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Biomedical subjects

Murali Sastry

Publications and source records attributed to Murali Sastry.

At least 37 records · Page 2Linked to original sources

Using the dynamic, expanding liquid-liquid interface in a Hele-Shaw cell in crystal growth and nanoparticle assembly.

The liquid-liquid interface has been used with considerable success in the synthesis of advanced materials ranging from (bio)minerals to inorganic membranes to nanoparticles. In almost all such cases, the interface is static. The Hele-Shaw cell in which a viscous fluid is displaced by a less viscous one in a constrained manner has been invaluable in the study of dynamic instabilities at interfaces and in the study of viscous fingering pattern formation. However, the potential of the Hele-Shaw cell in carrying out reactions at the interface between the two fluids leading to the formation of inorganic materials has been largely unrecognized and underexploited. Realizing that the dynamic liquid-liquid interface in a Hele-Shaw cell would provide opportunities to control a variety of time-scales associated with material formation, we have started a program on the use of the Hele-Shaw cell in materials synthesis. In this discussion paper, we present some of our recent results on the growth of calcium carbonate crystals in the Hele-Shaw cell by the reaction of Ca2+ ions electrostatically complexed with carboxylate ions pinned to the interface with carbonate ions present in the aqueous part of the biphasic reaction medium. We show that both polymorph selectivity and the morphology of the crystals may be modulated by varying the experimental conditions in the cell. We also discuss the possibility of using the dynamic interface in the Hele-Shaw cell to cross-link gold nanoparticles in water through bifunctional linkers present in the oil phase and investigate the nature of the structures formed.

Journal Article↗

Biosynthesis of gold and silver nanoparticles using Emblica Officinalis fruit extract, their phase transfer and transmetallation in an organic solution.

The design, synthesis and characterization of biologically synthesized nanomaterials have become an area of significant interest. In this paper, we report the extracellular synthesis of gold and silver nanoparticles using Emblica Officinalis (amla, Indian Gooseberry) fruit extract as the reducing agent to synthesize Ag and Au nanoparticles, their subsequent phase transfer to an organic solution and the transmetallation reaction of hydrophobized silver nanoparticles with hydrophobized chloroaurate ions. On treating aqueous silver sulfate and chloroauric acid solutions with Emblica Officinalis fruit extract, rapid reduction of the silver and chloroaurate ions is observed leading to the formation of highly stable silver and gold nanoparticles in solution. Transmission Electron Microscopy analysis of the silver and gold nanoparticles indicated that they ranged in size from 10 to 20 nm and 15 to 25 nm respectively. Ag and Au nanoparticles thus synthesized were then phase transferred into an organic solution using a cationic surfactant octadecylamine. Transmetallation reaction between hydrophobized silver nanoparticles and hydrophobized chloroaurate ions in chloroform resulted in the formation of gold nanoparticles.

Colloids↗

Synthesis of gold nanospheres and nanotriangles by the Turkevich approach.

Gold nanoparticles of triangular morphology possess interesting optical properties with potential application in medicine and infrared absorbing coatings, however, little is known about conditions that favor their growth. In this paper, we have reinvestigated a time-tested recipe for the formation of gold nanospheres by citrate reduction of aqueous gold ions under boiling conditions (Turkevich recipe). Our principle findings are that gold nanotriangle formation is kinetically controlled and is highly favored at low temperatures. Furthermore, the presence of chloride ions from the precursor chloroaurate ions plays a major role in promoting the growth of <111> oriented triangular/truncated triangular particles. The presence of bromide and iodide ions that possess the ability to replace surface-bound chloride ions inhibits triangle formation to varying degrees.

Crystallization↗

Synthesis of CdS and alloyed CdMnS nanocrystals using aqueous foams.

Certain surfactant-stabilized aqueous foams provide a potentially efficient and simple chemical route for the synthesis of various nanomaterials with controllable structure, size, and shape. In the present work, a one-step process for the synthesis of CdS and Cd1-xMn(x)S (0 < x < 10) nanocrystals has been described. Aqueous CdCl2 and the aerosol-OT solutions are homogeneously mixed together and thereafter, nitrogen is bubbled through this solution to produce stable aqueous foam. After drainage of the foam, the freestanding dry foam consisting of cadmium cations electrostatically complexed with the anionic aerosol-OT molecules at the liquid-gas interface is treated with H2S vapor. The foam turns yellowish-orange and collapses, in the process yielding CdS nanoclusters of variable morphology. This morphology variation is appropriately attributed to growth of the CdS as well as alloyed Cd1-xMn(x)S nanoparticles in different regions of the foam contributing to the varying topological structure. Optical absorption spectra of both CdS and Cd1-xMn(x)S nanoparticles clearly show a well-defined exciton absorption feature around 450 nm due to quantum confinement effects. The interesting band edge emission characteristics of these AOT-capped CdS and Cd1-xMn(x)S nanoparticles produced in the foam are discussed with respect to their size and shape. Particular interest in the present novel aqueous foam approach arises due to the fact that the cubic zincblende CdS and alloyed Cd1-xMn(x)S nanocrystals could easily be obtained even under ambient experimental conditions itself.

Alloys↗

Hydrophobic, organically dispersible gold nanoparticles of variable shape produced by the spontaneous reduction of aqueous chloroaurate ions by hexadecylaniline molecules.

In addition to control over the size and monodispersity of nanoparticle, nanomaterial synthesis procedures are increasingly required to control their shape and assembly as well. We demonstrate in this paper synthesis of organically dispersible, hydrophobic gold nanoparticles of spherical shape and encased in triangular thin polyaniline shells by doing reaction under static conditions and assembly of these particles onto polymer nanorod/nanowire-like templates by varying the molar ratio of chloroaurate ions to hexadecylaniline and varying the solvent by the spontaneous reduction of aqueous chloroaurate ions by hexadecylaniline molecules in a biphasic reaction setup. Under stationary conditions (no stirring), a biphasic mixture of hexadecylaniline in toluene and chloroaurate ions in water leads to the electrostatic complexation of chloroaurate ions with hexadecylaniline at the liquid-liquid interface and their phase transfer into the organic phase, followed by their reduction by the hexadecylaniline molecules. By varying the conditions, the templating action of gold nanoparticles or the polyaniline nanodispersions can be tuned in the organic medium and resulting assembly.

Journal Article↗

Isothermal titration calorimetry studies on the binding of DNA bases and PNA base monomers to gold nanoparticles.

An isothermal titration calorimetric (ITC) investigation of the interaction of DNA bases and PNA base monomers with gold nanoparticles is described revealing a binding sequence in the order C > G > A > T. Direct measurement of the strength of interaction of ligands with nanogold by ITC has important implications in surface modification strategies for biomedical, catalysis, and nanoarchitecture applications.

Adenine↗

Liquid foam as a template for the synthesis of iron oxyhydroxide nanoparticles.

Liquid foams have been used as a template to prepare iron oxyhydroxide nanoparticles. This is achieved by a process of electrostatic entrapment of Fe2+/Fe3+ ions in the foam stabilized by the surfactant sodium dodecyl sulfate followed by the in situ hydrolysis of the metal ions. Infrared and selected area electron diffraction measurements suggest the formation of a mixture of beta-FeO(OH) and gamma-FeO(OH) crystallographic phases after the in situ hydrolysis of the metal ions in the foam template. Transmission electron microscopy analysis of the powders obtained from the foam indicates that the particles are fairly monodisperse with an average size of around 50 nm. Scanning electron microscopy pictures reveal that the particles form loosely bound aggregates of around 300 nm. After the powders obtained in the foam are annealed at 400 degrees C, X-ray diffraction measurements show that the FeO(OH) particles are converted to alpha-Fe2O3. The mechanistic aspects of metal ion hydrolysis in a foam are discussed, and some of the advantages of this method vis-à-vis the normal solution-based methods are outlined.

Journal Article↗

Synthesis of aqueous Au core-Ag shell nanoparticles using tyrosine as a pH-dependent reducing agent and assembling phase-transferred silver nanoparticles at the air-water interface.

We demonstrate that the amino acid tyrosine is an excellent reducing agent under alkaline conditions and may be used to reduce Ag+ ions to synthesize stable silver nanoparticles in water. The tyrosine-reduced silver nanoparticles may be separated out as a powder that is readily redispersible in water. The silver ion reduction at high pH occurs due to ionization of the phenolic group in tyrosine that is then capable of reducing Ag+ ions and is in turn converted to a semi-quinone structure. These silver nanoparticles can easily be transferred to chloroform containing the cationic surfactant octadecylamine by an electrostatic complexation process. The now hydrophobic silver nanoparticles may be spread on the surface of water and assembled into highly ordered, linear superstructures that could be transferred as multilayers onto suitable supports by the versatile Langmuir-Blodgett technique. Further, tyrosine molecules bound to the surface of Au nanoparticles through amine groups in the amino acid may be used to selectively reduce silver ions at high pH on the surface of the Au nanoparticles, thus leading to a simple strategy for realizing phase-pure Au core-Ag shell nanostructures.

Air↗

Biological synthesis of strontium carbonate crystals using the fungus Fusarium oxysporum.

The total biological synthesis of SrCO3 crystals of needlelike morphology arranged into higher order quasi-linear superstructures by challenging microorganisms such as fungi with aqueous Sr2+ ions is described. We term this procedure "total biological synthesis" since the source of carbonate ions that react with aqueous Sr2+ ions is the fungus itself. We believe that secretion of proteins during growth of the fungus Fusarium oxysporum is responsible for modulating the morphology of strontianite crystals and directing their hierarchical assembly into higher order superstructures.

Carbonates↗

Effect of salt on the hybridization of DNA by sequential immobilization of oligonucleotides at the air-water interface in the presence of ODA/DOTAP monolayers.

The effect of low ionic strength on the binding of preformed DNA duplexes and the hybridization of single-stranded oligonucleotides at the air-water interface in the presence of cationic Langmuir monolayers of octadecylamine (ODA), as well as 1,2-dioleoyloxytrimethylammonium propane (DOTAP), is investigated. The complexation of the single-stranded DNA molecules and preformed duplexes with NaCl in solution with ODA/DOTAP Langmuir monolayers was followed in time by monitoring the pressure-area isotherms, wherein a very large and rapid expansion of the ODA/DOTAP monolayer was observed. In the case of sequential immobilization of complementary oligonucleotides, after addition of the complementary strand and intercalator, there was not much expansion, indicative of the fact that equilibrium had been rapidly achieved. Langmuir-Blodgett (LB) films of the ODA/DOTAP-DNA complex were formed on different substrates and characterized using quartz-crystal microgravimetry (QCM), fluorescence spectroscopy, and thermal melting studies. These measurements clearly showed that the preformed duplexes retained their native form as double helices and further, hybridization of the complementary single-stranded DNA molecules had occurred at the air-water interface, leading to the characteristic double-helical structure.

Amines↗

Rapid synthesis of Au, Ag, and bimetallic Au core-Ag shell nanoparticles using Neem (Azadirachta indica) leaf broth.

We report on the use of Neem (Azadirachta indica) leaf broth in the extracellular synthesis of pure metallic silver and gold nanoparticles and bimetallic Au/Ag nanoparticles. On treatment of aqueous solutions of silver nitrate and chloroauric acid with Neem leaf extract, the rapid formation of stable silver and gold nanoparticles at high concentrations is observed to occur. The silver and gold nanoparticles are polydisperse, with a large percentage of gold particles exhibiting an interesting flat, platelike morphology. Competitive reduction of Au3+ and Ag+ ions present simultaneously in solution during exposure to Neem leaf extract leads to the synthesis of bimetallic Au core-Ag shell nanoparticles in solution. Transmission electron microscopy revealed that the silver nanoparticles are adsorbed onto the gold nanoparticles, forming a core-shell structure. The rates of reduction of the metal ions by Neem leaf extract are much faster than those observed by us in our earlier studies using microorganisms such as fungi, highlighting the possibility that nanoparticle biological synthesis methodologies will achieve rates of synthesis comparable to those of chemical methods.

Journal Article↗

Biological synthesis of triangular gold nanoprisms.

The optoelectronic and physicochemical properties of nanoscale matter are a strong function of particle size. Nanoparticle shape also contributes significantly to modulating their electronic properties. Several shapes ranging from rods to wires to plates to teardrop structures may be obtained by chemical methods; triangular nanoparticles have been synthesized by using a seeded growth process. Here, we report the discovery that the extract from the lemongrass plant, when reacted with aqueous chloroaurate ions, yields a high percentage of thin, flat, single-crystalline gold nanotriangles. The nanotriangles seem to grow by a process involving rapid reduction, assembly and room-temperature sintering of 'liquid-like' spherical gold nanoparticles. The anisotropy in nanoparticle shape results in large near-infrared absorption by the particles, and highly anisotropic electron transport in films of the nanotriangles.

Aldehydes↗

Immobilization of biogenic gold nanoparticles in thermally evaporated fatty acid and amine thin films.

We have recently demonstrated the biological synthesis of gold nanoparticles by the reduction of aqueous chloroaurate ions by the fungus Fusarium oxysporum and with extract of geranium (Pelargonium graveolens) leaf. In this paper, we demonstrate the immobilization of biogenic gold nanoparticles in lipid thin films deposited by thermal evaporation. The charge on the gold nanoparticles synthesized by both the fungus and the geranium plant extract is used to facilitate their immobilization in both anionic and cationic lipid thin films. A rough estimate of the isoelectric point of the proteins capping the gold nanoparticles synthesized using the fungus could be made by pH-dependent microgravimetry studies of the immobilization process. An interesting size and shape selectivity in the immobilized gold nanoparticles is observed in the lipid thin films. The biogenic gold nanoparticle-lipid composite films were characterized using quartz crystal microgravimetry, UV-vis absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and transmission electron microscopy.

Amines↗

Free-standing nanogold membranes as scaffolds for enzyme immobilization.

We demonstrate herein the formation of a free-standing gold nanoparticle membrane and its use in the immobilization of the enzyme, pepsin. The nanogold membrane is synthesized by the spontaneous reduction of aqueous chloroaurate ions at the liquid-liquid interface by the bifunctional molecule bis(2-(4-aminophenoxy)ethyl) ether (DAEE) taken in chloroform. This process results in the formation of a robust, malleable free-standing nanogold membrane consisting of gold nanoparticles embedded in a polymeric background. Recognizing that gold nanoparticles are excellent candidates for immobilization of enzymes, we have immobilized pepsin on the nanogold membrane, leading to a new class of biocatalyst. A highlight of the new pepsin-nanogold biocatalyst is the ease with which separation from the reaction medium may be achieved. The catalytic activity of pepsin in the bioconjugate was comparable to that of the free enzyme in solution. The pepsin-nanogold membrane bioconjugate material exhibited excellent biocatalytic activity over 10 successive reuse cycles as well as enhanced pH, temperature, and temporal stability.

Caseins↗

Immobilization and biocatalytic activity of fungal protease on gold nanoparticle-loaded zeolite microspheres.

Gold nanoparticles are excellent biocompatible surfaces for the immobilization of enzymes. However, separation of the gold nanoparticle-enzyme bioconjugate material from the reaction medium is often difficult. In this study, we investigate the assembly of the gold nanoparticles on the surface of the amine-functionalized zeolite microspheres in the formation of zeolite-gold nanoparticle "core-shell" structures and, thereafter, the use of this structure in immobilization of fungal protease. The assembly of gold nanoparticles on the zeolite surface occurs through the amine groups present in 3-aminopropyltrimethoxysilane (3-APTS). The fungal proteases bound to the massive "core-shell" structures were easily separated from the reaction medium by mild centrifugation and exhibited excellent reuse characteristics. The biocatalytic activity of fungal protease in the bioconjugate was marginally enhanced relative to the free enzyme in solution. The bioconjugate material also showed significantly enhanced pH and temperature stability and a shift in the optimum temperature of operation.

Adsorption↗

Formation of platinum nanoparticles at air-water interfaces by the spontaneous reduction of subphase chloroplatinate anions by hexadecylaniline Langmuir monolayers.

The one-step electrostatic complexation, reduction of aqueous chloroplatinate ions, and capping of the platinum nanoparticles thus formed by hexadecylaniline Langmuir monolayers is described. The capping of the platinum nanoparticles formed spontaneously at the air-water interface by hexadecylaniline enables their facile transfer as multilayers onto suitable solid substrates by the Langmuir-Blodgett technique. The real-time reduction of the aqueous chloroplatinate ions at the air-water interface was followed by measurement of the pressure-area isotherms, while the multilayer Langmuir-Blodgett films were characterized by quartz crystal microgravimetry, transmission electron microscopy, electron diffraction, and X-ray photoemission spectroscopy.

Journal Article↗

Time-dependent complexation of glucose-reduced gold nanoparticles with octadecylamine Langmuir monolayers.

We report on the reduction of aqueous chloroaurate ions by glucose to form gold nanoparticles of uniform size. We further demonstrate the complexation of these particles with octadecylamine (ODA) monolayers at the air-water interface. Pressure-area (pi-A) isotherms as a function of time of complexation revealed a significant expansion of the monolayer. Surface pressure variation with time for constant areas after spreading of the monolayer was carried out to observe the kinetics of complexation of the colloidal particles at the interface. The kinetics of complexation of the particles at the interface was also monitored by Brewster angle microscopy (BAM) measurements. Langmuir-Blodgett films of the particles complexed with ODA were formed at a subphase pH of 9 onto different substrates. Quartz crystal microgravimetry (QCM) was used to quantify the amount of particles deposited per immersion cycle of the quartz crystal. The LB films were further characterized by UV-vis and transmission electron microscopy (TEM) measurements. TEM measurements indicate a close packed and equidistant arrangement of colloidal particles in the LB film, probably due to hydrogen-bonding interactions.

Amines↗