had a sharp periphery with a thickness in a nanoscale size, and the crystallite size ranged from approximately 150 to 300 nm. Postannealing the as-synthesized Sn2S3 thin films further in ambient air at 400 °C engendered roughened and oxidized surfaces on the Sn2S3 thin films. Transmission electron microscopy analysis revealed that the surfaces of the Sn2S3 thin films transformed into a SnO2 phase, and well-layered Sn2S3–SnO2 heterostructure thin films were thus formed. The Sn2S3–SnO2 heterostructure thin film exhibited a visible photoassisted room-temperature gas-sensing behavior toward low concentrations of NO2 gases (0.2–2.5 ppm). By contrast, the pure Sn2S3 thin film exhibited an unapparent room-temperature NO2 gas-sensing behavior under illumination. The suitable band alignment at the interface of the Sn2S3–SnO2 heterostructure thin film and rough surface features might explain the visible photoassisted room-temperature NO2 gas-sensing responses of the heterostructure thin film on exposure to NO2 gas at low concentrations in this work.
PMCID: PMC5112226  PMID: 27854080
Semiconductor; Sheets; Crystal feature; Surface; Gas-sensing response
24.  Dynamic Response of CoSb2O6 Trirutile-Type Oxides in a CO2 Atmosphere at Low-Temperatures 
Sensors (Basel, Switzerland)  2014;14(9):15802-15814.
Experimental work on the synthesis of the CoSb2O6 oxide and its CO2 sensing properties is presented here. The oxide was synthesized by a microwave-assisted colloidal method in presence of ethylenediamine after calcination at 600 °C. This CoSb2O6 oxide crystallized in a tetragonal structure with cell parameters a = 4.6495 and c = 9.2763 Å, and space group P42/mnm. To prove its physical, chemical and sensing properties, the oxide was subjected to a series of tests: Raman spectroscopy, Scanning Electron Microscopy (SEM) and impedance (Z) measurements. Microstructures, like columns, bars and hollow hemispheres, were observed. For the CO2 sensing test, a thick film of CoSb2O6 was used, measuring the impedance variations on the presence of air/CO2 flows (0.100 sccm/0.100 sccm) using AC (alternating current) signals in the frequency-range 0.1–100 kHz and low relative temperatures (250 and 300 °C). The CO2 sensing results were quite good.
PMCID: PMC4208146  PMID: 25162232
sensing properties; CoSb2O6; trirutile; chemical synthesis
25.  Preparation of hollow porous Cu2O microspheres and photocatalytic activity under visible light irradiation 
Nanoscale Research Letters  2012;7(1):347.
Cu2O p-type semiconductor hollow porous microspheres have been prepared by using a simple soft-template method at room temperature. The morphology of as-synthesized samples is hollow spherical structures with the diameter ranging from 200 to 500 nm, and the surfaces of the spheres are rough, porous and with lots of channels and folds. The photocatalytic activity of degradation of methyl orange (MO) under visible light irradiation was investigated by UV-visible spectroscopy. The results show that the hollow porous Cu2O particles were uniform in diameters and have an excellent ability in visible light-induced degradation of MO. Meanwhile, the growth mechanism of the prepared Cu2O was also analyzed. We find that sodium dodecyl sulfate acted the role of soft templates in the synthesis process. The hollow porous structure was not only sensitive to the soft template but also to the amount of reagents.
PMCID: PMC3443013  PMID: 22738162
Cu2O; Hollow porous microspheres; Photocatalytic; Visible light

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