RESUMO
Pesticides are used in the agricultural production process to ensure the yield and quality of agricultural products. However, in recent years, environmental pollution issues caused by pesticide residues have sparked widespread concern in society. It is important to develop convenient and efficient approaches to detect and monitor pesticide residues. In this study, targeting benzoylurea insecticides (BUs), polyamidoamine dendrimer-functionalized silica nanocomposite with polydopamine coating (SiO2-PAMAM-PDA) was designed and successfully synthesized. First, monodisperse silica nanoparticles were prepared by the hydrolysis of tetraethyl orthosilicate (TEOS) in mixed solution of ethanol, water and ammonia. The silane coupling agent (3-aminopropyl)triethoxysilane was then employed to introduce amino groups into the silica. Silica with the zeroth generation of polyamidoamine (PAMAM) modification (SiO2-PAMAM-G0) was obtained through Michael addition reaction of methyl acrylate. Ethylenediamine was added to polymerize with methyl acrylate using an amidation reaction to form the first-generation PAMAM (SiO2-PAMAM-G1). Finally, by polymerizing dopamine under alkaline conditions (pH=8.5), the SiO2-PAMAM-G1 was coated with PDA. Thus, the final product named SiO2-PAMAM-PDA was obtained. The composite was characterized using a transmission electron microscope (TEM) and an increase in surface roughness indicated the successful grafting of PDA coating. Dopamine structure contains abundant benzene rings and amino and hydroxyl groups. It could bind with BUs through multiple secondary interactions, such as hydrogen bond and π-π stacking interaction. Therefore, the introduction of PDA could effectively enhance the affinity of the material toward benzoylurea insecticides. The prepared nanocomposites were used as sorbents in a dispersive micro solid-phase extraction approach (D-µ-SPE). The established approach was employed to extract and enrich the BUs in water samples before high-performance liquid chromatography (HPLC) analysis. Diflubenzuron, triflumuron, hexaflumuron, and teflubenzuron were chosen as target analytes. The following was a typical D-µ-SPE procedure. The prepared adsorbents measuring 40 mg were first dispersed in an 8-mL sample solution containing 150 g/L NaCl. The dispersion was assisted by 120-s vortexing to ensure full contact between the SiO2-PAMAM-PDA and the targets. Next, the adsorbents were separated from the liquid phase by 4-min centrifugation (5000 r/min). Thereafter, the adsorbed benzoylureas were eluted using 1 mL acetonitrile as desorption solvent by 120-s vortexing. Separated by centrifugation, the eluate was dried under a mild nitrogen stream. The solid remains were redissolved in 0.1 mL of acetonitrile, filtered by filter membrane (0.22 µm), and then analyzed by HPLC. The experimental conditions in the D-µ-SPE process could have a great impact on the extraction efficiency. Experimental conditions were optimized using a single factor optimization approach to further enhance the extraction recoveries. The optimized conditions included adsorbent amount, extraction time, desorption solvent type, desorption solvent volume, desorption time, and NaCl addition amount. Under the optimal conditions, a linearity range of 10-500 µg/L and limits of detection (LODs, S/N=3) of 1.1-2.1 µg/L were obtained. The extraction recoveries and relative standard deviations (RSDs) of the four BUs were 82.8%-94.1% and 2.1%-8.0%, respectively. The established approach was compared with reported approaches targeting benzoylurea insecticides. It was discovered that this approach consumed less sample, material, organic solvent, and pretreatment time. It provided a more rapid and green choice for the determination of benzoylurea pesticides. To determine the applicability, the proposed approach was applied to analyze the four benzoylurea insecticides in three river water samples. The real water samples were pretreated using the developed approach ahead of instrumental analysis, and no benzoylurea pesticides residue was detected. Next, standard addition experiments were performed under three spiking levels, including 15, 50, and 200 µg/L. The established approach had good accuracy and feasibility with satisfactory recoveries (69.5%-99.4%) and RSDs (0.2%-9.5%).
Assuntos
Dendrímeros , Diflubenzuron , Inseticidas , Nanocompostos , Resíduos de Praguicidas , Acetonitrilas/análise , Acrilatos , Amônia/análise , Benzeno/análise , Cromatografia Líquida de Alta Pressão , Dendrímeros/análise , Diflubenzuron/análise , Dopamina/análise , Etanol/análise , Etilenodiaminas/análise , Indóis , Inseticidas/análise , Nanocompostos/análise , Nitrogênio/análise , Resíduos de Praguicidas/análise , Poliaminas , Polímeros , Silanos/análise , Dióxido de Silício/análise , Cloreto de Sódio/análise , Extração em Fase Sólida , Solventes/análise , Água/análiseRESUMO
We report the fabrication of 6-phenylhexylsilane derivatized, sputtered silicon, solid phase microextraction fibers that show parts per trillion detection limits for polyaromatic hydrocarbons, and negligible carry over and phase bleed. Their fabrication involves sputtering silicon on silica fibers under various conditions. Six different fibers were evaluated by generating three different thicknesses of sputtered silicon at two different throw distances, which altered the morphologies of the silicon surfaces. All of the fibers were coated with similar thicknesses of 6-phenylhexylsilane (ca. 2 nm). These fibers were characterized with multiple analytical techniques. The optimum fiber configuration was then used to analyze polyaromatic hydrocarbons via direct immersion, gas chromatography mass spectrometry. Our best fiber for the extraction of low molecular weight polyaromatic hydrocarbons in water had similar performance to that of a commercial fiber. However, our fiber demonstrated ca. 3 times the extraction efficiency for higher molecular weight polyaromatic hydrocarbons. In addition, it outperformed the commercial fiber by showing better linearity, repeatability, and detection limits. A method for analyzing polyaromatic hydrocarbons in baby formula was developed, which showed very good linearity (0.5-125 ppb), repeatability (2-26%), detection limits (0.12-0.81 ppb), and recoveries (103-135%). In addition, our fiber showed much less (negligible) carry over and phase bleed than the commercially available fibers.
Assuntos
Fórmulas Infantis/química , Hidrocarbonetos Policíclicos Aromáticos/análise , Microextração em Fase Sólida/métodos , Água/química , Cromatografia Gasosa-Espectrometria de Massas/métodos , Limite de Detecção , Fibras Minerais/análise , Silanos/análise , Silício/análise , Poluentes Químicos da Água/análise , Poluição da Água/análiseRESUMO
We present the results of research on the optimal conditions for the separation and determination of newly obtained hypercoordinated compounds, which belong to the group of electrostatically stabilized silanates. The research involved five stationary and four mobile phases. The best selectivity was obtained using the graphite phase and the mobile phase consisting of acetonitrile/water (80/20). The maximum selectivity of the determined electrostatically stabilized silanates was 1.13 and 1.06 for (1), (2), (3); 1.10 and 1.15 for (4), (5), (6); and 1.12 and 1.15 for (7), (8), (9). The octadecyl phase (which is recommended as standard) did not yield satisfactory results.
Assuntos
Silanos/análise , Cromatografia Líquida de Alta Pressão , Estrutura Molecular , Eletricidade EstáticaRESUMO
In this work, a new analytical method based on polydopamine functionalized magnetic graphene (PDA@MG) adsorbent material has been developed to determine three triazole fungicides in water samples. As previous step, a novel polydopamine functionalized PDA@MG adsorbent material has been successfully prepared, which was characterized by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM). Based on this novel material, a new magnetic solid phase extraction (MSPE) method coupled with high performance liquid chromatography (HPLC) has been established for the determination of triazole fungicides in water samples. The main factors which could affect the experimental results were optimized. Under the optimal conditions, good linarites has been achieved in the range of 0.2-50 µg L-1, with the correlation coefficients (R2) were between 0.9962 and 0.9996. The limits of detections (LODs) were 0.0048-0.0084 µg L-1, and the relative standard deviations (RSDs) were between 1.7% and 4.8%. In addition, enrichment factors (EFs) were 572-916 times, which showed triazole fungicides residues could be accurately extracted and analyzed in this way. In the final experiment, the established method was applied to the detection of target analyzes in water samples. Satisfied results could be obtained for tebuconazole, propiconazole, and flusilazole. The recoveries of five water samples were between 69.4% and 106.4%, and the RSD were between 1.0% and 6.5%. The development method is more easy, effective, green and environmental-friendly, and has potential for application.
Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Fungicidas Industriais/análise , Grafite/química , Indóis/química , Polímeros/química , Triazóis/análise , Adsorção , Fungicidas Industriais/isolamento & purificação , Limite de Detecção , Fenômenos Magnéticos , Silanos/análise , Extração em Fase Sólida/métodos , Triazóis/isolamento & purificaçãoRESUMO
RATIONALE: Nitrogen mustards (NMs) are vesicant class of chemical warfare agents. From the viewpoint of the Chemical Weapons Convention partially hydrolyzed products of nitrogen mustards (pHpNMs) are considered as important markers of nitrogen mustard exposure. The detection of pHpNMs from biological or environmental samples is highly useful for obtaining forensic evidence of exposure to NMs. METHODS: Gas chromatography interfaced with tandem mass spectrometry (GC/MS/MS) is a widely used tool for the identification and sensitive detection of metabolites of NMs in complex matrices. The pHpNMs were derivatized using silylating agents as they are highly polar and non-amenable to GC. The mass spectral studies of these silyl derivatives of pHpNMs were performed using GC/MS/MS in both electron ionization (EI) and chemical ionization (CI) mode. RESULTS: Various approaches have been proposed to assess the fragmentation pathways of the trimethylsilyl (TMS) and tert-butyldimethylsilyl (TBDMS) derivatives of pHpNMs. All the proposed fragmentation pathways were based on the product and/or precursor ion scanning of corresponding ions in both EI and CI mode. In the case of EI, most of the fragmentation pathways involved either α-cleavage or inductive cleavage. CONCLUSIONS: This is the first report on the MS study of the silyl derivatives of pHpNMs. The study of the two different derivatives of pHpNMs using both EI- and CI-MS provides a reliable, unambiguous identification of pHpNMs in complex environmental and biomedical matrices (such as plasma and urine) during any verification activities.
Assuntos
Substâncias para a Guerra Química/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Mecloretamina/análise , Silanos/análise , Biomarcadores/análise , Substâncias para a Guerra Química/química , Hidrólise , Mecloretamina/química , Silanos/química , Espectrometria de Massas em Tandem/métodosRESUMO
ß-Tryptase is released from mast cells upon degranulation in response to allergic and inflammatory stimuli. Human tryptase is a homotetrameric serine protease with 4 identical active sites directed toward a central pore. These active sites present an optimized scenario for the rational design of bivalent inhibitors, which bridge 2 adjacent active sites. Using (3-[1-acylpiperidin-4-yl]phenyl)methanamine as the pharmacophoric core and a disiloxane linker to span 2 active sites we have successfully produced a novel bivalent tryptase inhibitor, compound 1a, with a comparable profile to previously described inhibitors. Pharmacological properties of compound 1a were studied in a range of in vitro enzymic and cellular screening assays, and in vivo xenograft models. This non-peptide inhibitor of tryptase demonstrated superior activity (IC50 at 100 pmol/L tryptase = 1.82 nmol/L) compared to monomeric modes of inhibition. X-ray crystallography validated the dimeric mechanism of inhibition, and 1a demonstrated good oral bioavailability and efficacy in HMC-1 xenograft models. Furthermore, compound 1a demonstrated extremely slow off rates and high selectivity against-related proteases. This highly potent, orally bioavailable and selective inhibitor of human tryptase will be an invaluable tool in future studies to explore the therapeutic potential of attenuating the activity of this elusive target.
Assuntos
Mastócitos/efeitos dos fármacos , Silanos/química , Silanos/farmacologia , Triptases/antagonistas & inibidores , Animais , Linhagem Celular , Cristalografia por Raios X , Relação Dose-Resposta a Droga , Desenho de Fármacos , Humanos , Imuno-Histoquímica , Masculino , Mastócitos/enzimologia , Mastócitos/patologia , Camundongos , Camundongos Endogâmicos C57BL , Modelos Moleculares , Estrutura Molecular , Farmacocinética , Silanos/análise , Silanos/farmacocinéticaRESUMO
A series of fluorinated dental resin composites were prepared with two kinds of SiO2 particles. Bis-GMA (bisphenol A-glycerolate dimethacrylate)/4-TF-PQEA (fluorinated acrylate monomer)/TEGDMA (triethylene glycol dimethacrylate) (40/30/30, wt/wt/wt) was introduced as resin matrix. SiO2 nanopartices (30nm) and SiO2 microparticles (0.3µm) were silanized with 3-methacryloxypropyl trimethoxysilane (γ-MPS) and used as fillers. After mixing the resin matrix with 0%, 10%, 20%, 30% SiO2 nanopartices and 0%, 10%, 20%, 30%, 40%, 50% SiO2 microparticles, respectively, the fluorinated resin composites were obtained. Properties including double bond conversion (DC), polymerization shrinkage (PS), water sorption (Wp), water solubility (Wy), mechanical properties and cytotoxicity were investigated in comparison with those of neat resin system. The results showed that, filler particles could improve the overall performance of resin composites, particularly in improving mechanical properties and reducing PS of composites along with the addition of filler loading. Compared to resin composites containing SiO2 microparticles, SiO2 nanoparticles resin composites had higher DC, higher mechanical properties, lower PS and lower Wp under the same filler content. Especially, 50% SiO2 microparticles reinforced resins exhibited the best flexural strength (104.04 ± 7.40MPa), flexural modulus (5.62 ± 0.16GPa), vickers microhardness (37.34 ± 1.13 HV), compressive strength (301.54 ± 5.66MPa) and the lowest polymerization (3.42 ± 0.22%).
Assuntos
Resinas Acrílicas/química , Resinas Compostas/química , Metacrilatos/análise , Polímeros/análise , Poliuretanos/química , Silanos/análise , Dióxido de Silício/análise , Humanos , Teste de Materiais , Polimerização , Propriedades de SuperfícieRESUMO
The interaction between disulfiram (Antabus®) and silica was studied experimentally by adsorption from apolar solvent onto highly porous silica material (Santa Barbara amorphous material-3) with large surface area. The adsorption isotherm was fitted to the Langmuir model by accounting 2 different affinities contributing to the overall behavior, which were attributed to 2 different types of silanol groups (i.e., geminal and vicinal) present on amorphous silica surfaces. This assumption was supported by theoretical calculations. In addition, the model could describe the adsorption of ibuprofen to the carrier material, indicating that the model bears big potential for describing the interactions between silica surfaces and drug molecules.
Assuntos
Inibidores de Acetaldeído Desidrogenases/química , Dissulfiram/química , Dióxido de Silício/química , Adsorção , Anti-Inflamatórios não Esteroides/química , Ibuprofeno/química , Modelos Químicos , Modelos Moleculares , Porosidade , Silanos/análise , Solventes/química , Propriedades de Superfície , TermodinâmicaRESUMO
A mesoporous silica Santa Barbara Amorphous-15 (SBA-15) has been first functionalized with 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (a silane with three amines) and then reacted with an excess of phenyl glycidyl ether to generate a mixed-mode anion-exchanger containing both anion-exchange (three amines) and reversed-phase (multiple ether-linked phenyls) functionalities in a single branched ligand. The resulting material has been characterized by scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, Fourier-transform infrared spectroscopy, and elemental analysis. The results obtained indicated a BET specific surface area (SBET) of 362.5m2g-1, a pore volume of 0.70cm3g-1 with a narrow pore size distribution centered at 6.6nm, and carbon and nitrogen contents of 28.30% and 2.84%, respectively. The dimensions of these particles (â¼5µm diameter, â¼60µm length), their large surface areas, their high-density functionalities and anion-exchange mixed-mode characteristics make them very attractive for highly effective solid phase extraction (SPE) of acidic nonsteroidal anti-inflammatory drugs (NSAIDs). The important parameters on extraction efficiency including sample pH, breakthrough volume, type and volume of eluent were optimized. A simple and sensitive analytical method based on mixed-mode SPE coupled to high-performance liquid chromatography with ultraviolet detection (HPLC-UV) was developed and successfully applied to the analysis of four NSAIDs (ketoprofen, naproxen, diclofenac, and ibuprofen) in spiked real water samples with satisfactory recoveries (80.6-110.9%) and repeatability (relative standard deviation <11.3%, n=3). The limit of detections of four NSAIDs were 0.006-0.070µgL-1 for tap water, and 0.014-0.16µgL-1 for river water and wastewater, with the enrichment factors of 806-1109-fold.
Assuntos
Anti-Inflamatórios não Esteroides/isolamento & purificação , Monitoramento Ambiental/métodos , Água Doce/química , Dióxido de Silício/química , Extração em Fase Sólida/métodos , Adsorção , Anti-Inflamatórios não Esteroides/análise , Cromatografia Líquida de Alta Pressão , Ibuprofeno/análise , Cetoprofeno/análise , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Naproxeno/análise , Silanos/análise , Espectroscopia de Infravermelho com Transformada de Fourier , Águas Residuárias/química , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/isolamento & purificaçãoRESUMO
The encapsulation mechanism of DNA in sol-gel derived silica has been explored in order to elucidate the effect of DNA conformation on encapsulation and to identify the nature of chemical/physical interaction of DNA with silica during and after sol-gel transition. In this respect, double stranded DNA and dAMP (2'-deoxyadenosine 5'-monophosphate) were encapsulated in silica using an alkoxide-based sol-gel route. Biomolecule-encapsulating gels have been characterized using UV-Vis, 29Si NMR, FTIR spectroscopy and gas adsorption (BET) to investigate chemical interactions of biomolecules with the porous silica network and to examine the extent of sol-gel reactions upon encapsulation. Ethidium bromide intercalation and leach out tests showed that helix conformation of DNA was preserved after encapsulation. For both biomolecules, high water-to-alkoxide ratio promoted water-producing condensation and prevented alcoholic denaturation. NMR and FTIR analyses confirmed high hydraulic reactivity (water adsorption) for more silanol groups-containing DNA and dAMP encapsulated gels than plain silica gel. No chemical binding/interaction occurred between biomolecules and silica network. DNA and dAMP encapsulated silica gelled faster than plain silica due to basic nature of DNA or dAMP containing buffer solutions. DNA was not released from silica gels to aqueous environment up to 9 days. The chemical association between DNA/dAMP and silica host was through phosphate groups and molecular water attached to silanols, acting as a barrier around biomolecules. The helix morphology was found not to be essential for such interaction. BET analyses showed that interconnected, inkbottle-shaped mesoporous silica network was condensed around DNA and dAMP molecules.
Assuntos
DNA/administração & dosagem , Nucleotídeos de Desoxiadenina/administração & dosagem , Sílica Gel/química , Dióxido de Silício/química , DNA/química , Nucleotídeos de Desoxiadenina/química , Portadores de Fármacos/química , Conformação de Ácido Nucleico , Transição de Fase , Porosidade , Silanos/análiseRESUMO
Method validations in addition to decline patterns of fluquinconazole and flusilazole in lettuce grown under greenhouse conditions at two different locations were investigated. Following the application of fluquinconazole and flusilazole at a dose rate of 20 mL/20 L water, lettuce samples were collected randomly for up to 7 days post-application, and simultaneously extracted with acetone, purified through solid-phase extraction, analyzed via gas chromatography with a nitrogen phosphorus detector, and confirmed through gas chromatography-mass spectrometry. The linearity was excellent, with determination coefficients (R(2) ) between 0.9999 and 1.0. The method was validated in triplicate at two different spiking levels (0.2 and 1.0 mg/kg) with satisfactory recoveries between 75.7 and 97.9% and relative standard deviations of <9. The limit of quantification was 0.01 mg/kg. Both analytes declined very quickly, as can be seen from the short half-life time of <4 days. Statistical analysis revealed significant differences between residues at different days of sampling, except at 7 days post-application (triple application). At that point, the decline patterns of fluquinconazole and flusilazole were independent of application rate, location, temperature and humidity. Copyright © 2015 John Wiley & Sons, Ltd.
Assuntos
Cromatografia Gasosa-Espectrometria de Massas/métodos , Lactuca/química , Quinazolinonas/análise , Silanos/análise , Triazóis/análise , Cromatografia Gasosa-Espectrometria de Massas/instrumentação , Limite de DetecçãoRESUMO
A precise and simplified method of sample preparation for the simultaneous quantification of the antibiotics ß-lactam, macrolide, tetracycline, sulfonamide, and quinolone in bovine milk was developed. The central composite design of response surface methodology was used to design and optimize the method for the determination of six different antibiotic residues in milk. The recovery of each antibiotic was studied using a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. Octadecylsilane (C18), primary secondary amine (PSA), and sodium acetate (Na acetate) were the main factors affecting the recovery of each antibiotic. After optimization, the maximum predicted recovery rate was 84.18% for erythromycin under the optimized conditions of 101.20 mg C18, 52.00 mg PSA, and 1.01 g Na acetate. The recovery rates of the five other antibiotic residues ranged from 86.09% to 115.99%. The results suggested that modified QuEChERS could effectively be implemented in the analysis of antibiotic residues in milk.
Assuntos
Antibacterianos/análise , Cromatografia Líquida/métodos , Resíduos de Drogas/análise , Leite/química , Espectrometria de Massas em Tandem/métodos , Animais , Eritromicina/análise , Contaminação de Alimentos/análise , Modelos Lineares , Reprodutibilidade dos Testes , Silanos/análise , Acetato de Sódio/análiseRESUMO
Pressure assisted capillary electrophoresis was applied to determination of acid dissociation constants (pKa) of six widely used triazole fungicides (cyproconazole, epoxiconazole, flusilazole, tebuconazole, penconazole and propiconazole) in aqueous medium. The pKa values were determined from the dependence of effective electrophoretic mobility of the triazole fungicides on p[H(+)] of the background electrolyte (BGE) using non-linear regression analysis. The p[H(+)] was used instead of pH to reflect the increased ionic strength of the strongly acidic BGEs (pH<1.75) as compared to the BGEs at pH equal to or greater than 1.75. Prior to the pKa calculation, the measured effective electrophoretic mobilities were corrected to the reference temperature (25°C) and constant ionic strength (25mM). The regression function was modified to allow the determination of pKa in the BGEs of varying ionic strength. The electrophoretic measurements showed that the above triazole fungicides are very weak bases - their pKa values were found to be in the range 1.05-1.97 and were in a good agreement with the values calculated by SPARC online pKa calculator.
Assuntos
Fungicidas Industriais/análise , Triazóis/análise , Eletrólitos , Eletroforese Capilar/métodos , Compostos de Epóxi/análise , Concentração de Íons de Hidrogênio , Concentração Osmolar , Pressão , Silanos/análiseRESUMO
The present study described the preparation and application of zwitterionic stationary phases (ACS) with controllable ratio of positively charged tertiary amine groups and negatively charged carboxyl groups. Various parameters, including water content, pH values and ionic strength of the mobile phase, were investigated to study the chromatographic characteristics of ACS columns. The prepared ACS columns demonstrated a mix-mode retention mechanism composed of surface adsorption, partitioning and electrostatic interactions. The elemental analysis of different batches of the ACS phases demonstrated good reproducibility of the preparation strategy. Additionally, various categories of compounds, including nucleosides, water-soluble vitamins, benzoic acid derivatives and basic compounds were successively employed to evaluate the separation selectivity of the prepared ACS stationary phases. These ACS phases exhibited entirely different selectivity and retention behavior from each other for various polar analytes, demonstrating the excellent application potential in the analysis of polar compounds in HILIC.
Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Adsorção , Ácido Benzoico/análise , Ácido Benzoico/química , Cromatografia Líquida de Alta Pressão/instrumentação , Cromatografia Gasosa-Espectrometria de Massas , Concentração de Íons de Hidrogênio , Interações Hidrofóbicas e Hidrofílicas , Espectroscopia de Ressonância Magnética , Nucleosídeos/análise , Concentração Osmolar , Reprodutibilidade dos Testes , Silanos/análise , Silanos/química , Eletricidade Estática , Vitaminas/análiseRESUMO
A new, simple and sensitive method was developed for the determination of silicon tetrahydride in the air of workplace in this study. The alkaline resin-based spherical activated carbon was used to collect sample of silicon tetrahydride at workplace. Silicon tetrahydride was then desorbed from active carbon in 100°C hot water. After reacting with ammonium molybdate, oxalic acid and 1,2,4-trichlorobenzene alpha-naphthol amino sulfonic acid under acid condition, silicon tetrahydride was transformed into silicon molybdenum blue. The absorbance of silicon molybdenum blue was quantitatively measured at the wavelength of 680 nm. The results showed that the average sampling efficiency and desorption efficiency were 97.53% and 94.94%, respectively by this method. Detection limits were 0.054 µg/mL for the spectrophotometric method and 0.14 mg/m(3) for the determination of silicon tetrahydride in the air of workplace (sampling volume was 7.5 L). The conversion rate of silicon tetrahydride gradually decreased when storage time of samples was extended. The descent rate of sample was less than 10% when the sample was sealed for 7 days in the room temperature. It was concluded that this spectrophotometric method can be successfully used to determine silicon tetrahydride in the worksites.
Assuntos
Poluentes Ocupacionais do Ar/análise , Silanos/análise , Espectrofotometria/métodos , Local de Trabalho , Humanos , Limite de Detecção , Reprodutibilidade dos TestesRESUMO
In the present work, we demonstrate the potential of double gate junctionless (JL) architecture for enhanced sensitivity for detecting biomolecules in cavity modulated field effect transistors (FETs). The higher values of body factor, achieved in asymmetric gate operation under impact ionization is utilized for enhanced sensing margin which is nearly five times higher than compared to symmetrical mode operation. The intrinsic detection sensitivity is evaluated in terms of threshold voltage change, and the ratio of drain current in the presence and absence of biomolecules in JL nanotransistors. It is shown that asymmetric mode JL transistor achieves a higher degree of detection sensitivity even for a partially filled cavity. The work demonstrates the potential of JL channel architecture for cavity based dielectric modulated FET biosensors.
Assuntos
Técnicas Biossensoriais/instrumentação , Nanotecnologia/instrumentação , Transistores Eletrônicos , Biotina/análise , Eletricidade , Propilaminas/análise , Silanos/análise , Estreptavidina/análiseRESUMO
The preparation of aminated monolayers with a controlled density of functional groups on silica surfaces through a simple vapor deposition process employing different ratios of two suitable monoalkoxysilanes, (3-aminopropyl)diisopropylethoxysilane (APDIPES) and (3-cyanopropyl)dimethylmethoxysilane (CPDMMS), and advances in the reliable quantification of such tailored surfaces are presented here. The one-step codeposition process was carried out with binary silane mixtures, rendering possible the control over a wide range of densities in a single step. In particular, APDIPES constitutes the functional silane and CPDMMS the inert component. The procedure requires only small amounts of silanes, several ratios can be produced in a single batch, the deposition can be carried out within a few hours and a dry atmosphere can easily be employed, limiting self-condensation of the silanes. Characterization of the ratio of silanes actually bound to the surface can then be performed in a facile manner through contact angle measurements using the Cassie equation. The reliable estimation of the number of surface functional groups was approached with a dual-mode BODIPY-type fluorescence label, which allows quantification by fluorescence and XPS on one and the same sample. We found that fluorescence and XPS signals correlate over at least 1 order of magnitude, allowing for a direct linking of quantitative fluorescence analysis to XPS quantification. Employment of synchrotron-based methods (XPS; reference-free total reflection X-ray fluorescence, TXRF) made the traceable quantification of surface functional groups possible, providing an absolute reference for quantitative fluorescence measurements through a traceable measurement chain.
Assuntos
Reagentes de Ligações Cruzadas/química , Espectroscopia Fotoeletrônica/métodos , Silanos/análise , Silanos/química , Fluorescência , Microscopia de Força Atômica , Propriedades de SuperfícieRESUMO
This paper discusses the concentrations and congener patterns of PCBs unintentionally present in chlorophenylsilanes. Chlorophenylsilanes are used in the production of silicone-based adhesives and phenyl silicones. The concentration of PCBs in adhesives was found to range from not-detectable concentrations to 40mg/kg. The concentrations of PCBs in trichlorophenylsilane, dichlorodiphenylsilane, chlorotriphenylsilane, and diphenylsilanediol were 0.00072-2.7, 6.5-1,500, 0.019-1.1, and 0.12-120mg/kg, respectively. Dichlorodiphenylsilane and diphenylsilanediol, in particular, had high PCB concentrations. The PCB concentration of some specimens exceeded the 50mg/kg limit set by the transportation regulations of the Stockholm Convention. In the adhesives and chlorophenylsilanes, mono- and di-chlorinated biphenyls were detected in high proportions. The congeners detected in dichlorinated biphenyls had a structure in which one chlorine atom was substituted at each of the two aryls of the biphenyl backbone. This indicated that the chlorobenzene used for synthesizing chlorophenylsilanes undergoes dimerization. The congener and homologue patterns of the adhesives containing PCBs were similar to dichlorodiphenylsilane and diphenylsilanediol. It was concluded that the production of the adhesives is based on these substances. In addition, these results indicate that silicone-based products may become a source of PCBs in the environment, leading to irregular PCB values in environmental analysis.
Assuntos
Adesivos/análise , Bifenilos Policlorados/análise , Silanos/análise , Adesivos/química , Bifenilos Policlorados/química , Silicones/síntese químicaRESUMO
Of the tens of thousands of chemicals in use, only a small fraction have been analyzed in environmental samples. To effectively identify environmental contaminants, methods to prioritize chemicals for analytical method development are required. We used a high-throughput model of chemical emissions, fate, and bioaccumulation to identify chemicals likely to have high concentrations in specific environmental media, and we prioritized these for target analysis. This model-based screening was applied to 215 organosilicon chemicals culled from industrial chemical production statistics. The model-based screening prioritized several recognized organosilicon contaminants and generated hypotheses leading to the selection of three chemicals that have not previously been identified as potential environmental contaminants for target analysis. Trace analytical methods were developed, and the chemicals were analyzed in air, sewage sludge, and sediment. All three substances were found to be environmental contaminants. Phenyl-tris(trimethylsiloxy)silane was present in all samples analyzed, with concentrations of â¼50 pg m(-3) in Stockholm air and â¼0.5 ng g(-1) dw in sediment from the Stockholm archipelago. Tris(trifluoropropyl)trimethyl-cyclotrisiloxane and tetrakis(trifluoropropyl)tetramethyl-cyclotetrasiloxane were found in sediments from Lake Mjøsa at â¼1 ng g(-1) dw. The discovery of three novel environmental contaminants shows that models can be useful for prioritizing chemicals for exploratory assessment.
Assuntos
Monitoramento Ambiental/métodos , Poluentes Ambientais/análise , Modelos Teóricos , Poluentes Ambientais/química , Sedimentos Geológicos/química , Lagos/química , Noruega , Esgotos/análise , Silanos/análise , SuéciaRESUMO
Today's fluoride-releasing varnishes (F-varnish) contain a wide variety of ingredients which present analytical challenges for measuring their total fluoride content. This study reports improved methods to measure fluoride content in F-varnishes. Six different commercially available F-varnishes that contain difluorosilane (0.1% F) or NaF (2.26% F) alone or in combination with calcium-phosphates were analyzed. In a vial, 1-3 drops (0.05-0.15 g) of varnish product was dispensed, dissolved in chloroform, equilibrated in TISAB and analyzed via fluoride ion-selective electrode. The average weight percentage of fluoride for all F-varnishes containing NaF ranged from 2.03 to 2.24% F, which is within 90% of the declared label concentration of 2.26% F. Analysis of the difluorosilane-containing product required an additional hydrolysis step. ANOVA found no significant difference between the 5% NaF varnishes at p < 0.05. This method for fluoride analysis yields reliable and reproducible results and can be used for a wide variety of F-varnishes. The standard uncertainty for this method is ±4%. This method may become the basis for national and international standards that ensure the F-varnish products used in clinical practice have the fluoride content declared in the product literature.