Ag and Au Nanoparticles as Color Indicators for Monomer/Micelle-Nanoparticle Interactions.

Ag and Au nanoparticles (NPs) were used as color indicators to determine the monomer/micelle adsorption on the NP surface. A simple methodology based on the color change of Ag/Au NPs upon interacting with surface-active molecules was developed. A contrasting color change occurred when NPs interact with the monomer/micelle. This was demonstrated by monitoring the adsorption behavior of a series of Gemini surfactants. UV-visible measurements showed a large change in the intensity and wavelength of Ag/Au NP absorbance upon the surface adsorption of the monomer/micelle of Gemini surfactants. The mechanism of surface adsorption and molecular orientation on the solid-liquid interface of NPs was determined by performing the FT-IR and XPS measurements. Results demonstrated that sharp color changes from yellow to red for Ag NPs and red to purple for Au NPs happened when the Gemini surfactant monomer/micelle adsorbs on the NP surface. This colorimeter-based methodology highlighted the applicability of Ag/Au NPs in complex media where such NPs frequently encounter surface-active molecules.

Extraction of Bionanomaterials from the Aqueous Bulk by Using Surface Active and Water-Soluble Magnetic Nanoparticles.

Surface active and water-soluble magnetic nanoparticles (NPs) were used to demonstrate the extraction of bionanomaterials from the aqueous bulk. Au NPs conjugated with different water-insoluble and water-soluble proteins were used as model bionanomaterials. UV-visible studies, zeta potential, and microscopic analyses were performed to quantify the extraction. Sodium dodecyl sulfate and dimethylene bis(dodecyldimethylammonium bromide) (12-2-12) stabilized surface active magnetic NPs were fully capable of extracting Au NPs conjugated with predominantly hydrophobic proteins from the aqueous bulk when placed at the aqueous-air interface. However, they were poor in extracting Au NPs from the aqueous bulk which were coated with predominantly hydrophilic water-soluble protein. On the other hand, water-soluble dodecyldimethyl-3-ammonio-1-propanesulfonate stabilized magnetic NPs proved to be fully capable of extracting all kinds of Au NPs conjugated with either water-soluble or water-insoluble proteins. The results highlight the remarkable ability of magnetic NPs in the extraction of bionanomaterials when placed at either biointerfaces or in the aqueous bulk of biological systems.

Colloidal Stabilization of Sodium Dilauraminocystine for Selective Nanoparticle-Nanoparticle Interactions: Their Screening and Extraction by Iron Oxide Magnetic Nanoparticles.

Nanoparticle-nanoparticle (NP-NP) interactions between Au and Ag NPs were studied by using sodium dilauraminocystine (SDLC)- and Gemini surfactant-stabilized NPs to demonstrate the unique NP surface adsorption behavior of SDLC in controlling and mimicking such interactions in complex mixtures. They were significantly affected by the spacer as well as the polymeric nature of the head group of Gemini surfactants. A longer spacer impeded while a polymeric head group facilitated the interactions. The Au-Ag NPs interactions in an aqueous phase were also controlled by placing surface-active magnetic NPs at an aqueous-air interface, which interacted with either or both kinds of interacting NPs in an aqueous phase and reduced their ability to interact with each other. On the other hand, water-soluble zwitterionic magnetic NPs proved to be excellent extractants of both Au and Ag NPs from the aqueous phase. Extraction efficiency depended on the strength of interactions between the water-soluble magnetic NPs and aqueous-solubilized Au and/or Ag NPs.

Avoiding Hemolytic Anemia by Understanding the Effect of the Molecular Architecture of Gemini Surfactants on Hemolysis.

Hemolytic behavior of a series of different categories of Gemini surfactants was determined in their low concentration range. Cationic Gemini surfactants of different molecular architectures prove to be highly cytotoxic even at 0.1 mM. Anionic and amino acid-based Gemini surfactants were minimally cytotoxic, although their toxicity was concentration-dependent. With respect to monomeric surfactants of comparable hydrocarbon chain lengths, cationic Gemini surfactants were much more toxic than anionic Gemini surfactants. Incubation temperature was another important parameter that significantly drove the hemolysis irrespective of the molecular structure of the surfactant. Results indicated that the surface activity or liquid-blood cell membrane adsorption tendency of a surfactant molecule determined the degree of hemolytic anemia. Greater surface activity induced greater cytotoxicity, especially when the surfactant possessed a stronger ability to interact with the membrane proteins through hydrophilic interactions. That provided cationic Gemini surfactants a higher ability for hemolytic anemia because they were able to interact with an electronegative cell membrane with favorable interactions in comparison to anionic or amino acid-based Gemini surfactants. These findings are expected to help in designing surface-active drugs with a suitable molecular architecture that can avoid hemolytic anemia.

Mechanistic Aspects of Simultaneous Extraction of Silver and Gold Nanoparticles across Aqueous-Organic Interfaces by Surface Active Iron Oxide Nanoparticles.

Surface active iron oxide nanoparticles (NPs) were used for the simultaneous extraction of water soluble Ag and Au NPs across an aqueous-organic interface from aqueous bulk. The surface activity of iron oxide NPs was achieved by using cationic Gemini surfactants of different architectures during the in situ synthesis of iron oxide NPs in hydrothermal synthesis. Aqueous bulk solubility of Ag and Au NPs was achieved by stabilizing them with conventional surfactants of different polarities such as SDS, CTAB, and DDM. The amphiphilic nature of iron oxide NPs demonstrated their remarkable ability to extract Ag and Au NPs through both hydrophilic and hydrophobic interactions. The mechanism of extraction from aqueous bulk was monitored by placing different amounts of surface active iron oxide NPs on the aqueous-organic interface and was studied with the help of UV-visible, DLS, and IR measurements. XPS and TEM measurements were used for the quantitative estimation of efficiency of extraction. Extraction was facilitated when both hydrophilic and hydrophobic interactions were participating simultaneously. Results may help in designing a suitable method for purification of industrial effluents contaminated with metal particulates simply by applying an external magnetic field rather than going through a complicated conventional filtration process.

Impact of nanomaterials on ecosystems: Mechanistic aspects in vivo.

Nanotechnologies are becoming increasingly popular in modern era of human development in every aspect of life. Their impact on our ecosystem in air, soil, and water is largely unknown because of the limited amount of information available, and hence, they require considerable attention. This account highlights the important routes of nanomaterials toxicity in air, soil, and water, their possible impact on the ecosystem and aquatic life. The mechanistic aspects have been focused on the size, shape, and surface modifications of nanomaterials. The preventive measures and future directions along with appropriate designs and implementation of nanotechnologies have been proposed so as to minimize the interactions of nanomaterials with terrestrial flora and aquatic life. Specifically, the focus largely remains on the toxicity of metallic nanoparticles such as gold (Au) and silver (Ag) because of their applications in diverse fields. The account lists some prominent mechanistic routes of nanotoxicity along with in vivo experimental results based on the fundamental understanding that how nanometallic surfaces interact with plant as well as animal biological systems. The appropriate modifications of the nanometallic surfaces with biocompatible molecules are considered to be the most effective preventive measures to reduce the nanotoxicity.

Applications of Molecular Structural Aspects of Gemini Surfactants in Reducing Nanoparticle-Nanoparticle Interactions.

Oppositely charged nanoparticle (NP)-nanoparticle (NP) interactions were studied by titrating sodium dodecyl sulfate (SDS) stabilized NPs with cetyltrimethylammonium bromide (CTAB) stabilized NPs at constant temperature with the help of UV-visible and dynamic light scattering measurements. CTAB stabilized NPs were systematically replaced with a series of cationic gemini surfactants to demonstrate the effect of head group and hydrocarbon tail modifications on the electrostatic interactions with SDS stabilized NPs. Introduction of the dimeric gemini head group (alkylammonium or imidazolium), spacer length, and double tail hydrocarbon length all significantly reduced the NP-NP interactions and delayed their salting-out process. They lead to the formation of stable colloidal aqueous solubilized NP-NP complexes. The results concluded that NP-NP interactions can be overcome if appropriately stabilized NPs are used to maintain their colloidal stability so as to achieve maximum applicability.

Nanotoxicity in Systemic Circulation and Wound Healing.

Nanotoxicity of nanomaterials is an important issue in view of their potential applications in systemic circulation and wound healing dressing. This account specifically deals with several characteristic features of different nanomaterials which induce hemolysis and how to make them hemocompatible. The shape, size, and surface functionalities of naked metallic as well as nonmetallic nanoparticles surfaces are responsible for the hemolysis. An appropriate coating of biocompatible molecules dramatically reduces hemolysis and promotes their ability as safe drug delivery vehicles. The use of coated nanomaterials in wound healing dressing opens several new strategies for rapid wound healing processes. Properly designed nanomaterials should be selected to minimize the nanotoxicity in the wound healing process. Future directions need new synthetic methods for engineered nanomaterials for their best use in nanomedicine and nanobiotechnology.

pH and thermo-responsive tetronic micelles for the synthesis of gold nanoparticles: effect of physiochemical aspects of tetronics.

Micelles of the star shaped block polymers "tetronics" were employed for the synthesis of gold (Au) nanoparticles (NPs) under the effect of pH and temperature variation. The presence of the diamine core in the tetronic macromolecule made its micelles highly pH responsive, thereby dramatically altering the physiochemical properties. Likewise, a high degree of hydration made the micelles temperature sensitive. UV-visible studies, transmission electron microscopy (TEM), gel electrophoresis, and structure optimization by energy minimization were applied to understand the physiochemical aspects of tetronic micelles and their further role in the synthesis of Au NPs. Synthesis of Au NPs was triggered by the surface cavities of the micelles and hence the NPs simultaneously adsorbed on the micelle surface. Low pH induced high hydration and temperature responsive well defined vesicular morphologies bearing Au NPs, while high pH produced mainly large and compact compound micelles carrying NPs. Both pH and temperature responsive behaviors of different tetronics significantly influenced the synthesis of Au NPs and thus demonstrated their ability to act as nanoreactors for the materials synthesis under different experimental conditions.

Protein mixtures of environmentally friendly zein to understand protein-protein interactions through biomaterials synthesis, hemolysis, and their antimicrobial activities.

Industrially important zein protein has been employed to understand its interactions with two model proteins bovine serum albumin (BSA) and cytochrome c (Cyc,c) following the in vitro synthesis of Au NPs so as to expand its applicability for biological applications. Interactions were studied under the effect of temperature variation by UV-visible and fluorescence emission studies. Temperature induced unfolding in the protein mixtures indicated their degree of mutual interactions through simultaneous nucleation of gold nanoparticles (Au NPs) and their subsequent shape control effects. Zein + BSA mixtures showed favorable protein-protein interactions over the entire mole fraction range with maximum close to x(BSA) = 0.24, whereas zein + Cyc,c showed such interactions only in the zein rich region with significant demixing in the Cyc,c rich region of the mixtures. Both hydrophobic as well as hydrophilic domains in the unfolded states were driving such interactions in the case of zein + BSA mixtures while demixing was the result of the predominant hydrophilic nature of Cyc,c and its self-aggregation behavior in the Cyc,c rich region in contrast to the predominant hydrophobic nature of zein. Zein + BSA mixtures produced small roughly spherical Au NPs fully coated with protein, whereas the demixing zone of zein + Cyc,c mixtures generated highly anisotropic NPs with little protein coating. To explore their biological applications, protein conjugated NPs of both mixtures were subjected to hemolysis where NPs coated with the former mixture showed little hemolysis and may act as drug delivery vehicles in systemic circulation in comparison to the latter. Both kinds of NPs further demonstrated their extraordinary antimicrobial activities with different kinds of strains and proved to be highly important environmentally friendly biomaterials.

Hemolytic Response of Iron Oxide Magnetic Nanoparticles at the Interface and in Bulk: Extraction of Blood Cells by Magnetic Nanoparticles.

Surface-active and water-soluble magnetic nanoparticles (NPs) were synthesized in the presence of a series of amphiphilic molecules of different functional groups to determine the hemolytic response and their ability to extract blood cells across the interface and aqueous bulk while maintaining minimum hemolysis. Amphiphilic molecules such as Gemini surfactants of strong hydrophobicity and low hydrophilic-lipophilic balance produced surface-active magnetic NPs, which were highly cytotoxic even when placed at the blood suspension (aqueous)-air interface. A similar behavior was shown by water-soluble magnetic NPs produced using monomeric ionic and nonionic surfactants and different amino acids. The NPs produced using mild biological surfactants and mono- and oligosaccharides of the same functional group proved to be excellent blood cell extractors with minimum hemolysis. α/ß-cyclodextrin and dextrose-stabilized magnetic NPs induced negligible hemolysis and extracted more than 50% of blood cells. The results showed that nontoxic magnetic NPs are excellent blood cell extractors from the blood suspension when tagged with amphiphilic molecules possessing good biocompatibility with cell membranes without inducing hemolysis. The work highlights the biological applicability of nontoxic magnetic NPs at biointerfaces and in blood suspensions.

Bovine serum albumin driven interfacial growth of selenium-gold/silver hybrid nanomaterials.

Selenium (Se) nanorods (NRs) capped with BSA were used as precursor to synthesize Se-Au/Ag hybrid nanocrystals (NCs). Aqueous Au/Ag ions in the presence of fixed amount of purified dried Se NRs were reduced by ascorbic acid at 80 degrees C to generate respective nucleating centres which subsequently grew on the capped BSA hot spots. The hybrid NCs thus obtained were characterized by SEM, TEM, and EDS analysis while their synthesis was monitored simultaneously by UV-visible absorbance due to the surface plasmon resonance of Au and Ag nanoparticles (NPs). In both cases, a gradual decrease in the absorbance of Au/Ag NPs with respect to reaction time was observed which indicated a diminishing number density of such particles in colloidal aqueous phase. SEM and TEM analyses then explained the presence of Au NPs in self assembled ball shaped aggregates and their selective adsorption on Se NRs, whereas no self aggregated balls of Ag NPs were observed and they always grew on the Se NRs. The results were discussed on the basis of different routes followed by the Au and Ag nucleating centres to produced hybrid nanomaterials.

Biomineralization of gold nanoparticles by lysozyme and cytochrome C and their applications in protein film formation.

Lysozyme (Lys) and cytochrome c (Cyc,c) proteins were used as mild reducing and stabilizing agents to synthesize gold nanoparticles (NPs) at precisely 40 and 80 degrees C. All reactions were monitored simultaneously by UV-visible measurements to determine changes in the nature of the protein during the course of reaction. The synthesis of Au NPs caused the simultaneous denaturation of protein due to the formation of bioconjugate NPs, and the denaturation temperature decreased with the number of NPs. Lys entrapped NPs in a typical gel state, and Cyc,c carried them on well-defined micelles at 80 degrees C or in the form of long fibrils or strands at 40 degrees C. The shape, size, and arrangement of bioconjugate NPs were characterized by atomic force microscopy and transmission electron microscopy measurements. Purified bioconjugate NPs were further used in zein protein film formation. The resulting films were characterized by photophysical and mechanical measurements. The induction of bioconjugate NPs made protein films isotropic and relatively more brittle (with a greater effect for Cyc,c than for Lys conjugate NPs) than in their absence and was considered to be well suited for biomedical applications.

How PEO-PPO-PEO triblock polymer micelles control the synthesis of gold nanoparticles: temperature and hydrophobic effects.

Aqueous micellar solutions of F68 (PEO(78)-PPO(30)-PEO(78)) and P103 (PEO(17)-PPO(60)-PEO(17)) triblock polymers were used to synthesize gold (Au) nanoparticles (NPs) at different temperatures. All reactions were monitored with respect to reaction time and temperature by using UV-visible studies to understand the growth kinetics of NPs and the influence of different micellar states on the synthesis of NPs. The shape, size, and locations of NPs in the micellar assemblies were determined with the help of TEM, SEM, and EDS analyses. The results explained that all reactions were carried out with the PEO-PPO-PEO micellar surface cavities present at the micelle-solution interface and were precisely controlled by the micellar assemblies. Marked differences were detected when predominantly hydrophilic F68 and hydrophobic P103 micelles were employed to conduct the reactions. The UV-visible results demonstrated that the reduction of gold ions into nucleating centers was channeled through the ligand-metal charge-transfer complex (LMCT) and carried out by the surface cavities. Excessive hydration of the surface cavities in the case of F68 micelles produced a few small NPs, but their yield and size increased as the micelles were dehydrated under the effect of increasing temperature. The results concluded that the presence of well-defined predominantly hydrophobic micelles with a compact micelle-solution interfacial arrangement of surface cavities ultimately controlled the reaction.

Room temperature surfactant assisted crystal growth of silver nanoparticles to nanoribbons.

This study presents a simple and systematic growth of Ag nanoparticles (NPs) to nanoribbons by changing the hydrophobicity parameter of a series of cationic Gemini surfactants by using seed-mediated approach in aqueous phase at room temperature. At lowest hydrophobicity of a Gemini surfactant (i.e., dimethylene bis(decyldimethyl-ammonium bromide), 10-2-10), Ostwald ripening process was observed which caused fusion among growing Ag NPs. This process was quite prominent when 0.5 ml of Ag seed solution was used for the growth process but weakened as the amount of seed decreased to 0.125 ml. Similar behavior was demonstrated by Au NPs studied for comparison. The nanostructures were characterized by TEM, XRD, and UV-visible measurements. Further increase in the hydrophobicity of a Gemini surfactant from 10-2-10 to dimethylene bis(tetradecyldimethylammonium bromide) (14-2-14) through dimethylene bis(dodecyldimethylammonium bromide) (12-2-12), resulted in the participation of threads like micelles and liquid crystalline phase as soft-templates towards the nanoribbon formation. Fine polycrystalline Ag nanoribbons were obtained in the presence 14-2-14 and were characterized by the HRTEM and EDX analysis.

Solution phase interactions controlled ordered arrangement of gold nanoparticles in dried state.

Gold (Au) nanoparticles (NPs) were synthesized in the presence of water soluble biomolecules such as DNA, chitosan, phospholipids, and BSA by using seed-mediated approach at room temperature. All reactions produced mostly spherical geometries with comparable size (< or = 20 nm). The NPs were arranged in a typical pearl-necklace type arrangement except in the presence of BSA. Different measurements such as UV-visible, TEM, XRD, and XPS were used to characterize the Au NPs. Fluorescence spectroscopy was used to identify the interactions between biomolecules and blank (uncapped) Au NPs in aqueous colloidal solutions. It was concluded that the favorable interactions between Au NPs and biomolecules in aqueous phase, in fact, drive them into pearl-necklace type arrangement in the dried state.

Photophysical behavior of heme group: Unfolding of hemoglobin and myoglobin in the presence of Gemini surfactants of different molecular architectures.

Fluorescence studies were performed to determine the photophysical behavior of heme group in the presence of cationic Gemini surfactants of different architectures. Both hemoglobin and myoglobin were used to understand the heme group interactions with Gemini surfactants under the influence of temperature variation and were compared with homologous monomeric surfactants. The results were also supplemented from the size and zeta potential measurements of both proteins. Gemini surfactants showed marked effect on the unfolding behavior of hemoglobin that mainly contributed by the stronger hydrophobic interactions of double hydrocarbon chains as well as methylene spacer in the head group region with the hydrophobic domains of hemoglobin. Myoglobin with single polypeptide chain did not show similar unfolding behavior in the presence of Gemini surfactants rather it was readily solubilized in the surfactant solution and that too in the presence of monomeric surfactants rather than Gemini surfactants. The results highlighted the mechanistic aspects by which water soluble globular proteins interact with amphiphilic molecules of different functionalities and thus, helped to predict the interactions of both hemoglobin and myoglobin with the complex biological molecules possessing similar functionalities.

A simple method of superlattice formation: step-by-step evaluation of crystal growth of gold nanoparticles through seed-growth method.

Self-assembled arrangement of monodisperse nanoparticles (NPs) forms one-dimensional (1D) to three-dimensional (3D) superlattice (SL) with many useful applications. A simple seed growth (S-G) method is presented to achieve monodisperse gold (Au) NPs and simultaneously arrange them into SL formation. It can simply be done by controlling the hydrophobicity of a capping surfactant and can very well be extended to semiconductor NPs such as PbS as well. It is demonstrated by step-by-step evaluation of a three-step S-G method in the presence of a series of strongly hydrophobic Gemini surfactants. NPs of each step are analyzed by transmission electron microscopy (TEM) and UV-visible measurements to evaluate the mode of aggregation in dried and colloidal bulk phases, respectively. Both studies show complementary results. Crystal growth of NPs is followed through different steps by measuring the X-ray diffraction (XRD) patterns. It allows one to identify different reaction conditions such as the number of nucleating centers (seeds) and concentration of the surfactant to achieve monodisperse morphologies of NPs. All studies pertaining to different steps of the S-G method under different reaction conditions collectively lead to a single conclusion that better capping ability of strongly hydrophobic surfactants allows NPs to achieve both monodisperse morphologies as well as SL formation simultaneously.

Role of Gluten in Surface Chemistry: Nanometallic Bioconjugation of Hard, Medium, and Soft Wheat Protein.

Hard, medium, and soft wheat proteins, based on gluten content, were studied for their important roles in nanometallic surface chemistry. In situ synthesis of Au nanoparticles (NPs) was followed to determine the surface adsorption behavior of wheat protein based on the gluten contents. A greater amount of gluten contents facilitated the nucleation to produce Au NPs. X-ray photoelectron spectroscopy (XPS) surface analysis clearly showed the surface adsorption of protein on nanometallic surfaces which was almost equally prevalent for the hard, medium, and soft wheat proteins. Wheat protein conjugated NPs were highly susceptible to phase transfer from aqueous to organic phase that was entirely related to the amount of gluten contents. The presence of higher gluten content in hard wheat protein readily enabled the hard wheat protein conjugated NPs to move across the aqueous-organic interface followed by medium and soft wheat protein conjugated NPs. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS page) analysis allowed us to determine molar masses of nanometallic surface adsorbed protein fractions. Only two protein fractions of high molar masses (74 and 85 kDa) from SDS solubilized hard, medium, and soft wheat proteins preferred to adsorb on nanometallic surfaces out of more than 15 protein fractions of pure wheat protein. This made the surface adsorption of wheat protein highly selective and closely related to gluten content. Cetyltrimethylammonium bromide (CTAB) solubilized wheat protein conjugated NPs demonstrated their strong antimicrobial activities against both Gram negative and Gram positive bacteria making them suitable for their applications in food industry.

Metal nanoparticle pollutants interfere with pulmonary surfactant function in vitro.

Reported associations between air pollution and pulmonary and cardiovascular diseases prompted studies on the effects of gold nanoparticles (Au NP) on pulmonary surfactant function. Low levels (3.7 mol % Au/lipid, 0.98% wt/wt) markedly inhibited adsorption of a semisynthetic pulmonary surfactant (dipalmitoyl-phosphatidylcholine (DPPC)/palmitoyl-oleoyl-phosphatidylglycerol/surfactant protein B (SP-B); 70:30:1 wt %). Au NP also impeded the surfactant's ability to reduce surface tension (gamma) to low levels during film compression and to respread during film expansion. Transmission electron microscopy showed that Au NP generated by a seed-growth method were spherical with diameters of approximately 15 nm. Including palmitoyl-oleoyl-phosphatidylglycerol appeared to coat the NP with at least one lipid bilayer but did not affect NP shape or size. Similar overall observations occurred with dimyristoyl phosphatidylglycerol. Dipalmitoyl-phosphatidylglycerol was less effective in NP capping, although similar sized NP were formed. Including SP-B (1% wt/wt) appears to induce the formation of elongated strands of interacting threads with the fluid phosphatidylglycerols (PG). Including DPPC resulted in formation of aggregated, less spherical NP with a larger size distribution. With DPPC, strand formation due to SP-B was not observed. Agarose gel electrophoresis studies demonstrated that the aggregation induced by SP-B blocked migration of PG-coated NP. Migration was also influenced by the fluidity of the PGs. It is concluded that Au NP can interact with and sequester pulmonary surfactant phospholipids and, if inhaled from the atmosphere, could impede pulmonary surfactant function in the lung.