Tunable metallization by assembly of metal nanoparticles in polymer thin films by photo- or electron beam lithography

The technique of patterning of surfaces with metal-rich structures on micro- or nanoscales was developed by assembling metal nanoparticles into a thin film of polymer in a controllable way. Palladium (Pd) nanoparticles were incorporated into a thin film of poly(methyl methacrylate) (PMMA) using palladium (II) bis(acetylacetonato), Pd(acac)(2), as a precursor vaporized in a nitrogen atmosphere. Depending upon its dose, the irradiation of a PMMA film by UV light or an electron beam (EB) enhances its reducing capability against Pd(acac)(2). This dependency on dose can be used to control the formation and assembly of Pd nanoparticles. Using this technique, binary patterns consisting of metal-rich and metal-poor regions in the polymer film can be created simply by irradiating the surface of the polymer through a binary photomask. Besides the creation of binary patterns, it is also possible to create grayscale patterns where the density of Pd nanoparticles can be tuned to provide shades of gray by the use of light with continuously modulated intensity. Because the electron beam also enhances the reducing power of PMMA against Pd(acac)(2), it is thus possible to obtain highly metallized films with nanoscale pattern features. The PMMA film can be selectively removed by oxygen plasma treatment or by pyrolysis. Thus, highly metallized surfaces with binary or grayscale patterns can be obtained by selective removal of the PMMA films. The metallized regions possess relatively high resistivity against CF(4) plasma compared to the bare silicon surface; therefore, the metallized surface patterns can be transferred onto the underlying silicon substrate by CF(4) plasma treatment. Because of the nanosize effect of metal nanoparticles, the thermal treatment at 900 degrees C, which is significantly lower than the melting temperature of the bulk Pd, yields continuous metallic features by binding the assembled nanoparticles.     

Synthesis of Silver Nanoparticles Using Ionic‐Liquid‐Based Microwave‐Assisted Extraction from Polygonum minus and Photodegradation of Methylene Blue

A green biogenic, nontoxic, high‐yielding synthetic method is introduced for the synthesis of silver nanoparticles (AgNPs) using ionic‐liquid‐based, microwave‐assisted extraction (ILMAE) from Polygonum minus . The aqueous ionic liquid (1‐butyl‐3‐methylimidazolium chloride [BMIM]Cl)‐based plant extract was used as reducing agent to reduce silver ions to AgNPs. The synthesis of AgNPs was confirmed by UV–visible spectrophotometry. Fourier transforms infrared (FTIR) spectra showed that the plant bioactive compounds capped the AgNPs. The particle size and morphology of Ag NPs were characterized by dynamic light scattering (DLS) and field emission scanning electron microscopy (FESEM), respectively. Elemental analysis was carried out by energy‐dispersive X‐ray (EDX) spectroscopy. Photodegradation studies showed that the AgNPs degraded 98% of methylene blue in 12 min.     

Free‐standing Graphene/Poly(methylene blue)/AgNPs Composite Paper for Electrochemical Sensing of NADH

Highly flexible graphene/poly(methylene blue)/AgNPs composite paper was successfully prepared for amperometric biosensing of NADH. For this purpose, a dispersion including graphene oxide (GO), methylene blue (MB) and silver nanoparticles (AgNPs) was prepared and GO/MB/AgNPs paper was acquired by vacuum‐filtration of this dispersion through a suitable membrane. After peeling it off from membrane, it was transformed to rGO/MB/AgNPs paper by performing reduction with hydriodic acid. In a three‐electrode cell, which is containing 0.1 M phosphate buffer solution (pH: 9.0), rGO/MB/AgNPs paper was used as working electrode and rGO/poly(MB)/AgNPs composite paper was generated by surface‐confined electropolymerization of MB using successive cyclic voltammetry approach in a suitable potential window. Characterization of this composite paper was carried out by using scanning electron microscopy, scanning tunneling microscopy, X‐ray photoelectron spectroscopy, powder X‐ray diffraction spectroscopy, Raman spectroscopy, four‐point probe conductivity measurement and cyclic voltammetry techniques. Flexible rGO/poly(MB)/AgNPs composite paper has demonstrated high sensitivity, wide linear range and low detection limit for amperometric quantification of NADH.     

Photo-catalytic degradation of different toxic dyes using silver nanoparticles as photo-catalyst,mediated via Citrus aurantium peels extract

Green synthesis of silver nanoparticles was accomplished using peels (rind) extract of Citrus aurantium as a reducing as well as capping agent. Biosynthesized AgNPs (silver nanoparticle) has been characterized via UV–Visible spectroscopy, XRD, SEM, EDAX, TEM and TGA. The observed UV–Vis analysis resulted in the formation of characteristic surface plasmon resonance absorption band centered at 465 ​nm. The observed XRD patterns, having hkl values (111), (200), (220) and (222), confirms the cubic crystalline structure of AgNPs. The average grain size 9.5 ​μm was observed by the SEM technique. Bio synthesized AgNPs were efficiently degrading the methylene blue dye nearly 95.35% in 98 ​h of exposure time. It also degraded acridine orange dye 87.34% and rose bengal dye 90.09% followed by 4h of continuous UV absorption. It also degrades methyl orange dye nearly 51% in 10h of solar irradiation. Synthesized AgNPs can be used as photo-catalyst for degrading toxic dyes.     

A new green method for the synthesis of silver nanoparticles and their antibacterial activities against gram‐positive and gram‐negative bacteria

This study aims to evaluate the capability of Ageratum conyzoides and Mikania micrantha extracts to synthesize silver nanoparticles (AgNPs) and their antibacterial capability against gram‐positive and gram‐negative bacteria. Several properties of the synthesized AgNPs, including plasmonic, biomolecule bonding, shape, size, and antibacterial, were investigated. Ultraviolet–visible (UV–vis) spectroscopy was employed for characterizing their plasmonic properties. Functional groups on the produced AgNPs were investigated by Fourier‐transform infrared (FT‐IR) spectroscopy. The size and shape of the AgNPs were identified using the field‐emission scanning electron microscopy (FESEM). Inhibition zone measurement was carried out for evaluating the antibacterial capability. This study showed that the extracts of A. conyzoides and M. micrantha were able reducing agents as evidenced by the formation of the spherical AgNPs. UV–vis spectroscopy, FT‐IR spectroscopy, and FESEM confirmed the physicochemical characteristics of AgNPs. AgNPs that were synthesized using M. micrantha were slightly smaller than those produced using A. conyzoides. In general, the present work establishes that the synthesized AgNPs have antibacterial capability depending on their size and synthesis procedure.     

Low energy proton beam induces tumor cell apoptosis through reactive oxygen species and activation of caspases

Proton beam is useful to target tumor tissue sparing normal cells by allowing precise dose only into tumor cells. However, the cellular and molecular mechanisms by which proton beam induces tumor cell death are still undefined. We irradiated three different tumor cells (LLC, HepG2, and Molt-4) with low energy proton beam (35 MeV) with spread out Bragg peak (SOBP) in vitro, and investigated cell death by MTT or CCK-8 assay at 24 h after irradiation. LLC and HepG2 cells were sensitive to proton beam at over 10 Gy to induce apoptosis whereas Molt-4 showed rather low sensitivity. Relative biological effectiveness (RBE) values for the death rate relative to gamma-ray were ranged from 1.1 to 2.3 in LLC and HepG2 but from 0.3 to 0.7 in Molt-4 at 11 d after irradiation by colony formation assay. The typical apoptotic nuclear DNA morphological pattern was observed by staining with 4'-6-diamidino-2-phenylindole (DAPI). Tiny fragmented DNA was observed in HepG2 but not in Molt-4 by the treatment of proton in apoptotic DNA fragment assay. By FACS analysis after stained with FITC-Annexin-V, early as well as median apoptotic fractions were clearly increased by proton treatment. Proton beam-irradiated tumor cells induced a cleavage of poly (ADP-ribose) polymerase-1 (PARP-1) and procaspases-3 and -9. Activity of caspases was highly enhanced after proton beam irradiation. Reactive oxygen species (ROS) were significantly increased and N-acetyl cysteine pretreatment restored the apoptotic cell death induced by proton beam. Furthermore, p38 and JNK but not ERK were activated by proton and dominant negative mutants of p38 and JNK revived proton-induced apoptosis, suggesting that p38 and JNK pathway may be activated through ROS to activate apoptosis. In conclusion, our data clearly showed that single treatment of low energy proton beam with SOBP increased ROS and induced cell death of solid tumor cells (LLC and HepG2) in an apoptotic cell death program by the induction of caspases activities.     

A completely green approach to the synthesis of dendritic silver nanostructures starting from white grape pomace as a potential nanofactory

A simple, eco-friendly, cost-effective and rapid microwave-assisted method has been developed to synthetize dendritic silver nanostructures, composed of silver nanoparticles (AgNPs), using white grape pomace aqueous extract (WGPE) as both reducing and capping agent. With this aim, WGPE and AgNO₃ (1 mM) were mixed at different ratio, and microwave irradiated at 700 W, for 40 s. To understand the role of bioactive compounds involved in the green synthesis of AgNPs, preliminary chemical characterization, FT-IR analysis and ¹H NMR metabolite profiling of WGPE were carried out. The effects of bioactive extract concentration and stability over time on AgNPs formation were also evaluated. WGPE-mediated silver nanostructures were then characterized by UV–vis, FTIR analyses, and scanning electron microscopy. Interestingly, the formation of dendritic nanostructures, originated from the self-assembly of Ag rounded nanoparticles (average diameter of 33 ± 6 nm), was observed and ascribed to the use of microwave power and the presence of organic components within the used WGPE, inducing an anisotropic crystal growth and promoting a diffusion-limited aggregation mechanism. The bio-dendritic synthetized nanostructures were also evaluated for potential applications in bio-sensing and agricultural fields. Cyclic voltammetry measurements in 0.5 M phosphate + 0.1 M KCl buffer, pH 7.4 showed that green AgNPs possess the electroactive properties typical of AgNPs produced using chemical protocol. The biological activity of synthetized AgNPs was evaluated by in-vitro antifungal activity against F. graminearum. Additionally, a phytotoxicity evaluation of synthetized green nanostructures was carried out on wheat seed germination. Results highlighted the potential of WGPE as green agent for bio-inspired nanomaterial synthesis, and of green Ag nanostructures, which can be used as antifungal agent and in biosensing applications.     

Biosynthesis of silver nanoparticles using citrus sinensis peel extract and its antibacterial activity

Biosynthesis of silver nanoparticles (AgNPs) was achieved by a novel, simple green chemistry procedure using citrus sinensis peel extract as a reducing and a capping agent. The effect of temperature on the synthesis of silver nanoparticles was carried out at room temperature (25°C) and 60°C. The successful formation of silver nanoparticles has been confirmed by UV-vis, FTIR, XRD, EDAX, FESEM and TEM analysis and their antibacterial activity against Escherichia coli, Pseudomonas aeruginosa (gram-negative), and Staphylococcus aureus (gram-positive) has been studied. The results suggest that the synthesized AgNPs act as an effective antibacterial agent.     

纳米银粒子在氨基注入氧化铟锡玻璃基体表面的高密度吸附

研究了纳米银（AgNPs）在氨基注入氧化铟锡（ITO）薄膜表面的吸附.通过氨基注入的疗法得到了氨基功能化的ITO表面（NH₂/ITO）,并将纳米银直接吸附在NH₂/ITO上得到纳米银修饰NH₂/ITO基体（AgNPs/NH₂/ITO）.使用傅里叶红外光谱、X射线光电子能谱、原子力显微镜、扫描电镜、紫外可见光谱和电化学方法对AgNPs/NH₂/ITO制备过程进行了表征.结果显示纳米银可在NH₂/ITO表面高密度地吸附,并且纳米银有良好的电化学活性.这种不借助于有机连接分子吸附纳米银的方法为制备纳米银修饰材料提供了新的选择.     

Synthesis of newly cationic surfactant based on dimethylaminopropyl amine and their silver nanoparticles: Characterization; surface activity and biological activity

The chemical structure of newly synthesized cationic surfactants based on Schiff base was confirmed using Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and mass spectroscopy. The synthesized surfactants were used in the synthesis of silver nanoparticles by a simple one-step method. The silver nanoparticle (AgNPs) formation was confirmed using transmission electron microscopy (TEM), electron diffraction (SAED), dynamic light scattering (DLS), and energy dispersive X-ray spectroscopy (EDX). The structure of the surfactant played an important role in the synthesis process. Increasing the hydrophobic chain length, the stability, and the amount of surfactant increased the quantity of AgNPs formed. The surface activity of the synthesized cationic surfactants was determined using surface tension measurements at three different temperatures. The synthesized surfactants showed a high tendency toward adsorption and micellization. Increasing the hydrophobic chain length of the synthesized surfactant increased its adsorption. Screening the synthesized cationic surfactants and their nano-form against bacteria and fungi showed that they are highly effective. The silver nanoparticles enhanced the biological activity of the synthesized cationic surfactants.     

Comparison of GO and polymer microcapacitors prepared by ion beam writing

Carbon beam writing was employed as a method for maskless production of microscale capacitors in both insulating graphene oxide (GO) and poly(methyl methacrylate) (PMMA) matrix. The GO and PMMA foils were irradiated using a 5-MeV C³⁺ beam with micrometer scale resolution. As follows, the shape of the created microstructures and compositional changes was studied using the scanning electron microscopy/energy-dispersive X-ray spectroscopy method (SEM/EDS). The structural and compositional progression was characterized by Raman spectroscopy, Rutherford backscattering spectroscopy (RBS), and elastic recoil detection analysis (ERDA) spectroscopy. The improvement of the prepared structures' electrical properties was also studied, and it can be concluded that carbon irradiation leads to the removal of oxygen and hydrogen and to growth of the carbon domains, which is connected with the conductivity increase of the irradiated parts and capacitance of the final products in the order of pF.     

Applications of silver nanoparticles capped with different functional groups as the matrix and affinity probes in surface-assisted laser desorption/ionization time-of-flight and atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry for rapid analysis of sulfur drugs and biothiols in human urine

A strategy is presented for the analysis of sulfur drugs and biothiols using silver nanoparticles (AgNPs) capped with different functional groups as the matrix and affinity probes in surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF MS) and atmospheric pressure-matrix assisted laser desorption/ionization ion trap mass spectrometry (AP-MALDI-ITMS). Biothiols adsorbed on the surface of AgNPs through covalent bonding were subjected to ultraviolet (UV) radiation that enabled desorption and ionization due to the excellent photochemical property of NPs. The proposed method has been successfully applied for the determination of cysteine and homocysteine in human urine samples using an internal standard. The limit of detection (LOD) and limit of quantification (LOQ) for cysteine and homocysteine in urine sample are 7 and 22 nM, respectively, with a relative standard deviation (RSD) of <10%. The advantages of the present method compared with the methods reported in the literature for biothiol analysis are simplicity, rapidity and sensitivity without the need for time-consuming separation and tedious preconcentration processes. Additionally, we also found that the bare AgNPs can be directly used as the matrix in MALDI-TOF MS for the analysis of sulfur drugs without the addition of an extra proton source. Copyright (c) 2008 John Wiley & Sons, Ltd.     

On the use of edge cracked short bend beam specimen for PMMA fracture toughness testing under mixed-mode I/II

In this paper an inclined edge cracked short beam specimen subjected to symmetric three-point bend loading was designed and examined for conducting mixed-mode I/II fracture toughness experiments. The aspect ratio (i.e. length to width ratio) and the loading span distance are considered much lower than the other conventional cracked bend beam samples. Crack tip parameters such as stress intensity factors and T-stress were computed numerically for this specimen by several finite element analyses and it was demonstrated that the specimen is able to produce full combinations of mode I and II including pure mode II. The practical capability of the short bend beam specimen was studied experimentally by conducting a set of mixed-mode fracture tests on PolymethylMethacrylate (PMMA) as a well-known model brittle material. The critical stress intensity factors, the direction of fracture kinking and the path of fracture trajectory were investigated both experimentally and theoretically using two stress and strain-based fracture criteria. The fracture toughness of tested PMMA was decreased by moving towards mode II case due to the effect of T-stress on the fracture mechanism of the short bend beam specimen.     

Antibacterial and Antifungal Studies of Biosynthesized Silver Nanoparticles against Plant Parasitic Nematode Meloidogyne incognita,Plant Pathogens Ralstonia solanacearum and Fusarium oxysporum

The possibility of using silver nanoparticles (AgNPs) to enhance the plants growth, crop production, and control of plant diseases is currently being researched. One of the most effective approaches for the production of AgNPs is green synthesis. Herein, we report a green and phytogenic synthesis of AgNPs by using aqueous extract of strawberry waste (solid waste after fruit juice extraction) as a novel bioresource, which is a non-hazardous and inexpensive that can act as a reducing, capping, and stabilizing agent. Successful biosynthesis of AgNPs was monitored by UV-visible spectroscopy showing a surface plasmon resonance (SPR) peak at ~415 nm. The X-ray diffraction studies confirm the face-centered cubic crystalline AgNPs. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques confirm the rectangular shape with an average size of ~55 nm. The antibacterial and antifungal efficacy and inhibitory impact of the biosynthesized AgNPs were tested against nematode, Meloidogyne incognita, plant pathogenic bacterium, Ralstonia solanacearum and fungus, Fusarium oxysporum. These results confirm that biosynthesized AgNPs can significantly control these plant pathogens.     

Synthesis and spectroscopic studies of stable aqueous dispersion of silver nanoparticles

A facile approach for the synthesis of stable aqueous dispersion of silver nanoparticles (AgNPs) using glucose as the reducing agent in water/micelles system, in which cetyltrimethylammonium bromide (CTAB) was used as capping agent (stabilizer) is described. The evolution of plasmon band of AgNPs was monitored under different conditions such as (a) concentration of sodium hydroxide, (b) concentration of glucose, (c) concentration of silver nitrate (d) concentration of CTAB, and (e) reaction time. AgNPs were characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), fluorescence spectroscopy and FT-IR spectroscopy. The results revealed an easy and viable strategy for obtaining stable aqueous dispersion of AgNPs with well controlled shape and size below 30 nm in diameter.     

Significant effects of sodium acetate, an impurity present in poly(vinyl alcohol) solution on the radiolytic formation of silver nanoparticle

A silver nanoparticle (AgNPs) stabilizer, polyvinyl alcohol (PVA) generally contains a relatively large amount of sodium acetate (NaOAc) as an impurity (up to several weight percentages) as a result of a base-catalyzed hydrolysis of poly(vinyl acetate) (PVAc). In this study, the effects of NaOAc on the radiolytic formation of AgNPs in PVA solutions were studied by using UV/vis spectroscopy. Several AgNPs were prepared by γ-ray irradiation using ⁶⁰Co source at various doses in the presence of various amounts of NaOAc. The UV data of the AgNPs observed at around 410 nm show that more AgNPs are generally produced as the NaOAc concentration in the PVA solution increases. Furthermore, no significant absorption band of the AgNPs was observed when the purified PVA containing a very small amount of NaOAc (less than 3×10⁻⁴ M) was applied with 1×10⁻³ M AgNO₃ up to 10 kGy. These results reveal that NaOAc present as an impurity in PVA, plays an important role in the radiolytic formation of AgNPs.     

In situ generation of Ag nanoparticles during photopolymerization by using newly developed dyes-based three-component photoinitiating systems and the related 3D printing applications and their shape change behavior

Silver nanoparticles (AgNPs) play a crucial role in biology and medical research as their extensive and efficient antibacterial activity and high electrical and thermal conductivity. However, the generation of them with a certain morphology under mild conditions (under air, solvent-free, room temperature, etc.,) is still a huge challenge. Herein, a simple one-step method is proposed to generate AgNPs in situ at room temperature under air by combining the photopolymerization process with the formation process of AgNPs within a few minutes. In detailed, 12 different dyes based on 2,5-diethylene-cyclopentan-1-one were first synthesized and used as high-performance type II photoinitiator. When using in conjunction of bis-(4-tert-butylphenyl) iodonium hexafluorophosphate (Iod) and ethyl 4-dimethylaminobenzoate (EDB), they can effectively boost the free radical photopolymerization (FRP) of polyethylene glycol diacrylate (PEG-DA) and the cationic photopolymerization (CP) of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (EPOX) upon irradiation with LED@405 nm. Furthermore, all the formulations containing/without AgNPs can be successfully used to perform the direct laser write experiment. However, even if all of the obtained 3D patterns exhibited reversible swelling performance and shape-memory effects caused by swelling and dehydration for the access to 4D printing, the presence of AgNPs will affect these properties.     

Preparation and characterization of PVDF‐based blend membranes as polymer electrolyte membranes in fuel cells: Study of factor affecting the proton conductivity behavior

There is a huge demand especially for polyvinylidene fluoride (PVDF) and its copolymers to provide high performance solid polymer electrolytes for use as an electrolyte in energy supply systems. In this regard, the blending approach was used to prepare PVDF‐based proton exchange membranes and focused on the study of factor affecting the ir proton conductivity behavior. Thus, a series of copolymers consisting of poly (methyl methacrylate) (PMMA), polyacrylonitrile (PAN), and poly(2‐acrylamido‐2‐methyl‐l‐propanesulfonic acid) (PAMPS) as sulfonated segments were synthesized and blended with PVDF matrix in order to create proton transport sites in PVDF matrix. It was found that addition of PMMA‐co‐PAMPS and PAN‐co‐PAMPS copolymers resulted in a significant increase in porosity, which favored the water uptake and proton transport at ambient temperature. Furthermore, crystallinity degree of the PVDF‐based blend membranes was increased by addition of the related copolymers, which is mainly attributed to formation of hydrogen bonding interaction between PVDF matrix and the synthesized copolymers, and led to a slight decrease in proton conductivity behavior of blend membranes. From impedance data, the proton conductivity of the PVDF/PMMA‐co‐PAMPS and PVDF/PAN‐co‐PAMPS blend membranes increases to 10 and 8.4 mS cm⁻¹ by adding only 50% of the related copolymer (at 25°C), respectively. Also, the blend membranes containing 30% sulfonated copolymers showed a power density as high as 34.30 and 30.10 mW cm⁻² at peak current density of 140 and 79.45 mA cm⁻² for the PVDF/PMMA‐co‐PAMPS and PVDF/PAN‐co‐PAMPS blend membranes, respectively. A reduction in the tensile strength was observed by the addition of amphiphilic copolymer, whereas the elongation at break of all blend membranes was raised.     

Visible light transformation of Rhodamine 6G using tetracarbazole zinc phthalocyanine when embedded in electrospun fibers and in the presence of ZnO and Ag particles

Herein, we report the photocatalytic transformation of Rhodamine 6G (Rh 6G) using tetracarbazole zinc phthalocyanine (TCbZnPc) when alone or when conjugated with ZnO macroparticles (ZnOMPs) and silver nanoparticles (AgNPs), represented as TCbZnPc–ZnOMPs and TCbZnPc–AgNPs, respectively. The photocatalysts were supported onto electrospun polystyrene fibers. The efficiency of TCbZnPc was improved by the presence of both ZnOMPs and AgNPs. HPLC equipped with UV–vis was used to study phototransformation products. The mechanism of transformation was via the N-de-ethylation of Rh 6G.     

Surface patterns induced by laser irradiation on thin polymer bilayer films

We report on the preparation of wavelike surface patterns with characteristic wavelengths on thin bilayers of poly(methyl methacrylate) on azobenzene liquid crystalline polymer films (LCP/PMMA) by irradiation of a single polarized pulsed laser beam. The formation of such patterns was influenced by the thickness of the upper layer and the laser fluence. We were also able to guide the wavelike pattern to have a specific orientation by placing an elastic polydimethylsiloxane (PDMS) mold on the surface of bilayer film prior to laser irradiation. Moreover, the property of the laser irradiation, that is, the selectivity through mask-projection systems, allowed us fabricating complicated micropatterns for novel microdevices.