Ultrasonic assisted functionalization of MWCNT and synergistic electrocatalytic effect of nano-hydroxyapatite incorporated MWCNT-chitosan scaffolds for sensing of nitrofurantoin

In the present work, we report the fabrication of stable composite of chitosan hydrogels (CHI) on multiwalled carbon nanotubes (MWCNT) using a simple ultrasonic-assisted method. Also, rod-like hydroxyapatite nanoparticles (HA NPs) were synthesised using a hydrothermal route and were incorporated into the highly conductive MWCNT-CHI scaffolds using an ultrasonication method. The functionalization of MWCNT and preparation of HA NPs on MWCNT-CHI nanocomposite were done using the sonication over the frequency of 37 kHz with the ultrasonic power capable of 150 W (Elmasonic Easy 60H bath sonicator). The resulting hybrid HA NPs/MWCNT-CHI nanocomposites have an excellent surface area and high surface to volume ratio, which leads to the sensitive detection of nitrofurantoin than pristine MWCNT and HA NPs. The complete elemental and morphological analyses of the HA NPs/MWCNT-CHI nanocomposites were characterised by XRD, FTIR, RAMAN, FESEM, TEM, EDX, and elemental mapping techniques. Electrochemical analysis of the HA NPs/MWCNT-CHI nanocomposites was carried out by cyclic voltammetry, electrochemical impedance spectroscopy and amperometry methods. The modified glassy carbon electrode (GCE) of HA NPs/MWCNT-CHI nanocomposites exhibit the nitrofurantoin detection activity at the linear range of 0.005–982.1 µM with the detection limit of 1.3 nM. The synergistic electrocatalytic activity of HA NPs/MWCNT-CHI nanocomposites modified GCE is correlated to the sensitivity of 0.16 µAµM⁻¹ cm⁻² with excellent precision and accuracy towards the sensing of nitrofurantoin.     

Fabrication and characterization chitosan/functionalized zinc oxide bionanocomposites and study of their antibacterial activity

This study deals with preparation and evaluation of properties of chitosan/zinc oxide bionanocomposites (CT/ZnO BNCs) with different amounts of modified zinc oxide nanoparticles (ZnO NPs) through ultrasonic irradiation technique. Due to the high surface energy and tendency for agglomeration, the surface ZnO NPs was modified by a coupling agent as 3-aminopropyltriethoxysilane (APS) to form APS–ZnO nanoparticles. Fourier transform infrared (FTIR) spectroscopy confirmed that APS was successfully grafted onto the ZnO nanoparticles surface. Thermogravimetric analysis (TGA) revealed a surface coverage of the coupling molecule of 2.6 wt%. The resulting bionanocomposites were characterized by FTIR spectra, X-ray diffraction patterns, and TGA. The antibacterial activity of bionanocomposite films was tested against gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) and gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). The results of CT/ZnO BNCs revealed that the thermal and antibacterial properties obviously improved the presence of ZnO NPs in comparison with the pure CT and that this increase is higher when the NP content increases. Further, it was observed that antibacterial activity of the resulting hybrid biofilms showed somewhat higher for gram-positive bacteria compared to gram-negative bacteria.     

Characterization and antimicrobial activity of silver nanoparticles prepared by a thermal decomposition technique

Recently, there has been an increasing need of efficient synthetic protocols using eco-friendly conditions including low costs and green chemicals for production of metal nanoparticles. In this work, silver nanoparticles (silver NPs) with average particle size about 10 nm were synthesized by using a thermal decomposition technique. Unlike the colloidal chemistry method, the thermal decomposition method developed has advantages such as the high crystallinity, single-reaction synthesis, and easy dispersion ability of the synthesized NPs in organic solvents. In a modified synthesis process, we used sodium oleate as a capping agent to modify the surface of silver NPs because the oleate has a C₁₈ tail with a double bond in the middle, therefore, forming a kink which is to be effective for aggregative stability. Importantly, the as-synthesized silver NPs have demonstrated strong antimicrobial effects against various bacteria and fungi strains. Electron microscopic studies reveal physical insights into the interaction and bactericidal mechanism between the prepared silver NPs and tested bacteria in question. The observed excellent antibacterial and antifungal activity of the silver NPs make them ideal for disinfection and biomedicine applications.     

Folate-decorated chitosan/doxorubicin poly(butyl)cyanoacrylate nanoparticles for tumor-targeted drug delivery

A novel chitosan coated poly(butyl cyanoacrylate) (PBCA) nanoparticles loaded doxorubicin (DOX) were synthesized and then conjugated with folic acid to produce a folate-targeted drug carrier for tumor-specific drug delivery. Prepared nanoparticles were surface modified by folate for targeting cancer cells, which is confirmed by FTIR spectroscopy and characterized for shape, size, and zeta potential measurements. The size and zeta potential of prepared DOX-PBCA nanoparticles (DOX-PBCA NPs) were almost 174 ± 8.23 nm and +23.14 ± 4.25 mV, respectively with 46.8 ± 3.32% encapsulation capacity. The transmission electron microscopy study revealed that preparation allowed the formation of spherical nanometric and homogeneous. Fluorescent microscopy imaging and flow cytometry analysis revealed that DOX-PBCA NPs were endocytosed into MCF-7 cells through the interaction with overexpressed folate receptors on the surface of the cancer cells. The results demonstrate that folate-conjugated DOX-PBCA NPs drug delivery system could provide increased therapeutic benefit by delivering the encapsulated drug to the folate receptor positive cancer cells.     

Imparting superhydrophobic and biocidal functionalities to a polymeric substrate by the sonochemical method

Multifunctional substrates with superhydrophobic and biocidal properties are gaining interest for a wide range of applications; however, the production of such surfaces remains challenging. Here, the sonochemical method is utilized to impart superhydrophobicity and antimicrobial properties to a polyethylene (PE) sheet. This is achieved by sonochemically depositing nanoparticles (NPs) of a hydrophobic fluoro-polymer (FP) on the PE sheets. The polymer is a flexible, transparent fluoroplastic composed of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride in the form of a powder. The NPs of polymers are generated and deposited on the surface of the PE using ultrasound irradiation. Optimizing the process results in a homogeneous distribution of 110–200 nm of NPs on the PE surface. The coated surface displays a water-contact angle of 160°, indicating excellent superhydrophobicity. This superhydrophobic surface shows high stability under outdoor conditions for two months, which is essential for various applications. In addition, metal-oxide nanoparticles (CuO or ZnO NPs) were integrated into the polymer coating to achieve antibacterial properties and increase the surface roughness. The metal oxides were also deposited sonochemically. The antibacterial activity of the FP@ZnO and FP@CuO PE composites was tested against the bacterium Staphylococcus aureus, and the results show that the FP@CuO PE can effectively eradicate the bacteria. This study highlights the feasibility of using the sonochemical method to deposit two separate functions, opening up new possibilities for producing “smart” novel surfaces.     

Facile synthesis of SERS active Ag nanoparticles in the presence of tri-n-octylphosphine sulfide

A facile and novel way was reported here for the synthesis of hydrophobic Ag nanoparticles (NPs), using AgNO₃, tri-n-octylphosphine (TOP) and sulfur (S) powder in process. TOP was used as solvent, reducing agent and stabilizer. S could chelate with excessive TOP to form trioctylphosphine sulfide (TOPS), which served as second capping agent. The hydrophobic Ag NPs could be transformed into hydrophilic state through ligand exchange. Furthermore, surface-enhanced Raman scattering (SERS) spectra of 4-aminothiophenol (4-ATP) were obtained on the hydrophobic and hydrophilic Ag NPs modified substrates, indicating that the as-synthesized Ag NPs had great potential for high sensitive optical detection applications.     

Self-assembled Ag nanoparticles for surface enhanced Raman scattering

Uniform and reproducible substrates for surface enhanced Raman scattering (SERS) are fabricated by self-assembly of Ag nanoparticles (NPs) on 3-aminopropyltrimethoxysilane (APTES) modified glass. Experimental results indicate that the Ag NPs with a narrow size distribution were assembled as a sub-monolayer which exhibits an excellent SERSactivity. The SERS enhancement factor is estimated to be 7.5 × 10⁶ and the detection limit for crystal violet (CV) solution is about ～10^?11 M. The uniformity and reproducibility of the SERS signals are tested by point-to-point and batch-to-batch measurements. It is confirmed that the self-assembled Ag NPs substrates has a high SERS reproducibility and a low standard deviation with respect to the Ag NPs on non-functionalized glass substrates. The self-assembled Ag NPs substrates can be widely used for the application of chemical and biochemical sensing.     

Annealing of magnetic nanoparticles for their encapsulation into microcarriers guided by vascular magnetic resonance navigation

Cellular uptake, cytotoxicity, and mechanisms of cytotoxicity of the positively charged Au nanoparticles (NPs) were examined in A549 cells, which are one of the most characterized pulmonary cellular systems. Positively charged Au NPs were prepared by chemical reduction using chitosan. The dimension and surface charge of Au NPs were examined by transmission electron microscopy (TEM), dynamic light scattering, and zeta potential measurements. The uptake of Au NPs into A549 cells was also monitored using TEM and dark-field microscopy (DFM) and z-stack confocal microRaman spectroscopy. DFM live cell imaging was also performed to monitor the entry of chitosan Au NPs in real time. The cytotoxic assay, using both methylthiazol tetrazolium and lactate dehydrogenase assays revealed that positively charged Au NPs decreased cell viability. Flow cytometry, DNA fragmentation, real-time PCR, and western blot analysis suggest that positively charged chitosan Au NPs provoke cell damage through both apoptotic and necrotic pathways.     

Charge‐dependent adsorption of rhodamine 6G on gold nanoparticle surfaces: fluorescence and Raman study

We study the adsorption behaviors of rhodamine dyes on gold nanoparticles (Au NPs) depending on their surface charges. Rhodamine 6G (Rh6G) dye is tested comparatively for positively and negatively charged Au NPs prepared by the reduction of chitosan and citric acid, respectively. The adsorption of Rh6G is found to be weaker on the positively charged Au NPs, whereas more substantial aggregation is found on negatively charged Au NPs. An increase in the concentration of Au NPs enhances the surface‐enhanced Raman scattering (SERS) intensities only for the Au(−) NPs, whereas the Au(+) NPs do not exhibit any strong SERS signals. Our findings suggest that SERS and reciprocal fluorescence measurements of Rh6G can be used to estimate the surface charges and atomic percentages of Au NPs less than ∼5 ppm. Copyright © 2011 John Wiley & Sons, Ltd.     

Nanoindentation of gold nanoparticles functionalized with proteins

The hardness and Young's modulus of 10 and 20 nm gold nanoparticles (Au NPs) modified with bovine serum albumin and streptavidin were measured using a nanoindenter. The Au NPs were immobilized on a semiconductor surface through organic self-assembled monolayers. Changes in mechanical properties occurred when the Au NPs were immobilized on the surface. The hardness and Young's modulus were dependent on the size of the NPs, and the proteins on the particles showed highly plastic and elastic behavior compared to flat surfaces modified with self-assembled monolayers.     

New Perspectives of Using Chitosan,Silver, and Chitosan–Silver Nanoparticles against Multidrug-Resistant Bacteria

Nanomaterials with antimicrobial activity are promising alternatives to overcome microbial resistance in medical devices. Catheters, probes, and wound dressings are among the medical devices mostly affected by microbial contamination and the formation of polymicrobial biofilms. Nanoparticles (NPs) derived from natural sources, such as chitosan nanoparticles (CsNPs), and metal-based nanoparticles, including silver nanoparticles (AgNPs), are receiving increased interest in nanomedicine. CsNPs have been widely explored as a coating material and antimicrobial agent. AgNPs have a strong antimicrobial effect against bacteria and fungi. The nanocomposite chitosan–silver nanoparticles (Cs-AgNPs) can be more effective against several microorganisms, including multidrug-resistant bacteria, due to the synergistic effect between chitosan and silver. This review addresses the most used synthesis methods, including green routes, to produce CsNPs, AgNPs, and Cs–AgNPs. It also discusses physicochemical characteristics and antimicrobial properties of these NPs in medical, pharmaceutical, and biotechnological areas.     

Laser based fabrication of chitosan mediated silver nanoparticles

We report fabrication of silver nanoparticles (Ag NPs) by laser ablation technique in different concentrations of aqueous chitosan solution. The ablation process of silver plate was carried out by using a nanosecond Q-switched Nd:YAG pulsed laser and the characterization of Ag NPs was done by Transmission electron microscopy, UV-Vis spectroscopy, and X-ray diffraction. UV-visible plasmon absorption spectra revealed that the formation efficiency as well as the stability of nanoparticles was increased by addition of chitosan. On the other hand, the size decrement of nanoparticles was more remarkable in the higher chitosan concentration.     

Research on the Raman properties of NiFe/cicada wing composite SERS platform modified by silver nanoparticles

Composite structures have been widely concerned in the preparation of surface enhanced Raman scattering (SERS) substrates. In this paper, by solving the problem that the magnetic material was difficult to glow in magnetron sputtering, ferro-nickel (NiFe) alloy was deposited on the cicada wing (CW) and the NiFe/CW substrate was obtained. The results of sliver nanoparticles (Ag NPs) modified on the substrate were subsequently compared, and the SERS properties of the new Ag/NiFe/CW substrate were analyzed. Obviously, the intensity of SERS signals has been greatly improved after the modification of Ag NPs, and the substrate exhibits excellent reproducibility. The Ag NPs modified substrates were also applied to the detection of toxic crystal violet (CV) solution, which showed remarkable SERS activity. It has been proved that the strategy of modifying Ag NPs on the substrate to form a composite structure has great potential for improving the SERS performance of the substrate.     

Surface modification of the nanoparticles by an atmospheric room-temperature plasma fluidized bed

Using hexamethyldisiloxane (HMDSO) monomer, the magnetic nanoparticles (NPs) of nickel oxide (NiO) were modified by using an atmospheric room-temperature plasma fluidized bed (ARPFB). The plasma gas temperature of the ARPFB was not higher than 325 K, which was favorable for organic polymerization. The plasma optical emission spectrum (OES) of the gas mixture consisting of argon (Ar) and HMDSO was recorded by a UV-visible monochromator. The as-treated NPs were characterized by means of scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results show that the assembling NPs were isolated greatly after modified by the organosilicon polymer. Moreover, this treatment process changed the wettability of the NPs from super-hydrophilicity to super-hydrophobicity, and the contact angle (CA) of water on the modified NPs surface exceeded 150°. Therefore, the ARPFB is a prospective technology for the NPs surface modification according to the different requirements.     

1-Hexadecylamine as both reducing agent and stabilizer to synthesize Au and Ag nanoparticles and their SERS application

1-Hexadecylamine (HDA)-capped Au and Ag nanoparticles (NPs) have been successfully prepared by a one-pot solution growth method. The HDA is used as both reducing agent and stabilizer in the synthetic process is favorable for investigating the capping mechanism of Au and Ag NPs’ surface. The growth process and characterization of Au and Ag NPs are determined by Ultraviolet–visible (UV–vis) spectroscopy, transmission electron microscopy (TEM), and X-ray diffraction (XRD). Experimental results demonstrate that the HDA-capped Au and Ag NPs are highly crystalline and have good optical properties. Furthermore, surface-enhanced Raman scattering (SERS) spectra of 2-thionaphthol are obtained on the Au and Ag NPs modified glass surface, respectively, indicating that the as-synthesized noble metal NPs have potentially high sensitive optical detection application.     

Simple method to prepare size‐controllable gold nanoparticles in solutions and their applications on surface‐enhanced Raman scattering

We report here, for the first time, a simple method to prepare size‐controllable Au nanoparticles (NPs) in aqueous solutions from bulk Au substrates. First, chitosan (Ch)‐capped Au‐containing complexes were prepared by electrochemical oxidation–reduction cycles in 0.1 N NaCl and 1 g/l Ch solutions. Then the solutions were heated from room temperature to boiling at different heating rates to synthesize size‐controllable Au NPs. The particle sizes of the prepared Au(111) NPs could be controlled from 5 to 30 nm with an increase of the heating rate during preparation. Experimental results indicate that the prepared Au(111) NPs with diameters ranging from 10 to 30 nm can serve as surface‐enhanced Raman scattering active probes for molecules of rhodamine 6G. Copyright © 2010 John Wiley & Sons, Ltd.     

Hydrodynamic cavitation: A feasible approach to intensify the emulsion cross-linking process for chitosan nanoparticle synthesis

Chitosan nanoparticles (NPs) exhibit great potential in drug-controlled release systems. A controlled hydrodynamic cavitation (HC) technique was developed to intensify the emulsion crosslinking process for the synthesis of chitosan NPs. Experiments were performed using a circular venturi and under varying operating conditions, i.e., types of oil, addition mode of glutaraldehyde (Glu) solution, inlet pressure (P_in), and rheological properties of chitosan solution. Palm oil was more appropriate for use as the oil phase for the HC-intensified process than the other oil types. The addition mode of water-in-oil (W/O) emulsion containing Glu (with Span 80) was more favorable than the other modes for obtaining a narrow distribution of chitosan NPs. The minimum size of NPs with polydispersity index of 0.342 was 286.5 nm, and the maximum production yield (P_y) could reach 47.26%. A positive correlation was found between the size of NPs and the droplet size of W/O emulsion containing chitosan at increasing P_in. Particle size, size distribution, and the formation of NPs were greatly dependent on the rheological properties of the chitosan solution. Fourier transform infrared spectroscopy (FTIR) analysis indicated that the molecular structure of palm oil was unaffected by HC-induced effects. Compared with ultrasonic horn, stirring-based, and conventional drop-by-drop processes, the application of HC to intensify the emulsion crosslinking process allowed the preparation of a finer and a narrower distribution of chitosan NPs in a more energy-efficient manner. The novel route developed in this work is a viable option for chitosan NP synthesis.     

Effect of chitosan and thiolated chitosan coating on the inhibition behaviour of PIBCA nanoparticles against intestinal metallopeptidases

Surface modified nanoparticles composed of poly(isobutylcyanoacrylate) (PIBCA) cores surrounded by a chitosan and thiolated chitosan gel layer were prepared and characterized in previous works. The presence of such biopolymers on the nanoparticle surface conferred those nanosystems interesting characteristics that might partially overcome the gastrointestinal enzymatic barrier, improving the oral administration of pharmacologically active peptides. In the present work, the antiprotease behaviour of this family of core–shell nanoparticles was in vitro tested against two model metallopeptidases present in the gastrointestinal tract (GIT): Carboxypeptidase A -CP A- (luminal protease) and Leucine Aminopeptidase M -LAP M- (membrane protease). As previous step, the zinc-binding capacity of these nanoparticles was evaluated. Interestingly, an improvement of both the zinc-binding capacity and the antiprotease effect of chitosan was observed when the biopolymers (chitosan and thiolated chitosan) were used as coating component of the core–shell nanoparticles, in comparison with their behaviour in solution, thanks to the different biopolymer chains rearrangement. The presence of amino, hydroxyl and thiol groups on the nanoparticle surface promoted zinc binding and hence the inhibition of the metallopeptidases analysed. On the contrary, the occurrence of a cross-linked structure in the gel layer surrounding the PIBCA cores of thiolated formulations, due to the formation of interchain and intrachain disulphide bonds, partially limited the inhibition of the proteases. The low accessibility of cations to the active groups of the cross-linked polymeric shell was postulated as a possible explanation of this behaviour. Results obtained in this work make this family of surface-modified nanocarriers promising candidates for the successfull administration of pharmacologically active peptides and proteins by the oral route.     

Aqueous phase Ag nanoparticles with controlled shapes fabricated by a modified nanosphere lithography and their optical properties

We have developed a modified nanosphere lithography (NSL) process to fabricate surface-confined Ag nanoparticles (NPs) with controlled shapes. NPs with different shapes, such as triangular, quadrilateral, pentagon or trapezoidal with rounded tips or edges, can be fabricated by this process. These Ag NPs can be dislodged into water forming NPs in an aqueous environment. The developed process results in better NP shape retaining than those obtained using the routine NSL process. The UV-vis absorption of the surface-confined Ag NPs show distinct blue shift and reduced intensity after surface modification. The NPs produced by the modified NSL and dislodged in water have significantly less density of debris as observed by transmission electron microscopy and UV-vis absorption spectrum.     

Utilization of ultrasonic irradiation as a green and effective strategy to prepare poly(N-vinyl-2-pyrrolidone)/modified nano-copper (II) oxide nanocomposites

The present paper describes the result of investigations into preparation of novel nanocomposites (NCs) based on poly(N-vinyl-2-pyrrolidone) (PVP) as a biocompatible polymer and modified copper (II) oxide nanoparticles (NPs) as a nano-filler. To achieve optimum NCs properties, different ratios of modified copper (II) oxide NPs (3, 5, and 7 wt%) were used to fabricate PVP NCs and also the ultrasonic irradiation was utilized to perform these processes as a fast and effective method. Subsequently, the structure of the obtained nanohybrids was characterized by various techniques. The suitable incorporation between PVP matrix and modified CuO NPs can be seen from the FT-IR spectra. The obtained NCs indicated an efficient thermal improvement in comparison to the pristine polymer. Also, the uniform dispersion of modified CuO NPs in the PVP matrix was detected by FE-SEM and EDX. According to UV absorption spectra, it is clear that these NCs can be used in UV protecting applications.