Biofunctionalized surface-modified silver nanoparticles for gene delivery

Silver nanoparticles (AgNPs) find use in different biomedical applications including wound healing and cancer. We propose that the efficacy of the nanoparticles can be further augmented by using these particles for gene delivery applications. The objective of this work was to engineer biofunctionalized stable AgNPs with good DNA binding ability for efficient transfection and minimal toxicity. Herein, we report on the one-pot facile green synthesis of polyethylene glycol (PEG) stabilized chitosan-g-polyacrylamide modified AgNPs. The size of the PEG stabilized AgNPs was 38 +/- 4 nm with a tighter size distribution compared to the unstabilized nanoparticles which showed bimodal distribution of particle sizes of 68 +/- 5 nm and 7 +/- 4 nm. To enhance the efficiency of gene transfection, the Arg-Gly-Asp-Ser (RGDS) peptide was immobilized on the silver nanoparticles. The transfection efficiency of AgNPs increased significantly after immobilization of the RGDS peptide reaching up to 42 +/- 4% and 30 +/- 3% in HeLa and A549 cells, respectively, and significantly higher than 34 +/- 3% and 23 +/- 2%, respectively, with the use of polyethyleneimine (25 kDa). These nanoparticles were found to induce minimal cellular toxicity. Differences in cellular uptake mechanisms with RGDS immobilization resulting in improved efficiency are elucidated. This study presents biofunctionalized AgNPs for potential use as efficient nonviral carriers for gene delivery with minimal cytotoxicity toward augmenting the therapeutic efficacy of AgNPs used in different biomedical products.

Fracture behavior of magnesium alloys - Role of tensile twinning

In this work, Mode-I fracture experiments are conducted using notched compact tension specimens machined from a rolled AZ31 Mg alloy plate having near-basal texture with load applied along rolling direction (RD) and transverse direction (TD). Moderately high notched fracture toughness of J(C) similar to 46 N/mm is obtained in both RD and TD specimens. Fracture surface shows crack tunneling at specimen mid-thickness and extensive shear lips near the free surface. Dimples are observed from SEM fractographs suggesting ductile fracture. EBSD analysis shows profuse tensile twinning in the ligament ahead of the notch. It is shown that tensile twinning plays a dual role in enhancing the toughness in the notched fracture specimens with reduced triaxiality. It provides significant dissipation in the background plastic zone and imparts hardening to the material surrounding the fracture process zone via operation of several mechanisms which retards micro-void growth and coalescence. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

An ultrastable conjugate of silver nanoparticles and protein formed through weak interactions

In recent years, silver nanoparticles (AgNPs) have attracted significant attention owing to their unique physicochemical, optical, conductive and antimicrobial properties. One of the properties of AgNPs which is crucial for all applications is their stability. In the present study we unravel a mechanism through which silver nanoparticles are rendered ultrastable in an aqueous solution in complex with the protein ubiquitin (Ubq). This involves a dynamic and reversible association and dissociation of ubiquitin from the surface of AgNP. The exchange occurs at a rate much greater than 25 s(-1) implying a residence time of <40 ms for the protein. The AgNP-Ubq complex remains stable for months due to steric stabilization over a wide pH range compared to unconjugated AgNPs. NMR studies reveal that the protein molecules bind reversibly to AgNP with an approximate dissociation constant of 55 mu M and undergo fast exchange. At pH > 4 the positively charged surface of the protein comes in contact with the citrate capped AgNP surface. Further, NMR relaxation-based experiments suggest that in addition to the dynamic exchange, a conformational rearrangement of the protein takes place upon binding to AgNP. The ultrastability of the AgNP-Ubq complex was found to be useful for its anti-microbial activity, which allowed the recycling of this complex multiple times without the loss of stability. Altogether, the study provides new insights into the mechanism of protein-silver nanoparticle interactions and opens up new avenues for its application in a wide range of systems.

Developing acetylcholinesterase-based inhibition assay by modulated synthesis of silver nanoparticles: applications for sensing of organophosphorus pesticides

A novel and highly sensitive sensing strategy for the detection of organophosphorus compounds (OPs) based on the catalytic reaction of acetylcholinesterase (AChE) and acetylcholine (ATCh) during the modulated synthesis of silver nanoparticles (AgNPs) has been developed. The enzymatic hydrolysis of ATCh by AChE yields thiocholine (TCh), which induces the aggregation of AgNPs during synthesis, and the absorption peak at 382 nm corresponding to AgNPs decreases. The enzymatic reaction can be regulated by OPs, which can covalently bind to the active site of AChE and decrease the TCh formation, thereby decreasing the aggregation and significantly enhancing the absorption peak at 382 nm. The proposed system achieved good linearity and limits of detection of 0.078 nM and 2.402 nM for trichlorfon and malathion, respectively, by UV-visible spectroscopy. Further, the sensitivity of the proposed system was demonstrated through the determination of OPs in different spiked real samples. The described work shows the potential application for further development of a colorimetric sensor for other OP pesticide detection during the synthesis of AgNPs using enzyme-based assays.

A new class of high strength high temperature Cobalt based gamma-gamma ` Co-Mo-Al alloys stabilized with Ta addition

The present paper reports a new class of Co based superalloys that has gamma-gamma' microstructure and exhibits much lower density compared to other commercially available Co superalloys including Co-Al-W based alloys. The basic composition is Co-10Al-5Mo (at%) with addition of 2 at% Ta for stabilization of gamma' phase. The gamma-gamma' microstructure evolves through solutionising and aging treatment. Using first principles calculations, we observe that Ta plays a crucial role in stabilizing gamma' phase. By addition of Ta in the basic stoichiometric composition Co-3(Al, Mo), the enthalpy of formation (Delta H-f) of L1(2) structure (gamma' phase) becomes more negative in comparison to DO19 structure. The All of the L12 structure becomes further more negative by the occupancy of Ni and Ti atoms in the lattice suggesting an increase in the stability of the gamma' precipitates. Among large number of alloys studied experimentally, the paper presents results of detailed investigations on Co-10Al-5Mo-2Ta, Co-30Ni-10Al-5Mo-2Ta and Co-30Ni-10Al-5Mo-2Ta-2Ti. To evaluate the role alloying elements, atom probe tomography investigations were carried out to obtain partition coefficients for the constituent elements. The results show strong partitioning of Ni, Al, Ta and Ti in ordered gamma' precipitates. 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Organic alloys of room temperature liquids thiophenol and selenophenol

The first examples of organic alloys of two room temperature liquids, obtained and characterized via in situ cryo-crystallography, are presented. Thiophenol and selenophenol, which exhibit isostructurality and similar modes of S center dot center dot center dot S and Se center dot center dot center dot Se homo-chalcogen interactions along with weak and rare S-H center dot center dot center dot S and Se-H center dot center dot center dot Se hydrogen bonds, are shown to form solid solutions exhibiting Veggard's law-like trends.

Effect of Surface Energy Anisotropy on the Stability of Growth Fronts in Multiphase Alloys

Eutectic growth offers a variety of examples for pattern formation which are interesting both for theoreticians as well as experimentalists. One such example of patterns is ternary eutectic colonies which arise as a result of instabilities during growth of two solid phases. Here, in addition to the two major components being exchanged between the solid phases during eutectic growth, there is an impurity component which is rejected by both solid phases. During progress of solidification, there develops a boundary layer of the third impurity component ahead of the solidification front of the two solid phases. Similar to Mullins-Sekerka type instabilities, such a boundary layer tends to make the global solidification envelope unstable to morphological perturbations giving rise to two-phase cells. This phenomenon has been studied numerically in two dimensions for the conditions of directional solidification, by Plapp and Karma (Phys Rev E 66:061608, 2002) using phase-field simulations. While, in the work by Plapp and Karma (Phys Rev E 66:061608, 2002) all interfaces are isotropic, in our presentation, we extend the phase-field model by considering interfacial anisotropy in the solid-solid and solid-liquid interfaces and characterize the role of interfacial anisotropy on the stability of the growth front through phase-field simulations in two dimensions.

Hydrogelation of bile acid-peptide conjugates and in situ synthesis of silver and gold nanoparticles in the hydrogel matrix

Fabricating supramolecular hydrogels with embedded metal nanostructures is important for the design of novel hybrid nanocomposite materials for diverse applications such as biosensing and chemosensing platforms, catalytic and antibacterial functional materials etc. Supramolecular self-assembly of bile acid-dipeptide conjugates has led to the formation of new supramolecular hydrogels. Gelation of these molecules depends strongly on the hydrophobic character of the bile acids. The possibility of in situ fabrication of Ag and Au NPs in these supramolecular hydrogels by incorporating Ag+ and Au3+ salts was investigated via photoreduction. Chemical reductions of Ag+ and Au3+ salts in the hydrogels were performed without adding any external stabilizing agents. In this report we have shown that the color, size and shape of silver nanoparticles formed by photoreduction depend on the amino acid residue of the side chain.

Single-step, size-controlled synthesis of colloidal silver nanoparticles stabilized by octadecylamine

A single step process for the synthesis of size-controlled silver nanoparticles has been developed using a bifunctional molecule, octadecylamine (ODA). Octadecylamine complexes to Ag+ ions electrostatically, reduce them, and subsequently stabilizes the nanoparticles thus formed. Hence, octadecylamine simultaneously functions as both a reducing and a stabilizing agent. The amine-capped nanoparticles can be obtained in the form of dry powder, which is readily redispersible in aqueous and organic solvents. The particle size, and the nucleation and growth kinetics of silver nanoparticles could be tuned by varying the molar ratio of ODA to AgNO3. The UV-vis spectra of nanoparticles prepared with different concentrations of ODA displayed the well-defined plasmon band with maximum absorption around 425 nm. The formation of silver metallic nanoparticles was confirmed by their XRD pattern. The binding of ODA molecule on the surface of silver has been studied by FT-IR and NMR spectroscopy. The formation of well-dispersed spherical Ag nanoparticles has been confirmed by TEM analysis. The particle size and distribution are found to be dependent on the molar concentration of the amine molecule. Open aperture z-scans have been performed to measure the nonlinearity of Ag nanoparticles. (C) 2015 Published by Elsevier B.V.

Light Induced Metastable State of Silver Nitroprusside Probed by Raman Spectroscopy

Low temperature Raman spectroscopic measurements on silver nitroprusside (AgNP), Ag-2Fe(CN)(5)NO] powders display reversible features of a partially converted metastable state. The results are compared with similarly observed metastable state in case of sodium nitroprusside (NaNP) and the differences have been discussed in terms of possible resistance to metastable state formation offered by silver atoms on the basis of hard soft acid base (HSAB) theory.

On the Structural Stability of Melt Spun Ribbons of Fe95-x Zr (x) B4Cu1 (x=7 and 9) Alloys and Correlation with Their Magnetic Properties

Melt spun ribbons of Fe95-x Zr (x) B4Cu1 with x = 7 (Z7B4) and 9 (Z9B4) alloys have been prepared, and their structure and magnetic properties have been evaluated using XRD, DSC, TEM, VSM, and Mossbauer spectroscopy. The glass forming ability (GFA) of both alloys has been calculated theoretically using thermodynamical parameters, and Z9B4 alloy is found to possess higher GFA than that of Z7B4 alloy which is validated by XRD results. On annealing, the amorphous Z7B4 ribbon crystallizes into nanocrystalline alpha-Fe, whereas amorphous Z9B4 ribbon shows two-stage crystallization process, first partially to bcc solid solution which is then transformed to nanocrystalline alpha-Fe and Fe2Zr phases exhibiting bimodal distribution. A detailed phase analysis using Mossbauer spectroscopy through hyperfine field distribution of phases has been carried out to understand the crystallization behavior of Z7B4 and Z9B4 alloy ribbons. In order to understand the phase transformation behavior of Z7B4 and Z9B4 ribbons, molar Gibbs free energies of amorphous, alpha-Fe, and Fe2Zr phases have been evaluated. It is found that in case of Z7B4, alpha-Fe is always a stable phase, whereas Fe2Zr is stable at higher temperature for Z9B4. (C) The Minerals, Metals & Materials Society and ASM International 2015

Outstanding dielectric constant and piezoelectric coefficient in electrospun nanofiber mats of PVDF containing silver decorated multiwall carbon nanotubes: assessing through piezoresponse force microscopy

In order to enhance the piezoelectric b-phase, PVDF was electrospun from DMF solution. The enhanced b-phase was discerned by comparing the electrospun fibers against the melt mixed samples. While both the processes resulted in phase transformation of a-to electroactive b-polymorph in PVDF, the fraction of b-phase was strongly dependent on the adopted process. Two different nanoscopic particles: carboxyl functionalized multiwall carbon nanotubes (CNTs) and silver (Ag) decorated CNTs were used to further enhance the piezoelectric coefficient in the electrospun fibers. Fourier transform infrared spectroscopy (FTIR) and wide-angle X-ray diffraction (XRD) supports the development of piezoelectric b-phase in PVDF. It was concluded that electrospinning was the best technique for inducing the b-polymorph in PVDF. This was attributed to the high voltage electrostatic field that generates extensional forces on the polymer chains that aligns the dipoles in one direction. The ferroelectric and piezoelectric measurement on electrospun fibers were studied using piezo-response force microscope (PFM). The Ag-CNTs filled PVDF electrospun fibers showed the highest piezoelectric coefficient (d(33) = 54 pm V-1) in contrast to PVDF/CNT fibers (35 pm V-1) and neat PVDF (30 pm V-1). This study demonstrates that the piezoelectric coefficient can be enhanced significantly by electrospinning PVDF containing Ag decorated nanoparticles.

Enhanced nonlinear optical properties of graphene oxide-silver nanocomposites measured by Z-scan technique

Nonlinear optical properties (NLO) of a graphene oxide-silver (GO-Ag) nanocomposite have been investigated by the Z-scan setup at Q-switched Nd:YAG laser second harmonic radiation i.e., at 532 nm excitation in a nanosecond regime. A noteworthy enhancement in the NLO properties in the GO-Ag nanocomposite has been reported in comparison with those of the synthesized GO nanosheet. The extracted value of third order nonlinear susceptibility (chi(3)), at a peak intensity of I-0 = 0.2 GW cm(-2), for GO-Ag has been found to be 2.8 times larger than that of GO. The enhancement in NLO properties in the GO-Ag nanocomposite may be attributed to the complex energy band structures formed during the synthesis which promote resonant transition to the conduction band via surface plasmon resonance (SPR) at low laser intensities and excited state transition (ESA) to the conduction band of GO at higher intensities. Along with this photogenerated charge carriers in the conduction band of silver or the increase in defect states during the formation of the GO-Ag nanocomposite may contribute to ESA. Open aperture Z-scan measurement indicates reverse saturable absorption (RSA) behavior of the synthesized nanocomposite which is a clear indication of the optical limiting (OL) ability of the nanocomposite.

Thermal co-reduction approach to vary size of silver nanoparticle: its microbial and cellular toxicology

In recent years, silver nanoparticles (AgNPs) have attracted considerable interest in the field of food, agriculture and pharmaceuticals mainly due to its antibacterial activity. AgNPs have also been reported to possess toxic behavior. The toxicological behavior of nanomaterials largely depends on its size and shape which ultimately depend on synthetic protocol. A systematic and detailed analysis for size variation of AgNP by thermal co-reduction approach and its efficacy toward microbial and cellular toxicological behavior is presented here. With the focus to explore the size-dependent toxicological variation, two different-sized NPs have been synthesized, i.e., 60 nm (Ag60) and 85 nm (Ag85). A detailed microbial toxicological evaluation has been performed by analyzing minimum inhibitory concentration (MIC), minimum bactericidal concentration (MBC), diameter of inhibition zone (DIZ), growth kinetics (GrK), and death kinetics (DeK). Comparative cytotoxicological behavior was analyzed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. It has been concluded by this study that the size of AgNPs can be varied, by varying the concentration of reactants and temperature called as ``thermal co-reduction'' approach, which is one of the suitable approaches to meet the same. Also, the smaller AgNP has shown more microbial and cellular toxicity.

Characterization of silver-kaolinite (AgK): an adsorbent for long-lived I-129 species

Bentonite is a preferred buffer and backfill material for deep geological disposal of high-level nuclear waste (HLW). Bentonite does not retain anions by virtue of its negatively charged basal surface. Imparting anion retention ability to bentonite is important to enable the expansive clay to retain long-lived I-129 (iodine-129; half-life = 16 million years) species that may escape from the HLW geological repository. Silver-kaolinite (AgK) material is prepared as an additive to improve the iodide retention capacity of bentonite. The AgK is prepared by heating kaolinite-silver nitrate mix at 400 degrees C to study the kaolinite influence on the transition metal ion when reacting at its dehydroxylation temperature. Thermo gravimetric-Evolved Gas Detection analysis, X-ray diffraction analysis, X-ray photo electron spectroscopy and electron probe micro analysis indicated that silver occurs as AgO/Ag2O surface coating on thermally reacting kaolinite with silver nitrate at 400 degrees C.