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In modern era, wireless communications at ultrafast speed are need of the hour and search for its solution through cutting edge sciences is a new perspective. To address this issue, the data rates in order of terabits per second (TBPS) could be a key step for the realization of emerging sixth generation (6G) networks utilizing terahertz (THz) frequency regime. In this context, new class of transition metal dichalcogenides (TMDs) have been introduced as potential candidates for future generation wireless THz technology. Herein, a strategy has been adopted to synthesize high-quality monolayer of molybdenum di-sulfide (MoS2) using indigenously developed atmospheric pressure chemical vapor deposition (APCVD) set-up. Further, the time-domain transmission and sheet conductivity were studied as well as a plausible mechanism of terahertz response for monolayer MoS2 has been proposed and compared with bulk MoS2. Hence, the obtained results set a stepping stone to employ the monolayer MoS2 as potential quantum materials benefitting the next generation terahertz communication devices.
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The present study investigated the impacts of treated effluent discharge on physicochemical and biological properties of coastal waters from three pharmaceuticals situated along the coast of Visakhapatnam (SW Bay of Bengal). Seawater samples were collected (during the months of December 2013, March 2014 and April 2014) from different sampling locations (Chippada (CHP), Tikkavanipalem (TKP) and Nakkapalli (NKP)) at 0- and 30-m depths within 2-km radius (0.5 km = inner, 1 km = middle and 2 km = outer sampling circles) from the marine outfall points. Physicochemical and biological parameters, which differed significantly within the stations, were likely to be influenced by strong seasonality rather than local discharge. Dissolved oxygen variability was tightly coupled with both physical and biological processes. Phytoplankton cell density and total chlorophyll (TChla) concentrations were significantly correlated with dissolved inorganic nutrient concentrations. CHP (December) represented a diatom bloom condition where the highest concentrations of diatom cells, total chlorophyll (TChla), dissolved oxygen coupled with lower zooplankton abundance and low nutrient levels were noticed. The centric diatom, Chaetoceros sp. (> 50%) dominated the phytoplankton community. TKP (March) represented a post-diatom bloom phase with the dominance of Pseudo-nitzschia seriata; zooplankton abundance and nutrient concentrations were minimum. Conversely, NKP (April) represented a warm well-stratified heterotrophic period with maximum zooplankton and minimum phytoplankton density. Dinoflagellate abundance increased at this station. Relatively higher water temperature, salinity, inorganic nutrients coupled with very low concentrations of dissolved oxygen, TChla and pH were observed at this station. Copepods dominated the zooplankton communities in all stations and showed their highest abundance in the innermost sampling circles. Treated effluent discharge did not seem to have any significant impact at these discharge points.
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Bahías/química , Monitoreo del Ambiente , Agua de Mar/química , Eliminación de Residuos Líquidos/estadística & datos numéricos , Aguas Residuales/química , Animales , Clorofila/análisis , Copépodos , Diatomeas , Dinoflagelados , India , Fitoplancton , Salinidad , Estaciones del Año , Aguas Residuales/estadística & datos numéricos , ZooplanctonRESUMEN
Herein, we report a facile synthesis, characterization, and electrochemical sensing application of ZnO nanopeanuts synthesized by a simple aqueous solution process and characterized by various techniques in order to confirm the compositional, morphological, structural, crystalline phase, and optical properties of the synthesized material. The detailed characterizations revealed that the synthesized material possesses a peanut-shaped morphology, dense growth, and a wurtzite hexagonal phase along with good crystal and optical properties. Further, to ascertain the useful properties of the synthesized ZnO nanopeanut as an excellent electron mediator, electrochemical sensors were fabricated based on the form of a screen printed electrode (SPE). Electrochemical and current-voltage characteristics were studied for the determination of picric acid sensing characteristics. The electrochemical sensor fabricated based on the SPE technique exhibited a reproducible and reliable sensitivity of ~1.2 µA/mM (9.23 µA·mM-1·cm-2), a lower limit of detection at 7.8 µM, a regression coefficient (R²) of 0.94, and good linearity over the 0.0078 mM to 10.0 mM concentration range. In addition, the sensor response was also tested using simple I-V techniques, wherein a sensitivity of 493.64 µA·mM-1·cm-2, an experimental Limit of detection (LOD) of 0.125 mM, and a linear dynamic range (LDR) of 1.0 mM-5.0 mM were observed for the fabricated picric acid sensor.
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With an increasing focus on applied research, series of single/composite materials are being investigated for device development to detect several hazardous, dangerous, and toxic molecules. Here, we report a preliminary attempt of an electrochemical sensor fabricated using pristine Ni and Cr-doped nano tin oxide material (SnO2) as a tool to detect agro-hazardous material, i.e. Organophosphate (OP, chlorpyrifos). The nanomaterial was synthesized using the solution method. Nickel and chromium were used as dopant during synthesis. The synthesized material was calcined at 1000 °C and characterized for morphological, structural, and elemental analysis that showed the formation of agglomerated nanosized particles of crystalline nature. Screen-printed films of powder obtained were used as a matrix for working electrodes in a cyclic voltammogram (CV) at various concentrations of organophosphates (0.01 to 100 ppm). The CV curves were obtained before and after the immobilization of acetylcholinesterase (AChE) on the nanomaterial matrix. An interference study was also conducted with hydroquinone to ascertain the selectivity. The preliminary study indicated that such material can be used as suitable matrix for a device that can easily detect OP to a level of 10 ppb and thus contributes to progress in terms of desired device technology for the food and agricultural-industries.
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Here we report development of a hydroquinone (HQ) electrochemical sensor using nanosized manganese doped titanium oxide as a composite material. The nanomaterial was synthesized with sol gel method using calculated amount of Mn and Ti atoms resulting into a composite metal oxide. Morphological observations indicated a uniform particle size and shape distribution with almost spherical shape and size of about 2030 nm. While structural analysis indicated formation of mixed phase of TiO2 and MnO forming MnTiO3. The synthesized nanomaterial was used as a matrix for fabrication of hydroquinone electrochemical sensor and tested over a wide range from 2 mM to 10 mM. The developed electrochemical sensor exhibited sensitivity of 2.96 µA mM⻹ (23.55 µA mM⻹ cm⻲) with a detection limit of 7.5 µM, which is rarely reported for such composite nanomaterial.
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To better understand the spatial and temporal variation in surface water and sediment quality, parameters were evaluated from the three sites Chicalim Bay (CB), Nerul Creek (NC), and Chapora Bay (ChB) along the Goa coast, which has major oyster beds. Multivariate analysis such as cluster analysis (CA), Box-Whisker plot (Box plot), and principle component analysis (PCA) revealed that nitrate (NO3-N), nitrite (NO2-N), phosphate (PO4-P), particulate organic carbon (POC), total suspended solids (TSS), dissolved oxygen (DO), and phaeopigments are the responsible parameters for spatio-temporal variability among the studied sites. Results showed an elevated level of ecotoxicological hazard at CB while moderate toxicological risks were observed for organisms at NC. In contrast, ChB was considerably pristine compared with other two sampling sites. Results of present study showed marked dominance of nutrients, phaeopigments, POC, and TSS at CB and NC. The increased levels of these parameters are attributed to the anthropogenic activities which may cause potential risk to humans via consumption of oysters. Therefore, we suggest monitoring heavy metal concentrations in tissue of commercially important oyster species, and their ambient environment (water and sediment) from these estuaries is necessary to create a comprehensive pollution database.
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Monitoreo del Ambiente/métodos , Sedimentos Geológicos/química , Metales Pesados/análisis , Ríos/química , Agua de Mar/química , Contaminantes Químicos del Agua/análisis , Animales , Bahías , Análisis por Conglomerados , Monitoreo del Ambiente/estadística & datos numéricos , Estuarios , India , Análisis Multivariante , Ostreidae/química , Estaciones del AñoRESUMEN
Here we report a simple and effective method in tailoring the optoelectronic properties of semi-conducting metal oxide for suitable device application. Sol-gel synthesis was used to synthesize manganese doped TiO2 nanopowder and commercially available TiO2 nanopowder was used as reference material. Thick films of these powder were screen printed on FTO coated glass and annealed at 450 degrees C in ambient air. Separately, 60 µL of neodymium chloride prepared from neodymium oxide, 60 µL of ruthenium based commercial dye (N719) and 60 µL of extracts of calendula orange and dog flower were used as sensitizer to improve the photoconductance properties. Elemental analysis confirmed synthesis of composite material of Mn and TiO2. Morphological observation showed a uniform particles of 25 to 50 nm diameter. Optoelectronic properties were studied by using thick films of these powders as working electrode as a function of wavelength from 430 to 750 nm and the cyclic voltammogram were obtained by scanning potential from -1.5 V to +1.5 V at the illumination intensity of 1000 Wm(-2). Sensitization resulted in additional absorption and functional bands. Oxidation peak current was found decreasing with increasing wavelength. Sensitization with flower extract resulted in increased oxidation current at higher wavelength indicating the improved photoconduction in comparison with N719 and neodymium.
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To elucidate the effect of zinc oxide nanoparticles (ZnO-NPs) with different surface modifications in relieving the oxidative stress in cultured human embryonic kidney cells (HEK-293) following investigation was performed. Oxidative stress was artificially induced by hydrogen peroxide in HEK-293 cell culture and its management was studied. Alkyl amines modified ZnO-NPs with curcumin and reduced glutathione (GSH) functionalization was used in managing oxidative stress and had shown promising results. ZnO-NPs used in this study were synthesized via non-aqueous sol-gel method and FESEM characterisation showed them of spherical shape of about 20-50 nm size with amine, curcumin and GSH functionalization. UV-visible and FTIR spectroscopic characterizations confirmed functionalization of ZnO-NPs. Decrease in oxidative stress was found with the dose-dependent culture of HEK-293 cells with these functionalized ZnO-NPs. Cell viability and morphology, as observed using AFM and inverted microscope, was retained with the prescribed dosages of the functionalized nanoparticles while at higher dosages they caused cytotoxicity and death. Diethylamine (DEA) modified ZnO-NPs and their functionalization with GSH and curcumin were found more effective in managing oxidative stress in cells. Present study could help in designing economical and bio-compatible functionalized non-toxic nanoparticles designed for managing oxidative stress leading to possible therapeutical and medicinal uses.
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Curcumina/farmacología , Glutatión/farmacología , Nanopartículas del Metal/química , Estrés Oxidativo/efectos de los fármacos , Óxido de Zinc/farmacología , Curcumina/química , Glutatión/química , Células HEK293 , Humanos , Óxido de Zinc/químicaRESUMEN
Nanomaterial-based photoluminescence (PL) diagnostic devices offer fast and highly sensitive detection of pesticides, DNA, and toxic agents. Here we report a label-free PL genosensor for sensitive detection of Vibrio cholerae that is based on a DNA hybridization strategy utilizing nanostructured magnesium oxide (nMgO; size >30 nm) particles. The morphology and size of the synthesized nMgO were determined by transmission electron microscopic (TEM) studies. The probe DNA (pDNA) was conjugated with nMgO and characterized by X-ray photoelectron and Fourier transform infrared spectroscopic techniques. The target complementary genomic DNA (cDNA) isolated from clinical samples of V. cholerae was subjected to DNA hybridization studies using the pDNA-nMgO complex and detection of the cDNA was accomplished by measuring changes in PL intensity. The PL peak intensity measured at 700 nm (red emission) increases with the increase in cDNA concentration. A linear range of response in the developed PL genosensor was observed from 100 to 500 ng/µL with a sensitivity of 1.306 emi/ng, detection limit of 3.133 ng/µL and a regression coefficient (R(2)) of 0.987. These results show that this ultrasensitive PL genosensor has the potential for applications in the clinical diagnosis of cholera.
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Técnicas Biosensibles , Cólera/diagnóstico , ADN Bacteriano/aislamiento & purificación , Óxido de Magnesio/química , Nanoestructuras/química , Vibrio cholerae/aislamiento & purificación , Cólera/microbiología , Cólera/patología , Sondas de ADN/síntesis química , Sondas de ADN/química , ADN Bacteriano/genética , ADN Complementario/química , ADN Complementario/genética , Humanos , Límite de Detección , Mediciones Luminiscentes , Nanoestructuras/ultraestructura , Hibridación de Ácido Nucleico/métodos , Procesos Fotoquímicos , Espectroscopía Infrarroja por Transformada de Fourier , Vibrio cholerae/genética , Vibrio cholerae/patogenicidadRESUMEN
Nano-Tin oxide was synthesized using hydrothermal method at 150 °C for 6 h and then thin films were deposited by electrophoretic method at an optimized voltage of 100 V for 5 min on electropolished aluminum substrate. Spherical particles of about 30-50 nm diameters are observed with partial agglomeration when observed under electron microscope, which are tetragonal rutile structure. XPS results showed peaks related to Sn 4d, Sn 3d, O 1s & C 1s with spin-orbit splitting of 8.4 eV for Sn 3d. Feasibility studies of enzyme less urea sensing characteristics of nano-tin oxide thin films are exhibited herein. The deposited films have been used for enzyme less urea sensing from 1 to 20 mM concentration in buffer solution. The sensors were characterized electrochemically to obtain cyclic voltammogram as a function of urea concentration and scan rate. The sensitivity is estimated as 18.9 µA/mM below 5 mM and 2.31 µA/mM above 5 mM with a limit of detection of 0.6 mM.
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Técnicas Electroquímicas/métodos , Nanoestructuras/química , Compuestos de Estaño/síntesis química , Urea/análisis , Técnicas de Química Sintética , Técnicas Electroquímicas/instrumentación , Enzimas/química , Enzimas/metabolismo , Microscopía Electrónica de Rastreo , Nanotecnología/métodos , Espectroscopía de Fotoelectrones , Sensibilidad y Especificidad , Compuestos de Estaño/químicaRESUMEN
A novel organic-inorganic platform comprising of chitosan (CH) modified nanostructured magnesium oxide (nanoMgO) has been electrophoretically deposited on the indium-tin-oxide (ITO) substrate. The single stranded probe DNA (ssDNA) sequence of Vibrio cholerae has been covalently functionalized onto CH-nanoMgO/ITO surface. The cytotoxicity assay of nanoMgO particles, examined using human intestinal cell line (INT 407), reveals no significant cytotoxicity at the given doses in the range of 50-350 µg/mL. The X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and various microscopic techniques have been employed for the structural and morphological analysis of the fabricated electrodes. The electrochemical response studies of ssDNA and fragmented genomic DNA hybridized electrode (dsGDNA/CH-nanoMgO/ITO) have been carried out using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. The dsGDNA/CH-nanoMgO/ITO bioelectrode exhibits a linear response in the range 100-500 ng/µL with improved sensitivity of 36.72 nA/ng/cm(2), faster response time of 3s and high stability of 3-4 months under refrigerated condition. The lower detection limit of fabricated genosensor has been estimated as 35.20 ng/µL and it shows good reproducibility/repeatability.
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Quitosano/química , ADN de Cadena Simple/aislamiento & purificación , Nanoestructuras/química , Vibrio cholerae/aislamiento & purificación , Técnicas Biosensibles/métodos , Electroquímica , Humanos , Indio/química , Límite de Detección , Óxido de Magnesio/química , Espectroscopía Infrarroja por Transformada de Fourier , Compuestos de Estaño/química , Vibrio cholerae/patogenicidad , Difracción de Rayos XRESUMEN
The photoconducting properties of a unit microflower of zinc oxide are investigated as a function of wavelength from UV to IR region at constant illumination intensity. Synthesized flowers were trapped in 2 microm gap, between pre-prepared gold microelectrodes, using AC dielectrophoresis. Photocurrent drastically increases upon illumination in the UV region, whereas it gradually reduces when irradiated in visible and IR region. Higher photoconductivity in UV region is correlated to band to band transition upon illumination. In visible region, deep level transitions are expected which intern exhibits comparatively low photocurrent. Photoconduction in IR region is only due to the adsorbed surface oxygen species. This investigation suggests the potential application of ZnO nanostructures for various optoelectronic device applications.
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In biological fluids, nanoparticles are always surrounded by proteins. As the protein is adsorbed on the surface, the extent of adsorption and the effect on the protein conformation and stability are dependent on the chemical nature, shape, and size of the nanoparticle (NP). We have carried out a detailed investigation on the interaction of bovine serum albumin (BSA) with polyethyleneimine-functionalized ZnO nanoparticles (ZnO-PEI). ZnO-PEI was synthesized using a wet chemical method with a core size of ~3-7 nm (from transmission electron microscopy). The interaction of BSA with ZnO-PEI was examined using a combination of calorimetric, spectroscopic, and computational techniques. The binding was studied by ITC (isothermal titration calorimetry), and the result revealed that the complexation is enthalpy-driven, indicating the possible involvement of electrostatic interaction. To investigate the nature of the interaction and the location of the binding site, a detailed domain-wise surface electrostatic potential calculation was performed using adaptive Poisson-Boltzmann software (APBS). The result shows that the protein surface can bind the nanoparticle. On binding ZnO-PEI, the protein gets destabilized to some extent, as displayed by CD (circular dichroism) and FTIR (Fourier transform infrared) spectroscopy. Chemical and thermal denaturation of BSA, when carried out in the presence of ZnO-PEI, also indicated a small perturbation in the protein structure. A comparison of the enthalpy and entropy components of binding with those derived for the interaction of BSA with ZnO nanoparticles explains the effect of hydrophilic cationic species attached on the NP surface. The effect of the NP surface modification on the structure and stability of BSA would find useful applications in nanobiotechnology.
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Nanopartículas/química , Polietileneimina/química , Albúmina Sérica Bovina/química , Óxido de Zinc/química , Animales , Bovinos , Nanotecnología/métodos , Espectroscopía Infrarroja por Transformada de FourierRESUMEN
In the present study, 11-mercaptoundecanoic acid-modified gold nanoparticles (â¼7 nm) were conjugated with chloroquine to explore their potential application in cancer therapeutics. The anticancer activity of chloroquine-gold nanoparticle conjugates (GNP-Chl) was demonstrated in MCF-7 breast cancer cells. The MCF-7 cells were treated with different concentrations of GNP-Chl conjugates, and the cell viability was assayed using trypan blue, resulting in an IC(50) value of 30 ± 5 µg/mL. Flow cytometry analysis revealed that the major pathway of cell death was necrosis, which was mediated by autophagy. The drug release kinetics of GNP-Chl conjugates revealed the release of chloroquine at an acidic pH, which was quantitatively estimated using optical absorbance spectroscopy. The nature of stimuli-responsive drug release and the inhibition of cancer cell growth by GNP-Chl conjugates could pave the way for the design of combinatorial therapeutic agents, particularly nanomedicine, for the treatment of cancer.
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Antineoplásicos/farmacología , Neoplasias de la Mama/tratamiento farmacológico , Neoplasias de la Mama/patología , Cloroquina/farmacología , Oro/química , Nanopartículas del Metal/química , Antineoplásicos/síntesis química , Antineoplásicos/química , Muerte Celular/efectos de los fármacos , Proliferación Celular/efectos de los fármacos , Supervivencia Celular/efectos de los fármacos , Cloroquina/química , Relación Dosis-Respuesta a Droga , Ensayos de Selección de Medicamentos Antitumorales , Femenino , Citometría de Flujo , Humanos , Relación Estructura-Actividad , Células Tumorales CultivadasRESUMEN
Here we report an easy method to improve the optoelectronic properties of commercially available TiO2 nanopowder using extracts of various flowers viz. Calendula Orange (CO), Calendula Yellow (CY), Dahlia Violet (DV), Dahlia Yellow (DY), Rabbit flower (RF), Sweet Poppy (SP), Sweet Williams (SW) and their Mixed Extracts (ME). Various analysis techniques such as UV-Vis, FTIR, FESEM, XRD, and Raman spectroscopy were used to characterize for elemental, structural and morphological properties of the unmixed/mixed TiO2 nanopowder. TiO2 nanopowder was also calcined at 550 degrees C. Thick films of the these unmixed/mixed powder were printed, using conventional screen printing method, on fluorine doped tin oxide (FTO) substrate with organic binders and dried at 45 degrees C. The photoconducting properties are investigated as a function of wavelength from ultra-violet (UV) to infra-red (IR) region at a constant illumination intensity. Photocurrent gradually decreases when irradiated from UV to IR region. In case of unmixed and uncalcined TiO2, conductance decreased continuously whereas when extracts are added, a flat region of conductance is observed. The overall effect of extracts (colour pigments) is seen as an increase in the photoconductance. Highest photoconductance is observed in case of DY flower extract. Anthocyanins, present in flowers are known to have antioxidative properties and hence can contribute in photoconduction by reducing the surface adsorbed oxygen. This investigation indicates the potential use of flower extracts for dye sensitized solar cell (DSSC).
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Flores/química , Nanoestructuras , Extractos Vegetales/química , Titanio/química , Microscopía Electrónica de Rastreo , Espectrofotometría Ultravioleta , Espectroscopía Infrarroja por Transformada de Fourier , Espectrometría Raman , Difracción de Rayos XRESUMEN
Nanosized niobium oxide powders were synthesized with a yield of approximately 87% using a simple and facile soft-chemical process. Niobium pentachloride (Nb2Cl5) was used as the precursor which was first converted into niobium ethoxide and then hydrolysed with water to synthesize niobia nanopowder. The synthesized powder was calcined at 500 degrees C for phase conversion to end-centered monoclinic as confirmed by diffraction studies and elemental analysis with a chemical composition in the ratio of Nb:O as 1:2.5. The molecular framework of Nb-O-Nb stretching and asymmetric frequency was confirmed by FT-IR, UV-visible and Raman spectroscopic studies. The size, shape and surface morphology of the powders were observed by SEM and TEM which indicated particle sizes of approximately 20 nm. The surface area of 20 m2/g, pore volume of 0.0538 cm2/g and the average pore size of 6.5 nm2 for the calcined sample were obtained with the help of nitrogen adsorption/desorption method using the Barrett-Joyner-Halenda (BJH) method which indicates that the synthesized powder can be used for catalysis and other surface sensitive applications.
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The antibacterial activity of leaf extract of mangroves, namely, Rhizophora mucronata, Sonneratia alba and Exoecaria agallocha from Chorao island, Goa was investigated against human bacterial pathogens Staphylococcus aureus, Streptococcus sp., Salmonella typhi, Proteus vulgaris and Proteus mirabilis. As compared to aqueous, ethanol extract showed broad-spectrum activity. The multidrug-resistant (MDR) bacteria Salmonella typhi was inhibited by the ethanol extract of S. alba leaf whereas the other two resistant bacteria Staphylococcus aureus and Streptococcus sp. were inhibited by the ethanol extract of leaves of all the species. The aqueous extract of S. alba and E. agallocha showed their activity against P. vulgaris and P. mirabilis, respectively. Phytochemical analysis revealed the presence of saponins, glycosides, tannins, flavonoids, phenol and volatile oils in the leaves of mangroves. Further studies using different solvents for extraction are necessary to confirm that mangroves are a better source for the development of novel antibiotics.
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Various nanostructures of ZnO such as nanowires, sea urchin like and nano needles were grown using rapid thermal chemical vapor deposition technique (RTCVD), in oxygen ambient. For the growth of such structures, oxygen pressure was kept as 0.1 Torr whereas the chamber base pressure was 10(-5) Torr. The growth temperature was varied from 600 degrees C to 850 degrees C, which resulted in morphological variations. X-ray diffraction measurement revealed the hexagonal wurtzite structure of ZnO preferably oriented in [001] direction, which was further confirmed by high-resolution transmission electron microscopic (HRTEM) observations. X-ray photoelectron spectroscopy (XPS) analysis suggests the presence of Zn 2p and O 1s. Raman E2 high peaks at approximately 434 cm(-1) has the highest intensity compared to other modes supports XRD results. Presence of low E2 peaks at approximately 330 cm(-1) indicates defects and oxygen vacancies.
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Urea sensing properties of titanate nanotubes (TNT) are presented here. TNT films were deposited by electrophoretic deposition (EPD) method on aluminum substrate. Prior to EPD, commercial nanoparticles of TiO2 were hydrothermally treated at 70 degrees C for 48 h after sonicating the solution for 8 h. Hydrothermal method resulted in the conversion of particles to tubular structure following the established method. Urease was covalently attached with TNT (by soaking in urease solution for 3 h). In general, conductivity of film increases after urease immobilization. The urease immobilized films were characterized for urea sensing in the concentration range of 1 mM to 500 mM. Three different sensitivity regions are observed viz. (i) lower concentrations (below 10 mM); (ii) linear region up to 100 mM and a (iii) saturation region above 100 mM. Sensors are extremely sensitive in region (i). From the elemental analyses of the films after urease immobilization, urease was found attached with TiO2, as evident by N 1s peak in the photoelectron spectra. Cyclic voltammetric studies indicated surface-confined redox couple is responsible for sensing behavior. A possible sensing mechanism is presented and discussed.
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Técnicas Biosensibles/instrumentación , Conductometría/instrumentación , Nanotubos/química , Titanio/química , Urea/análisis , Ureasa/química , Electroforesis/métodos , Enzimas Inmovilizadas/química , Diseño de Equipo , Análisis de Falla de Equipo , Nanotubos/ultraestructura , Urea/químicaRESUMEN
Nanoparticles exposed to biofluids become coated with proteins, thus making protein-nanoparticle interactions of particular interest. The consequence on protein conformation and activity depends upon the extent of protein adsorption on the nanoparticle surface. We report the interaction of bovine serum albumin (BSA) with gold nanostructures, particularly gold nanoparticles (GNP) and gold nanorods (GNR). The difference in the geometry and surface properties of nanoparticles is manifested during complexation in terms of different binding modes, structural changes, thermodynamic parameters, and the activity of proteins. BSA is found to retain native-like structure and properties upon enthalpy-driven BSA-GNP complexation. On the contrary, the entropically favored BSA-GNR complexation leads to substantial loss in protein secondary and tertiary structures with the release of a large amount of bound water, as indicated by isothermal calorimetry (ITC), circular dichroism (CD), and Fourier transform infrared (FTIR) and fluorescence spectroscopies. The esterase activity assay demonstrated a greater loss in BSA activity after complexation with GNR, whereas the original activity is retained in the presence of GNP. The formation of large assemblies (aggregates) and reduced average lifetime, as evidenced from dynamic light scattering and fluorescence decay measurements, respectively, suggest that GNR induces protein unfolding at its surface. The effect of temperature on the CD spectra of BSA-GNP was found to be similar to that of pristine BSA, whereas BSA-GNR shows distortion in CD spectra at lower wavelengths, strengthening the perception of protein unfolding. High binding constant and entropy change for BSA-GNR complexation determined by ITC are consistent with large surfacial interaction that may lead to protein unfolding. The present work highlights the differential response of a protein depending on the nature of the nanostructure and its surface chemistry, which need to be modulated for controlling the biological responses of nanostructures for their potential biomedical applications.