World Congress on Biosensors 2014

World Congress on Biosensors 2014
Biosensors 2014

Tuesday, 10 July 2012


A new issue of this journal has just been published. To see abstracts of the papers it contains (with links through to the full papers) click here:
Selected papers from the latest issue:

Review of recent advances in the preparation of organic polymer monoliths for liquid chromatography of large molecules

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
R. Dario Arrua, Mohammad Talebi, Tim J. Causon, Emily F. Hilder
In recent years the use of monolithic polymers in separation science has greatly increased due to the advantages these materials present over particle-based stationary phases, such as their relative ease of preparation and good permeability. For these reasons, these materials present high potential as stationary phases for the separation and purification of large molecules such as proteins, peptides, nucleic acids and cells. An example of this is the wide range of commercial available polymer-based monolithic columns now present in the market. This review summarizes recent developments in the synthesis of monolithic polymers for separation science, such as the incorporation of nanostructures in the polymeric scaffold as well as the preparation of hybrid structures. The different methods used in the surface functionalization of monolithic columns are also reviewed. Finally, we critically discuss the recent applications of this column technology in the separation of large molecules under different chromatographic mode.

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► This review summarizes recent developments in the synthesis of polymer monoliths. ► Alternative preparation methods still remain an important area of research. ► The application of monoliths in the separation of large molecules is discussed. ► The use of polymer monoliths in the separation of real samples is still needed.

Microextraction techniques in the analysis of food flavor compounds: A review

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
Henryk H. Jeleń, Małgorzata Majcher, Mariusz Dziadas
Food flavor compounds due to the complexity of food as a matrix, and usually their very low concentrations in a product, as well as their low odor thresholds, create a challenge in their extraction, separation and quantitation. Food flavor volatiles represent compounds of different polarity, volatility and chemical character, which determine method of extraction for their isolation from food. Microextraction techniques, mainly SPME and SBSE have been used for food flavor compounds analysis for two decades. Microextraction methods other than SPME and SBSE are seldom used despite their analytical potential. The review discusses the nature of food flavor compounds, and different approaches to food flavor analysis. It summarizes the use of microextraction methods in food flavor compounds analysis based on papers published in the last 5years, and discusses the potential of microextraction methods in this field.

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► Microextraction methods in food flavors analysis based on 2006–2011 published papers discussed. ► SPME, SBSE, LPME methods as dominating summarized in detail. ► Potential of other, less popular in this field microextraction methods pronounced.

Mesoporous carbon amperometric glucose sensors using inexpensive, commercial methacrylate-based binders

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
Mingzhi Dai, Stephanie Maxwell, Bryan D. Vogt, Jeffrey T. La Belle
Two ordered, soft-templated mesoporous carbon powders with cubic and hexagonal framework structure and four different commercial, low cost methacrylate-based polymer binders with widely varying physical properties are investigated as screen printed electrodes for glucose sensors using glucose oxidase and ferricyanide as the mediator. Both the chemistry and concentration of the binder in the electrode formulation can significantly impact the performance. Poly(hydroxybutyl methacrylate) as the binder provides hydrophilicity to enable transport of species in the aqueous phase to the carbon surface, but yet is sufficiently hydrophobic to provide mechanical robustness to the sensor. The current from the mesoporous carbon electrodes can be more than an order of magnitude greater than for a commercial printed carbon electrode (Zensor) with improved sensitivity for model glucose solutions. Even when applying these sensors to rabbit whole blood, the performance of these glucose sensors compares favorably to a standard commercial glucose meter with the lower detection limit of the mesoporous electrode being approximately 20mgdL−1 despite the lack of a separation membrane to prevent non-specific events; these results suggest that the small pore sizes and high surface areas associated with ordered mesoporous carbons may effectively decrease some non-specific inferences for electrochemical sensing.

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► We prepared screen printed glucose sensor with two different mesoporous carbons. ► We investigated low cost, fluorine-free methacrylate-based as polymer binders. ► Cubic structure carbon provided higher signal than hexagonal structure carbon. ► Hydrophilicity of the binder greatly impacted the performance of the sensor. ► The best sensor accurately measured glucose level in rabbit blood.

Sensitive electrochemical sensor of tryptophan based on Ag@C core–shell nanocomposite modified glassy carbon electrode

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
Shuxian Mao, Weifeng Li, Yumei Long, Yifeng Tu, Anping Deng
We here reported a simple electrochemical method for the detection of tryptophan (Trp) based on the Ag@C modified glassy carbon (Ag@C/GC) electrode. The Ag@C core–shell structured nanoparticles were synthesized using one-pot hydrothermal method and characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), and Fourier transform-infrared spectroscopy (FTIR). The electrochemical behaviors of Trp on Ag@C/GC electrode were investigated and exhibited a direct electrochemical process. The favorable electrochemical properties of Ag@C/GC electrode were attributed to the synergistic effect of the Ag core and carbon shell. The carbon shell cannot only protect Ag core but also contribute to the enhanced substrate accessibility and Trp-substrate interactions, while nano-Ag core can display good electrocatalytic activity to Trp at the same time. Under the optimum experimental conditions the oxidation peak current was linearly dependent on the Trp concentration in the range of 1.0×10−7 to 1.0×10−4 M with a detection limit of 4.0×10−8 M (S/N=3). In addition, the proposed electrode was applied for the determination of Trp concentration in real samples and satisfactory results were obtained. The technique offers enhanced sensitivity and may trigger the possibilities of the Ag@C nanocomposite towards diverse applications in biosensor and electroanalysis.

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Ag@C and Colloidal carbon sphere modified glassy carbon electrodes were prepared. It was clear that the Ag@C/GCE exhibited enhanced electrocatalytic activity towards Trp, which could result from the synergistic effect between Ag core and carbon shell. The Ag@C/GCE showed excellent analytical properties in the determination of Trp.
► The electrochemical behavior of Ag@C core–shell nanocomposite was firstly proposed. ► Ag@C/GC electrode exhibited favorable electrocatalytic properties towards Trp. ► The good electrocatalysis was due to the synergistic effect of Ag-core and C-shell. ► The Ag@C/GC electrode displayed excellent analytical properties in determining Trp.

Electrodes with extremely high hydrogen overvoltages as substrate electrodes for stripping analysis based on bismuth-coated electrodes

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
Ye Tian, Lianzhe Hu, Shuang Han, Yali Yuan, Jianguo Wang, Guobao Xu
Hydrogen evolution bothers stripping analysis significantly. Dioctyl phthalate-based carbon paste electrode exhibits extremely wide cathodic potential window. It is explored as a powerful substrate electrode to solve the problem of hydrogen evolution and further improve reproducibility for stripping analysis using bismuth-coated electrodes for the first time. It was successfully applied to the simultaneous determination of Zn2+, Cd2+, and Pb2+. Linear responses are obtained for Zn2+ in the range of 10–100μgL−1 and for Pb2+ and Cd2+ in the range of 5–100μgL−1. The detection limits for Zn2+, Cd2+, and Pb2+ are 0.1μgL−1, 0.22μgL−1 and 0.44μgL−1, respectively. The method has been successfully applied to the determination of Zn2+, Cd2+, and Pb2+ in waste water samples. The detection strategy based on the combination of dioctyl phthalate-based carbon paste electrode and bismuth-coated electrodes holds great promise for stripping analysis.

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► Dioctyl phthalate-based CPE has extremely wide cathodic potential range. ► It has been used for bismuth-based stripping analysis for the first time. ► It can effectively avoid hydrogen evolution and improve reproducibility. ► It is suitable for detecting more active metals such as zinc. ► It is a powerful platform for bismuth-based electrochemical stripping analysis.

Fabrication of a sensor chip containing Au and Ag electrodes and its application for sensitive Hg(II) determination using chronocoulometry

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
Chaogui Chen, Yan Du, Jing Li, Xiurong Yang, Erkang Wang
In this work, we explored a novel fabrication method to construct Au and Ag electrodes on chip, utilizing the different solubility of gold and silver in different etching solutions. KI-I2 etching solution and 50% HNO3 were chosen to dissolve the metal layers alternatively. Planar electrodes with gold and silver could be simultaneously and accurately patterned on chip using photolithographic technique. The as-prepared electrode could be directly served as integrated three-electrode system for electrochemical measurement. Based on it, a sensing strategy has been carried out using home-made electrochemical sensing (ECS) chip, which depended on the competition of double strand DNA and Hg(II)-mediated T–T base pairs (T-Hg(II)-T). Actually, a mercury specific oligonucleotide (MSO) was immobilized onto the thus-fabricated gold working electrode and employed as the sensing element. Chronocoulometry (CC) was chosen to monitor the differences of surface charge volume and quantify the concentrations of Hg(II) ions with a low detection limit down to 1nM. Therefore, a facile method to fabricate Au and Ag electrodes has been demonstrated to simplify the production of ECS chip. The ECS chip was finally used for constructing an effective sensing platform for sensitive Hg(II) determination, which held promising potential for designing ECS chip in lab-on-a-chip device or point-of-care diagnosis.

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In this work, we explored a novel method to fabricate multi-metallic planar electrodes and constructed electrochemical sensing (ECS) chip for Hg(II) determination. Chronocoulometry was carried out to measure the differences of surface charge volume owing to specific activity of T-Hg(II)-T formation competed with double strand DNA. The facile fabrication of multi-planar electrodes and sensing platform endowed the ECS chip with great promise in environmental monitoring.
► A novel fabrication method was explored to prepare multi-metallic planar electrodes. ► Electrochemical sensing (ECS) chip has been constructed for Hg(II) analysis. ► Sensing strategy based on T-Hg(II)-T formation competed with dsDNA has been built. ► Chronocoulometry (CC) was carried out to measure the differences of surface charge. ► It resulted in a high sensitive, high selective Hg(II) determination in practical samples.

Identification of control parameters for the sulfur gas storability with bag sampling methods

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
Sang-Hee Jo, Ki-Hyun Kim, Zang-Ho Shon, David Parker
Air samples containing sulfur compounds are often collected and stored in sample bags prior to analysis. The storage stability of six gaseous sulfur compounds (H2S, CH3SH, DMS, CS2, DMDS and SO2) was compared between two different bag materials (polyvinyl fluoride (PVF) and polyester aluminum (PEA)) at five initial concentrations (1, 10, 100, 1000, and 10,000ppb). The response factors (RF) of these samples were determined after storage periods of 0, 1, and 3days by gas chromatography–pulsed flame photometric detector (GC–PFPD) combined with an air server (AS)/thermal desorber (TD) system. Although concentration reduction occurred more rapidly from samples of the high concentration standards (1000 and 10,000ppb), such trends were not evident in their low concentration counterparts (1, 10, and 100ppb). As such, temporal changes in RF values and the associated loss rates of most sulfur gases were greatly affected by their initial concentration levels. Moreover, the storability of oxidized sulfur compound (SO2) was greatly distinguished from that of reduced sulfur compounds (RSCs), as the former almost disappeared in the PVF bag even after one day. The results of our study confirm that storability of gaseous sulfur species is affected interactively by such variables as initial gas concentration level, bag material type, and oxidation status with the associated reactivity.

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► Many sampling methods have been developed and tested for various sulfur gas species. ► The analysis of actual field samples is yet subject to large sources in the sampling stage. ► The factors governing the sorptive loss of sulfur gases on bag sampling materials is assessed.

Direct rapid analysis of multiple PPCPs in municipal wastewater using ultrahigh performance liquid chromatography–tandem mass spectrometry without SPE pre-concentration

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
Ke Yu, Bing Li, Tong Zhang
Ultrahigh performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) was utilized to develop a rapid, sensitive and reliable method without solid phase extraction (SPE) pre-concentration for trace analysis of 11 pharmaceuticals and personal care products (PPCPs) in influent and effluent from municipal wastewater treatment plants (WWTPs). This method not only shortened the analysis time but also reduced analysis cost significantly by omitting SPE process and avoiding the consumption of SPE cartridge. Detection parameters for UHPLC–MS/MS analysis were optimized, including sample pH, eluent, mobile phase (solvent and additive), column temperature, and flow rate. Under the optimal conditions, all analytes were well separated and detected within 8.0min by UHPLC–MS/MS. The method quantification limits (MQLs) for the 11 PPCPs ranged from 0.040 to 88ngL−1 and from 0.030 to 90ngL−1 for influent and effluent, respectively. The matrix effect was systematically investigated and quantified for different types of samples. The analysis of influent and effluent samples of two WWTPs in Hong Kong revealed the presence of 11 PPCPs, including acyclovir, benzophenone-3, benzylparaben, carbamazepine, ethylparaben, fluconazole, fluoxetine, methylparaben, metronidazole, propylparaben, and ranitidine. Their concentrations ranged from 9.1 to 1810ngL−1 in influent and from 6.5 to 823ngL−1 in effluent samples collected from Hong Kong WWTPs.

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► Signal enhancements of 11 PPCPs were observed for non-SPE pre-concentrated samples. ► MTnon-SPE shortened analysis time, reduced analysis cost, and was more accurate. ► Good chromatographic separation of 11 PPCPs was achieved within 8.0min. ► Method quantification limits of 11 PPCPs were as low as 0.030–90ngL−1. ► Concentrations of 11 PPCPs were 6.5–1810ngL−1 in Hong Kong municipal wastewater.

Breath acetone monitoring by portable Si:WO3 gas sensors

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
Marco Righettoni, Antonio Tricoli, Samuel Gass, Alex Schmid, Anton Amann, Sotiris E. Pratsinis
Breath analysis has the potential for early stage detection and monitoring of illnesses to drastically reduce the corresponding medical diagnostic costs and improve the quality of life of patients suffering from chronic illnesses. In particular, the detection of acetone in the human breath is promising for non-invasive diagnosis and painless monitoring of diabetes (no finger pricking). Here, a portable acetone sensor consisting of flame-deposited and in situ annealed, Si-doped epsilon-WO3 nanostructured films was developed. The chamber volume was miniaturized while reaction-limited and transport-limited gas flow rates were identified and sensing temperatures were optimized resulting in a low detection limit of acetone (∼20ppb) with short response (10–15s) and recovery times (35–70s). Furthermore, the sensor signal (response) was robust against variations of the exhaled breath flow rate facilitating application of these sensors at realistic relative humidities (80–90%) as in the human breath. The acetone content in the breath of test persons was monitored continuously and compared to that of state-of-the-art proton transfer reaction mass spectrometry (PTR-MS). Such portable devices can accurately track breath acetone concentration to become an alternative to more elaborate breath analysis techniques.

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► Portable sensors were developed and tested for monitoring acetone in the human breath. ► Acetone concentrations down to 20ppb were measured with short response times (<30s). ► The present sensors were highly selective to acetone over ethanol and water. ► Sensors were applied to human breath: good agreement with highly sensitive PTR-MS. ► Tests with people at rest and during physical activity showed the sensor robustness.

Nanogold–polyaniline–nanogold microspheres-functionalized molecular tags for sensitive electrochemical immunoassay of thyroid-stimulating hormone

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
Yuling Cui, Huafeng Chen, Li Hou, Bing Zhang, Bingqian Liu, Guonan Chen, Dianping Tang
Methods based on nanomaterial labels have been developed for electrochemical immunosensors and immunoassays, but most involved low sensitivity. Herein a novel class of molecular tags, nanogold–polyaniline–nanogold microspheres (GPGs), was first synthesized and functionalized with horseradish peroxidase-conjugated thyroid-stimulating hormone antibody (HRP-Ab2) for sensitive electrochemical immunoassay of thyroid-stimulating hormone (TSH). X-ray diffraction, confocal Raman spectroscopy, scanning electron microscope and transmission electron microscope were employed to characterize the prepared GPGs. Based on a sandwich-type immunoassay format, the assay was performed in pH 5.0 acetate buffer containing 6.0mmolL−1 H2O2 by using GPG-labeled HRP-Ab2 as molecular tags. Compared with pure polyaniline nanospheres and gold nanoparticles alone, the GPG hybrid nanostructures increased the surface area of the nanomaterials, and enhanced the immobilized amount of HRP-Ab2. Several labeling protocols comprising HRP-Ab2, nanogold particle-labeled HRP-Ab2, and polyaniline nanospheres-labeled HRP-Ab2, were also investigated for determination of TSH and improved analytical features were obtained by using the GPG-labeled HRP-Ab2. With the GPG labeling method, the effects of incubation time and pH of acetate buffer on the current responses of the immunosensors were also studied. The strong attachment of HRP-Ab2 to the GPGs resulted in a good repeatability and intermediate precision down to 7%. The dynamic concentration range spanned from 0.01 to 20μIUmL−1 with a detection limit (LOD) of 0.005μIUmL−1 TSH at the 3s B criterion. Significantly, no significant differences at the 0.05 significance level were encountered in the analysis of 15 spiking serum samples between the developed electrochemical immunoassay and the commercially available enzyme-linked immunosorbent assay (ELISA) method for determination of TSH.

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► A novel immunosensing strategy was designed for detection of thyroid-stimulating hormone. ► Using nanogold–polyaniline–nanogold microspheres as molecular tags. ► Improvement of electrochemical activity of nanolabels. ► Combination enzyme labels with nanolabels for signal amplification.

Evaluation of novel amylose and cellulose-based chiral stationary phases for the stereoisomer separation of flavanones by means of nano-liquid chromatography

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
Kahina Si-Ahmed, Zeineb Aturki, Bezhan Chankvetadze, Salvatore Fanali
Three polysaccharide-based chiral stationary phases, Sepapak® 1, Sepapak® 2 and Sepapak® 3 have been evaluated in the present work for the stereoisomer separation of a group of 12 flavonoids including flavanones (flavanone, 4′-methoxyflavanone, 6-methoxyflavanone, 7-methoxyflavanone, 2′-hydroxyflavanone, 4′-hydroxyflavanone, 6-hydroxyflavanone, 7-hydroxyflavanone, hesperetin, naringenin) and flavanone glycosides (hesperidin, naringin) by nano-liquid chromatography (nano-LC). The behaviour of these chiral stationary phases (CSPs) towards the selected compounds was studied in capillary columns (100μm internal diameter (i.d.)) packed with the above mentioned CSPs using polar organic, reversed and normal elution modes. The influence of nature and composition of the mobile phase in terms of concentration and type of organic modifier, buffer type and water content (reversed phase elution mode) on the enantioresolution (R s ), retention factor (k) and enantioselectivity (α) was evaluated. Sepapak® 3 showed the best chromatographic results in terms of enantioresolution, enantioselectivity and short analysis time, employing a polar organic phase mode. A mixture of methanol/isopropanol (20/80, v/v) as mobile phase enabled the chiral separation of eight flavanones with enantioresolution factor (R s ) in the range 1.15–4.18. The same analytes were also resolved employing reversed and normal phase modes with mixtures of methanol/water and hexane/ethanol at different ratios as mobile phases, respectively. Loss in resolution for some compounds, broaden peaks and longer analysis times were observed with these last two chromatographic elution modes. Afterwards, a comparison with the other two CSPs was performed. A lower discrimination ability of Sepapak® 1 and Sepapak® 2 towards all the studied flavanoids was observed. However, Sepapak® 1 allowed the separation of naringenin enantiomers and naringin stereoisomers in polar organic phase which were not resolved with the other two CSPs. The nature of the chiral selector was found to be of utmost importance for the resolution of the selected compounds. Indeed, significant differences in enantioresolution among the three tested CSPs were observed. With regard to the only few data reported in the literature for the resolution of this class of compounds using polysaccharide-based CSPs by high performance liquid chromatography (HPLC), the results obtained in this study by means of nano-LC showed higher (R s ) values and shorter analysis time.

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Graphical abstract Highlights

► Stereoisomer separation of flavanones by nano-liquid chromatography. ► Use of polysaccharide chiral stationary phases based on cellulose and amylose. ► Evaluation of the CSPs in polar organic, reversed and normal elution modes. ► Good results concerning enantioresolution, and short analysis time were obtained.

A new imidazolium-embedded C18 stationary phase with enhanced performance in reversed-phase liquid chromatography

10 July 2012, 11:11:41
Publication year: 2012
Source:Analytica Chimica Acta, Volume 738
Hongdeng Qiu, Abul K. Mallik, Makoto Takafuji, Xia Liu, Shengxiang Jiang, Hirotaka Ihara
In this paper, a new imidazolium-embedded C18 stationary phase (SiImC18) for reversed-phase high-performance liquid chromatography is described. 1-Allyl-3-octadecylimidazolium bromide ionic liquid compound having a long alkyl chain and reactive groups was newly prepared and grafted onto 3-mercaptopropyltrimethoxysilane-modified silica via a surface-initiated radical-chain transfer addition reaction. The SiImC18 obtained was characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, diffuse reflectance infrared Fourier transform, and solid-state 13C and 29Si cross-polarization/magic angle spinning nuclear magnetic resonance spectroscopy. The selectivity toward polycyclic aromatic hydrocarbons relative to that toward alkylbenzenes exhibited by SiImC18 was higher than the corresponding selectivity exhibited by a conventional octadecyl silica (ODS) column, which could be explained by electrostatic π–π interaction cationic imidazolium and electron-rich aromatic rings. On the other hand, SiImC18 also showed high selectivity for polar compounds, which was based on the multiple interaction and retention mechanisms of this phase with different analytes. 1,6-Dinitropyrene and 1,8-dinitropyrene, which form a positional isomer pair of dipolar compounds, were separated successfully with the SiImC18 phase. Seven nucleosides and bases (i.e. cytidine, uracil, uridine, thymine, guanosine, xanthosine, and adenosine) were separated using only water as the mobile phase within 8min, which is difficult to achieve when using conventional hydrophobic columns such as ODS. The combination of electrostatic and hydrophobic interactions is important for the effective separation of such basic compounds without the use of any organic additive as the eluent in the octadecylimidazolium column.

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► Imidazolium-embedded C18 stationary phase was prepared and characterized. ► Enhanced chromatographic selectivity was observed in SiImC18 column. ► Seven nucleosides and bases were separated using only water as eluent within 8min. ► Multiple-interactions induced by embedded polar imidazolium was investigated.


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