A Novel QCM-based Biosensor for Detection of Microorganisms Producing Hydrogen Sulfide

Abstract

A novel piezoelectric quartz crystal microbalance (QCM) device with gas permeable membrane is proposed for the detection of microorganisms producing hydrogen sulfide (H₂S). The detection theory is based on the adsorption of hydrogen sulfide onto the silver electrode of the piezoelectric crystal sensor, which causes a dramatic decrease in the resonant frequency of QCM. A 100 Hz frequency shift is chosen as the criteria value to judge the presence of microorganisms producing H₂S. Factors affecting detection were investigated. Desiccant is of great practical importance in sensor response. This new biosensor can be a potential candidate for detecting bacteria which produce hydrogen sulfide.     

Solution-phase synthesis of ordered mesoporous carbon as resonant-gravimetric sensing material for room-temperature H_2S detection

H_2S can cause multiple diseases and poses a great threat to human health.However,the precise detection of extremely toxic H_2S at room temperature is still a great challenge.Here,a facile solvent evaporation induced aggregating assembly(EIAA) method has been applied for the production of ordered mesoporous carbon(OMCs) in an acidic THF/H_2 O solution with high-molecular-weight poly(ethylene oxide)-b-polystyrene(PEO-b-PS) copolymers as the structure-directing agent,formaldehyde and resorcinol as carbon precursors.Along with the continuous evaporation of THF from the mixed solution,cylindrical micelles are formed in the solution and further assemble into highly ordered mesostructure.The obtained OMCs possesses a two-dimensional(2 D) hexagonal mesostructure with uniform and large pore diameter(～19.2 nm),high surface area(599 m~2/g),and large pore volume(0.92 cm~3/g).When being used as the resonant cantilever gas sensor for room-temperature H_2S detection,the OMCs has delivered not only a superior gas sensing performance with ultrafast re s ponse(14 s) and recovery(21 s) even at low concentration(2 ppm) but also an excellent selectivity toward H_2S among various common interfering gases.Moreover,the limit of detection is better than 0.2 ppm,indicating its potential application in environmental monitoring and health protection.     

Gold Nanoparticles Monolayer Doping PEDOT : PSS Janus Film for Hydrogen Sulfide Sensor

AuNPs monolayer doping Poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT : PSS) film on interdigitated electrode had been fabricated into AuNPs/PEDOT : PSS Janus film sensor to detect hydrogen sulfide (H₂S). The results show that the Janus film sensors have a wide measurement range of H₂S concentration. The sensitivity of PEDOT : PSS/AuNPs sensor grows up with the thickness of Janus film increases. The resistance response of AuNPs Janus film was affected little by the rough surface states of PEDOT : PSS film. In addition, the PEDOT : PSS/AuNPs film sensor had been used again to detect H₂S. This work presents a platform to inspire a novel high sensitive chemiresistive sensor via nanoparticles monolayer.     

Indium-organic framework CPP-3（In） derived Ag/In2O3 porous hexagonal tubes for H2S detection at low temperature

There is a great demand for high-performance hydrogen sulfide（H₂S） sensors with low operating temperatures. Ag/In₂O₃ hexagonal tubes with different proportions were prepared by the calcination of Ag+-impregnated indium-organic frameworks(CPP-3（In）), and the developed sensors exhibit enhanced gassensing performance toward H₂S. Gas sensing measurements indicate that the response of Ag/In₂O₃（2.5 wt%） sensor to 5 ppm H₂S ha...     

Fabrication,characterization and exploration of cobalt (II) ion doped,modified zinc oxide thick film sensor for gas sensing characteristics of some pernicious gases

The present research deals with the synthesis of zinc oxide (ZnO) nanoparticles by the co-precipitation (CPT) method. The CPT method was successfully utilized for the synthesis of ZnO nanoparticles. The structural properties of undoped ZnO and cobalt doped ZnO were confirmed by employing an X-ray diffraction (XRD) study, from which the average particle size for each prepared material was calculated from the Debye Scherer formula. The average particle size confirms the nano range fabrication of undoped and cobalt doped ZnO material. The surface characteristics, morphology, texture, and porosity properties of undoped ZnO and cobalt doped ZnO were investigated from scanning electron microscopy (SEM). The elemental composition was investigated from energy dispersive spectroscopy (EDS). The High-resolution transmission electron microscopy (HRTEM) results revealed the hexagonal phase of prepared material. Furthermore, the undoped ZnO and 5% cobalt doped ZnO gas sensors prepared by screen printing technology were utilized for gas sensing purposes for testing the gases like H₂S, NO₂, SO₂, and methanol. For the gases examined, the cobalt modified ZnO sensor proved to be quite effective, especially for H₂S and NO₂ gas vapors. The Co²⁺ doped ZnO sensor showed 70.12% sensitivity for H₂S gas at 150 ⁰C and 68.75% gas response for NO₂ gas vapors at 120 ⁰C. In addition, the cobalt modified sensor was also investigated for reusability test to get concrete gas response results with the time interval of 15 days. In conclusion, it can be mentioned that the cobalt doped ZnO thick film sensor is a promising sensor for H₂S and NO₂ gas vapors.     

Piezoelectric Crystal Membrane Chemical Sensors Based on Fullerene and Macrocyclic Polyethers

Various reusable and sensitive piezoelectric (PZ) quartz crystal membrane sensors with home‐made computer interfaces for signal acquisition and data processing were developed to detect organic/inorganic vapors and organic/inorganic/biologic species in solutions, respectively. Fullerene(C60), fullerene derivatives and artificial macrocyclic polyethers, e.g., crown ethers and cryptands, were synthesized and applied as coating materials on quartz crystals of the PZ crystal sensors. The oscillating frequency of the quartz crystal decreased due to the adsorption of organic or inorganic species onto coating material molecules on the crystal surface. The crown ether‐coated PZ crystal gas detector exhibited high sensitivity with a frequency shift range of 10–340 Hz/(mg/L) for polar organic gases, a short response time (< 2.0 min.), good selectivity, and good reproducibility. The Ag(I)/crptand22 and Ru(III) / crptand22 coated PZ gas detectors were also prepared for nonpolar organic vapors, e.g., alkynes and alkenes. The frequency shifts of the nonpolar PZ sensors were in the order: alkynes > alkenes > alkanes. A Ti(IV)/Cryptand22‐coated PZ crystal sensor was also developed to detect the inorganic air pollutants, e.g., CO and NO₂. A piezoelectric gas sensor for both polar/nonpolar organic vapors based on C60‐cryptand22 was also prepared. The cryptand22‐coated PZ gas sensor was also employed as a GC detector for organic molecules. The cryptand22‐coated piezoelectric GC detectors compared well with the commercial thermal conductivity detector (TCD). The interaction between fullerene C60 and organic molecules was studied with a fullerene coated PZ gas detector. A multi‐channel PZ organic gas detector with PCA(Principal Component Analysis) and BPN (Back Propagation Neural) analysis methods was developed. Various liquid piezoelectric crystal sensors based on long‐chain macrocyclic polyethers, e.g., C₁₀H₂₁‐dibenzo‐16‐crown‐5, C₁₈H₃₇‐benzo‐15‐crown‐5, (C₁₇CO)₂‐cyptand22 and fullerene derivatives, e.g., C60‐NH‐cryptand22 and dibenzo‐16‐crown‐5‐C60, were also developed as HPLC detectors for metal ions, anions, and various organic compounds in solutions. The sensitive and highly selective PZ bio‐sensors based on enzymes, polyvinylaldehyde, polycinnaldehyde‐C60 and C60‐cryptand22 were developed to detect various biologic species, e.g., proteins, glucose, and urea. A quite sensitive EQCM (Electrochemical Quartz Crystal Micro‐balance) detection system was also developed for detection of trace heavy metal ions.     

A high-sensitivity H2S gas sensor based on optimized ZnO-ZnS nano-heterojunction sensing material

This paper reports a high-performance H₂S gas sensing material that is made of ZnO nanowires (NWs) modified by an optimal amount of ZnS to form nano-heterojunctions. Compared with the intrinsic ZnO-NWs, the three differently modified nano-heterostructure material ZnO-ZnS-x (x = 5, 10, 15) shows significant improvement in sensing performance to H₂S at the working temperatures of 100−400 °C, especially in the low temperature range (<300 °C). The chemiresistive sensor with ZnO-ZnS-10 sensing-material exhibits the largest response signal to H₂S among all the other ZnO-ZnS-x (x = 5, 10, 15, 20) sensors. Its response signal to 5 ppm H₂S at 150 °C is about 2.7 times to that of the ZnO-NWs sensor. Besides, the ZnO-ZnS-10 sensor also features satisfactory selectivity and repeatability at 150 °C. With the technical advantage attributed to the reduction of the redesigned band gap at the interface between ZnO and ZnS, the ZnO-ZnS heterostructure sensor rather than the traditional ZnO-NWs sensor can be used for high-sensitivity application at low working temperature.     

High throughput label-free platform for statistical bio-molecular sensing

Sensors are crucial in many daily operations including security, environmental control, human diagnostics and patient monitoring. Screening and online monitoring require reliable and high-throughput sensing. We report on the demonstration of a high-throughput label-free sensor platform utilizing cantilever based sensors. These sensors have often been acclaimed to facilitate highly parallelized operation. Unfortunately, so far no concept has been presented which offers large datasets as well as easy liquid sample handling. We use optics and mechanics from a DVD player to handle liquid samples and to read-out cantilever deflection and resonant frequency. Also, surface roughness is measured. When combined with cantilever deflection the roughness is discovered to hold valuable additional information on specific and unspecific binding events. In a few minutes, 30 liquid samples can be analyzed in parallel, each by 24 cantilever-based sensors. The approach was used to detect the binding of streptavidin and antibodies.     

Nanostructures-based sensing strategies for hydrogen sulfide

Hydrogen sulfide (H₂S) is a very toxic, flammable, and harmful gas. It may be formed naturally or be released into the environment due to human activities. Exposure of humans to a high level of H₂S leads to many hazardous effects. On the other hand, H₂S is produced in vivo and it has many physiological actions as the third physiological gas transmitter. Therefore, it is crucial to develop sensitive, selective, and easily operated sensors to monitor H₂S in its two-sided nature as toxic gas and as a physiological gas transmitter. Recently, the revolution in nanotechnology has a great impact on the development of many sensing techniques that adopt nanosensors for the detection of H₂S. Herein, we abridged the nanostructure-based electrochemical and optical sensors for H₂S in different matrices with a special emphasis on their advantages and applications. A discussion of the sensing mechanisms and the analytical features are also addressed. Finally, the future perspectives and recommended trends for H₂S detection are discussed.     

Electromechanical biosensors for pathogen detection

Rapid and sensitive detection of pathogen is critical for public health, defense and security. Methods such as culture and immunoassays, though highly selective and accurate, are time-consuming and not sufficient for fast decision-making in many situations. Biosensors have been developed to meet the challenges in pathogen detection. This article reviews the development and application of electromechanical biosensors for pathogen detection. It covers the most commonly used electromechanical biosensor systems, specifically quartz crystal microbalances, cantilever sensors and surface wave acoustic sensors. Sensing principles, immobilization of biorecognition elements, and applications to the detection of pathogens in food and water samples are sequentially discussed.

Synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>—Ag nanocomposites and their application to enzymeless hydrogen peroxide detection

To achieve highly sensitive nonenzymatic detection of H₂O₂, a novel electrochemical sensor based on Fe₃O₄-Ag nanocomposites was developed. Nanocomposites were synthesized by reducing [Ag(NH₃)₂]⁺ at the gas/liquid interface in the presence of silver seeds and confirmed by transmission electron microscopy and X-ray diffractometry. Electrochemical investigations indicate that the sensor is able to detect H₂O₂ within a wide linear range of 0.5 μM to 4.0 mM, sensitivity of 135.4 μA mM^?1 cm^?2 and low detection limit of 0.2 μM (S/N = 3). Additionally, the sensor exhibits good anti-interference ability, stability and repeatability. These results show that the Fe₃O₄-Ag nanocomposite is a promising electrocatalytic material for sensors construction.     

CuO–ZnO Micro/Nanoporous Array‐Film‐Based Chemosensors: New Sensing Properties to H2S

CuO–ZnO micro/nanoporous array‐films are synthesized by transferring a solution‐dipped self‐organized colloidal template onto a device substrate and sequent heat treatment. Their morphologies and structures are characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy, and X‐ray photoelectron spectrum analysis. Based on the sensing measurement, it is found that the CuO–ZnO films prepared with the composition of [Cu²⁺]/[Zn²⁺]=0.005, 0.01, and 0.05 all show a nice sensitivity to 10 ppm H₂S. Interestingly, three different zones exist in the patterns of gas responses versus H₂S concentrations: a platform zone, a rapidly increasing zone, and a slowly increasing zone. Further experiments show that the hybrid CuO–ZnO porous film sensor exhibits shorter recovery time and better selectivity to H₂S gas against other interfering gases at a concentration of 10 ppm. These new sensing properties may be due to a depletion layer induced by p–n junction between p‐type CuO and n‐type ZnO and high chemical activity of CuO to H₂S. This work will provide a new construction route of ZnO‐based sensing materials, which can be used as H₂S sensors with high performances.     

H2S Dosimetry by CuO: Towards Stable Sensors by Unravelling the Underlying Solid-State Chemistry

The precise detection of the toxic gas H₂S requires reliable sensitivity and specificity of sensors even at minute concentrations of as low as 10 ppm, the value corresponding to typical exposure limits. CuO can be used for H₂S dosimetry, based on the formation of conductive CuS and the concomitant significant increase in conductance. In theory, at elevated temperature the reaction is reversed and CuO is formed, ideally enabling repeated and long-term use of one sensor. Yet, the performance of CuO tends to drop upon cycling. Utilizing defined CuO nanorods we thoroughly elucidated the associated detrimental chemical changes directly on the sensors, by Raman and electron microscopy analysis of each step during sensing (CuO→CuS) and regeneration (CuS→CuO) cycles. We find the decrease in the sensing performance is mainly caused by the irreversible formation of CuSO₄ during regeneration. The findings allowed us to develop strategies to reduce CuSO₄ formation and thus to substantially maintain the sensing stability even for repeated cycles. We achieved CuO-based dosimeters possessing a response time of a few minutes only, even for 10 ppm H₂S, and prolonged life-time.     

Detection and classification of gaseous sulfur compounds by solid electrolyte cyclic voltammetry of cermet sensor array

Electrochemical sensors composed of a ceramic-metallic (cermet) solid electrolyte are used for the detection of gaseous sulfur compounds SO₂, H₂S, and CS₂ in a study involving 11 toxic industrial chemical (TIC) compounds. The study examines a sensor array containing four cermet sensors varying in electrode-electrolyte composition, designed to offer selectivity for multiple compounds. The sensors are driven by cyclic voltammetry to produce a current-voltage profile for each analyte. Raw voltammograms are processed by background subtraction of clean air, and the four sensor signals are concatenated to form one vector of points. The high-resolution signal is compressed by wavelet transformation and a probabilistic neural network is used for classification. In this study, training data from one sensor array was used to formulate models which were validated with data from a second sensor array. Of the 11 gases studied, 3 that contained sulfur produced the strongest responses and were successfully analyzed when the remaining compounds were treated as interferents. Analytes were measured from 10 to 200% of their threshold-limited value (TLV) according to the 8-h time weighted average (TWA) exposure limits defined by the National Institute of Occupational Safety and Health (NIOSH). True positive classification rates of 93.3, 96.7, and 76.7% for SO₂, H₂S, and CS₂, respectively, were achieved for prediction of one sensor unit when a second sensor was used for modeling. True positive rates of 83.3, 90.0, and 90.0% for SO₂, H₂S, and CS₂, respectively, were achieved for the second sensor unit when the first sensor unit was used for modeling. Most of the misclassifications were for low concentration levels (such 10-25% TLV) in which case the compound was classified as clean air. Between the two sensors, the false positive rates were 2.2% or lower for the three sulfur compounds, 0.9% or lower for the interferents (eight remaining analytes), and 5.8% or lower for clean air. The cermet sensor arrays used in this analysis are rugged, low cost, reusable, and show promise for multiple compound detection at parts-per-million (ppm) levels.     

基于硫堇掺杂的聚乙烯醇薄膜的光波导传感器检测硫化氢气体

采用旋转甩涂法将硫堇掺杂的聚乙烯醇薄膜固定在K⁺交换玻璃光波导表面,研制出一种高灵敏硫化氢气体传感器。 传感膜与硫化氢(H₂S)气体作用时,薄膜颜色从紫色变为无色,从而降低薄膜对倏逝波的吸收,使传感器的输出光强度（信号）增强。 采用流动注射法对H₂S气体进行检测。 实验结果表明,H₂S传感器对浓度在0.14~56 mg/m3范围的H₂S气体具有良好的线性响应（r=0.99667）,检出限为0.11 mg/m³(S/N=3),相对标准偏差为4.0%,响应时间（t90）＜2 s。 该传感器具有灵敏度高、响应快、可逆性和重复性好等特点。     

Rational design of a novel two-dimensional porous metal-organic framework material for efficient benzene sensor

As a common volatile organic compound, benzene (C₆H₆) exists in home decoration pollution gas widely, which causes great harm to the environment and human health. Therefore, it is necessary to rationally design advanced materials with high selectivity to detect and capture C₆H₆. Herein, combined with the d-band center theory and cohesive energy, a new two-dimensional metal-organic framework material, Ni-doped hexaaminobenzene-based coordination polymer (Ni-HAB-CP) is designed, and its application potential as a C₆H₆ sensor are systematically investigated by using first principles calculation. The result shows that Ni-HAB-CP has a strong adsorption for C₆H₆ without any additional method. In addition, Ni-HAB-CP can maintain good conductivity before and after adsorption, and C₆H₆ can be easily desorbed from the surface of Ni-HAB-CP by charge control. Moreover, the I-V curve calculated by Atomistix Toolkit (ATK) reveals that Ni-HAB-CP has high sensitivity and selectivity to C₆H₆. Hence, Ni-HAB-CP is expected to be used as a potential material for a highly efficient and recyclable C₆H₆ sensor in the future. The calculation and analysis methods used in this paper could provide a certain theoretical basis and reference for the future research of gas sensors.     

Sol-Gel Derived Thin Films for Hydrogen Sulphide Gas Sensing

Utilizing the sol-gel fabrication route, we have successfully modified and tailored the optical absorption in the visible spectrum of thionine dye trapped in an MTMS gel-matrix to coincide with the emission of a red diode laser operating at 660 nm. These thionine-doped MTMS thin films coated onto transparent substrates have shown a remarkable change in optical absorption in the presence of gaseous hydrogen sulphide (H₂S) diluted in air and in the absence of any buffer gas. The rapid response, sensitivity, reversibility and durability shown by this material can be exploited in developing absorption-based optical H₂S sensors in either an integrated optics or all-optical fiber approach using a red diode laser source.     

Two-photon dual-channel fluorogenic probe for in situ imaging the mitochondrial H2S/viscosity in the brain of drosophila Parkinson’s disease model

H₂S is an essential gas signal molecule in cells, and viscosity is a key internal environmental parameter. Recent studies have shown that H₂S acts as a cytoarchitecture agent and gas transmitter in many tissues, e.g., as a regulator of neuroendocrine in the brain for mediating vascular tone in blood vessels. Mitochondrial viscosity is an important parameter for judging whether mitochondrial function is normal. It has been reported that oxidative stress and mitochondrial dysfunction are connected with Parkinson’s disease (PD), and the protective role of H₂S in PD models has been extensively demonstrated. Herein, Mito-HS, a new two-photon fluorescent probe was demonstrated to detect cross-talk between the two channels of mitochondrial viscosity and H₂S content. Moreover, this probe could detect the relative amount of and changes in mitochondrial H₂S in situ due to the reduced mitochondrial targeting ability after reaction with H₂S. The results show that H₂S in mitochondria is inversely related to viscosity. The PD model has a lower H₂S in mitochondria and a higher mitochondrial viscosity than did the normal. This result is important for our deep understanding of PD and its causes.     

Data‐Driven Identification of Hydrogen Sulfide Scavengers

Hydrogen sulfide (H₂S) is an important signaling molecule whose up‐ and down‐regulation have specific biological consequences. Although significant advances in H₂S up‐regulation, by the development of H₂S donors, have been achieved in recent years, precise H₂S down‐regulation is still challenging. The lack of potent/specific inhibitors for H₂S‐producing enzymes contributes to this problem. We expect the development of H₂S scavengers is an alternative approach to address this problem. Since chemical sensors and scavengers of H₂S share the same criteria, we constructed a H₂S sensor database, which summarizes key parameters of reported sensors. Data‐driven analysis led to the selection of 30 potential compounds. Further evaluation of these compounds identified a group of promising scavengers, based on the sulfonyl azide template. The efficiency of these scavengers in in vitro and in vivo experiments was demonstrated.     

A Facile Strategy for the Construction of Purely Organic Optical Sensors Capable of Distinguishing D2O from H2O

Owing to the quite similar chemical properties of H₂O and D₂O, rational molecular design of D₂O optical sensors has not been realized so far. Now purely organic chromophores bearing OH groups with appropriate pK_a values are shown to display distinctly different optical responding properties toward D₂O and H₂O owing to the slight difference in acidity between D₂O and H₂O. This discovery is a new and facile strategy for the construction of D₂O optical sensors. Through this strategy, ratiometric colorimetric D₂O sensor of NIM‐2F and colorimetric/fluorescent dual‐channel D₂O sensor of AF were acquired successfully. Both NIM‐2F and AF can not only qualitatively distinguish D₂O from H₂O by the naked eye, but also quantitatively detect the H₂O content in D₂O.