Self‐Assembly of Functionalized Gold Nanoparticles with Rigid and Flexible Multifunctional Linkers

The interparticle spacing of carboxyl functionalized gold nanoparticles (Au–COOH) was mediated by rigid cross‐linkers, octa(3‐aminopropyl)octasilsesquioxane (POSS–NH₃ ⁺) and poly(amidoamine) dendrimer terminated with hydroxyl groups (PAMAM–OH), and a flexible polymeric linker, poly(hexanyl viologen) (6‐VP). Regular interparticle spacing was achieved by utilizing POSS–NH₃ ⁺ and PAMAM–OH dendrimer as cross‐linkers, whereas size growth of Au–COOH was observed featuring no interparticle spacing by utilizing 6‐VP as the cross‐linker.     

Multiple Emulsion Templating of Hybrid Ag/SiO2 Capsules for Antibacterial Applications

Silver nanoparticles (NPs) encapsulated in amorphous silica shells are synthesized and evaluated for their antibacterial action using the Gram‐negative Escherichia coli bacterium. These inorganic capsules are synthesized using a new approach that comprises the use of oil‐in‐water‐in‐oil (O/W/O) multiple emulsions to fabricate SiO₂ capsules incorporating organically capped Ag NPs. This strategy is explored as a mean to promote the bioadhesion of the microorganisms to the silica rough surfaces while still keeping the system with a high surface area for the active metal. The results have shown that the hybrid capsules enable a slow release of cationic silver from the interior of the silica microsphere to the external medium probably through the pore channels in the shell. The antibacterial activity against E. coli is mainly determined by the Ag⁺ ion release rate, suggesting that these particulates can be employed as a robust system for prolonged used as an antimicrobial material.     

Designing Zwitterionic SiO2NH2‐Au Particles with Tunable Patchiness using Wrinkles

A facile template‐based approach toward zwitterionic SiO₂NH₂‐Au patchy particles is presented. Therefore, wrinkle templates prepared by stress release in a bilayer system comprised of an elastic PDMS fundament and a thin SiO_x top layer are used. After aligning positively charged, amine‐functionalized silica particles in wrinkle grooves, their surfaces are partially modified with negatively charged gold nanoparticles in an electrostatic adsorption step. Patchiness is precisely controlled by the degree of immersion of the initial particles into wrinkles of varying dimensions. By ultrasonication or wetting with a water droplet, patchy particles are easily released from the substrate‐yielding particles with two oppositely charged hemispheres. Interfacial tension measurements prove the surface activity of the SiO₂NH₂‐Au particles in an oil/water system and are explained in the view of the Janus‐type surface charges of the particles and the charge of the oil/water interface.     

Electrostatically mediated adsorption by nanodiamond and nanocarbon particles

Nanodiamond (ND) and other nanocarbon particles are popular platforms for the immobilization of molecular species. In the present research, factors affecting adsorption and desorption of propidium iodide (PI) dye, chosen as a charged molecule model, on ND and sp ² carbon nanoparticles were studied, with a size ranging from 75 to 4,305 nm. It was found that adsorption of PI molecules, as characterized by ultraviolet–visible spectroscopy, on ND particles is strongly influenced by sorbent-sorbate electrostatic interactions. Different types of NDs with a negative zeta potential were found to adsorb positively charged PI molecules, while no PI adsorption was observed for NDs with a positive zeta potential. The type and density of surface groups of negatively charged NDs greatly influenced the degree and capacity of the PI adsorbed. Ozone-purified NDs had the highest capacity for PI adsorption, due to its greater density of oxygen containing groups, i.e., acid anhydrides and carboxyls, as assessed by TDMS and TOF–SIMS. Single wall nanohorns and carbon onion particles were found to adsorb PI regardless of their zeta potential; this is likely due to π bonding between the aromatic rings of PI and the graphitic surface of the materials and the internal cavity of the horns.     

Boat-like Au nanoparticles embedded mesoporous γ-Al2O3 films: an efficient SERS substrate

A new water-dispersible nanostructure based on magnetite (Fe₃O₄) and usnic acid (UA) was prepared in a well-shaped spherical form by a precipitation method. Nanoparticles were well individualized and homogeneous in size. The presence of Fe₃O₄@UA was confirmed by transmission electron microscopy, Fourier transform-infrared spectroscopy, and X-ray diffraction. The UA was entrapped in the magnetic nanoparticles during preparation and the amount of entrapped UA was estimated by thermogravimetric analysis. Fabricated nanostructures were tested on planktonic cells growth (minimal inhibitory concentration assay) and biofilm development on Gram-positive Staphylococcus aureus (S. aureus), Enterococcus faecalis (E. faecalis) and Gram-negative Escherichia coli (E. coli), Pseudomonas aeruginosa (P. aeruginosa) reference strains. Concerning the influence of Fe₃O₄@UA on the planktonic bacterial cells, the functionalized magnetic nanoparticles exhibited a significantly improved antimicrobial activity against E. faecalis and E. coli, as compared with the Fe₃O₄ control. The UA incorporated into the magnetic nanoparticles exhibited a very significant inhibitory effect on the biofilm formed by the S. aureus and E. faecalis, on a wide range of concentrations, while in case of the Gram-negative microbial strains, the UA-loaded nanoparticles inhibited the E. coli biofilm development, only at high concentrations, while for P. aeruginosa biofilms, no inhibitory effect was observed. The obtained results demonstrate that the new water-dispersible Fe₃O₄@UA nanosystem, combining the advantages of the intrinsic antimicrobial features of the UA with the higher surface to volume ratio provided by the magnetic nanocarrier dispersible in water, exhibits efficient antimicrobial activity against planktonic and adherent cells, especially on Gram-positive strains.     

Theoretical studies and antibacterial activity for Schiff base complexes

New ligand 4‐((2‐Hydroxy1‐naphthyl) methylene amino)‐1.5‐dimethyl‐2‐phenyl‐1H‐pyrazol‐3(2H)‐one (HL) was synthesized from the reaction of 2‐hydroxy‐1‐naphthaldehyde and 4‐aminophenaz one. A complexes of this ligand [VO(II)(HL)(SO₄)], [Pt(IV)(L)Cl₃], [Re(V)(L)Cl₃]Cl, and [M(II)(L)Cl] (M═Pd(II), Ni(II), Cu(II)) were synthesized. The resulted compounds were characterized by IR, NMR (¹H and ¹³C), mass spectrometry, element analysis, and UV‐Vis spectroscopy. Additionally, the spectroscopic studies revealed octahedral geometries for the Re(V), Pt(IV) complexes, and square pyramidal for VO(II), square planar for Pd(II) complex, and tetrahedral for the Ni(II) and Cu(II) complexes. Thermodynamic parameters (ΔE^*, ΔH^*, ΔS^*, ΔG^*, and K) were calculated using from the TGA curve Coats‐Red fern method. Therefore, hyper Chem‐8 program has been used to predict structural geometries of compounds in the gas phase. Finally, the synthesized Schiff base and its metal complexes were screened for their biological activity against bacterial species, 2 Gram‐positive bacteria (Bacillus subtilis and Staphylococcus aureus) and 2 Gram‐negative bacteria (Escherichia coli and Pseudomonas aeruginosa).     

Characterization of self-assembled monolayers (SAMs) on silicon substrate comparative with polymer substrate for Escherichia coli O157:H7 detection

This article presents the characterization of two substrates, silicon and polymer coated with gold, that are functionalized by mixed self-assembled monolayers (SAMs) in order to efficiently immobilize the anti-Escherichia coli O157:H7 polyclonal purified antibody.A biosurface functionalized by SAMs (self-assembled monolayers) technique has been developed. Immobilization of goat anti-E. coli O157:H7 antibody was performed by covalently bonding of thiolate mixed self-assembled monolayers (SAMs) realized on two substrates: polymer coated with gold and silicon coated with gold. The F(ab′)₂ fragments of the antibodies have been used for eliminating nonspecific bindings between the Fc portions of antibodies and the Fc receptor on cells. The properties of the monolayers and the biofilm formatted with attached antibody molecules were analyzed at each step using infrared spectroscopy (FTIR-ATR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV). In our study the gold-coated silicon substrates approach yielded the best results.These experimental results revealed the necessity to investigate each stage of the immobilization process taking into account in the same time the factors that influence the chemistry of the surface and the further interactions as well and also provide a solid basis for further studies aiming at elaborating sensitive and specific immunosensor or a microarray for the detection of E. coli O157:H7.     

Prevention of biofilm re‐development on Ti‐6Al‐4V alloy by cometary discharge with a metallic grid

The influence of a non‐thermal plasma (NTP) on the gram‐negative bacteria Escherichia coli and Pseudomonas aeruginosa, the gram‐positive bacterium Staphylococcus epidermidis, and the yeast Candida albicans grown on agar or in the biofilm form was compared. NTP was produced by a DC cometary discharge. The biofilms were grown on the surface of Ti‐6Al‐4V alloy often used in the manufacture of prosthetic implants. The exposure by NTP not only inhibited the surface growth of microorganisms in agar cultures but also significantly suppressed the viability of bacteria and yeast in biofilms and prevented its re‐developed from persistent cells remaining in the lower layers of the biofilm. An almost complete prevention of biofilm re‐development was achieved in the case of S. epidermidis; other microorganisms displayed substantial lowering of biofilm biomass and its metabolic activity.     

Leucine pools in Escherichia coli biofilm discovered by Raman imaging

In structured communities of bacteria known as biofilms, a variety of biomolecules have been shown to play a unique role as signals and/or regulators in biofilm formation. Here, we report that high levels of the amino acid leucine (leucine pool) were detected, for the first time, within microcolonies in a 30‐h‐old Escherichia coli biofilm by Raman imaging. Localization of leucine revealed by multifrequency Raman images indicates leucine accumulation during the early stage of the E. coli biofilm formation, which may have resulted from physiological environment‐specific metabolic adaptation. We demonstrate that our label‐free Raman imaging method provides a useful platform for directly identifying still unknown natural products produced in biofilms as well as for visualizing heterogeneous distributions of biofilm constituents in situ. Copyright © 2011 John Wiley & Sons, Ltd.     

Spectroscopic properties of polycrystals of supramolecular europium complexes with bathophenanthroline

Nanostructured supramolecular complex of europium(III) with bathophenanthroline (bphen), with detonation synthesis nanodiamonds (NDs) used as a structure-forming element, has been synthesized for the first time. The characteristics of the Eu(bphen)₂(NO₃)₃ complex and the supramolecular complex with NDs, ND–Eu(bphen)₂(NO₃)₂, are studied and compared using scanning electron microscopy (SEM), luminescence spectroscopy, IR spectroscopy, and electron-spin resonance (ESR) spectroscopy. The luminescence quantum yields of the complexes are estimated by the relative method using a β-diketonate complex of europium (III) with tris(thenoyltrifluoroacetone) and 1,10-phenanthroline (Eu(TTA)₃phen) as a reference. It is found that the ND–Eu(bphen)₂(NO₃)₂ supramolecular complex has a higher photoresistance than the complex without NDs and no worse thermal stability (up to a temperature of +150°C).     

Carbon‐Dot‐Decorated Nanodiamonds

The synthesis of a new class of fluorescent carbon nanomaterials, carbon‐dot‐decorated nanodiamonds (CDD‐ND), is reported. These CDD‐NDs are produced by specific acid treatment of detonation soot, forming tiny rounded sp² carbon species (carbon dots), 1–2 atomic layers thick and 1–2 nm in size, covalently attached to the surface of the detonation diamond nanoparticles. A combination of nanodiamonds bonded with a graphitic phase as a starting material and the application of graphite intercalated acids for oxidation of the graphitic carbon is necessary for the successful production of CDD‐ND. The CDD‐ND photoluminescence (PL) is stable, 20 times more intense than the intrinsic PL of well‐purified NDs and can be tailored by changing the oxidation process parameters. Carbon‐dot‐decorated DNDs are shown to be excellent probes for bioimaging applications and inexpensive additives for PL nanocomposites.     

Food additives characterization by infrared,Raman, and surface‐enhanced Raman spectroscopies

Fourier‐transform infrared (FT‐IR), Raman (RS), and surface‐enhanced Raman scattering (SERS) spectra of β‐hydroxy‐β‐methylobutanoic acid (HMB), L ‐carnitine, and N‐methylglycocyamine (creatine) have been measured. The SERS spectra have been taken from species adsorbed on a colloidal silver surface. The respective FT‐IR and RS band assignments (solid‐state samples) based on the literature data have been proposed. The strongest absorptions in the FT‐IR spectrum of creatine are observed at 1398, 1615, and 1699 cm⁻¹, which are due to ν_s(COOH) + ν(CN) + δ(CN), ρ_s(NH₂), and ν(C O) modes, respectively, whereas those of L ‐carnitine (at 1396/1586 cm⁻¹ and 1480 cm⁻¹) and HMB (at 1405/1555/1585 cm⁻¹ and 1437–1473 cm⁻¹) are associated with carboxyl and methyl/methylene group vibrations, respectively. On the other hand, the strongest bands in the RS spectrum of HMB observed at 748/1442/1462 cm⁻¹ and 1408 cm⁻¹ are due to methyl/methylene deformations and carboxyl group vibrations, respectively. The strongest Raman band of creatine at 831 cm⁻¹ (ρ_w(R NH₂)) is accompanied by two weaker bands at 1054 and 1397 cm⁻¹ due to ν(CN) + ν(R NH₂) and ν_s(COOH) + ν(CN) + δ(CN) modes, respectively. In the case of L ‐carnitine, its RS spectrum is dominated by bands at 772 and 1461 cm⁻¹ assigned to ρ_r(CH₂) and δ(CH₃), respectively. The analysis of the SERS spectra shows that HMB interacts with the silver surface mainly through the  COO⁻, hydroxyl, and  CH₂ groups, whereas L ‐carnitine binds to the surface via  COO⁻ and  N⁺(CH₃)₃ which is rarely enhanced at pH = 8.3. On the other hand, it seems that creatine binds weakly to the silver surface mainly by  NH₂, and C O from the  COO⁻ group. Copyright © 2006 John Wiley & Sons, Ltd.     

Chitosan Nanoparticles: Preparation and Application in Antibacterial Paper

Chitosan nanoparticles (CSNP) were obtained by H₂O₂ degradation of chitosan. Their morphology and size were determined by atomic force microscope (AFM), and the particles were found smooth and approximately 36 nm in size. CSNP-0.5% HAc solutions (1, 2, 5, and 10 mg/mL) were used in antibacterial paper by addition in pulp, impregnation, dispersion coating on the handsheets, and insufflation. The antibacterial activity of CSNP against Escherichia coli and Staphylococcus aureus was measured by the inhibition zone and bacterial reduction methods. Results showed that the antibacterial activity of CSNP was improved with the increase in concentration. For E. coli, at a CSNP concentration of 5 mg/mL, the antibacterial rate reached approximately 95%. However, for S. aureus, the antibacterial rate only reached 81%. In addition, the antibacterial activity of the antibacterial paper was determined by inhibition zone method. The paper prepared by insufflation had the greatest activity. For E. coli, at a CSNP concentration of 10 mg/mL, the inhibition zone reached 8.0 mm. For S. aureus, the inhibition zone was 6.8 mm.     

Shape-controlled synthesis of Cu2O nano/microcrystals and their antibacterial activity

Uniform cuprous oxides with different morphologies have been successfully synthesized using polyvinylpyrrolidone (PVP) as a capping agent. X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis spectrophotometer, Fourier transform infrared spectrometer (FTIR) and X-ray photoelectron spectroscopy were employed to characterize the structure and morphology of cuprous oxides. It was found that the reaction conditions such as PVP, reducing agent and complexing agent played important roles in the formation of regular cuprous oxide crystals. In addition, their antibacterial activity against Bacillus subtilis (B. subtilis), Staphylococcus aureus (S. aureus), Escherichia coli (E. coli) and Pseudomonas aeruginosa (P. aeruginosa) was also investigated by the Oxford cup method. Results suggested that cuprous oxides are selective in their antibacterial action. They display effective antibacterial activity against S. aureus, B. subtilis and P. aeruginosa. There is no bactericidal ability against E. coli in the tested concentration range, which indicates that E. coli may be a Cu(I)-tolerant bacterium.     

Calculated polar substituent effects on the stability of 3‐substituted(X) bicyclo[1.1.1]pent‐1‐yl cations and 4‐substituted(X) bicyclo[2.2.1]hept‐1‐yl cations: a DFT study

The effects of substituents on the stability of 3‐substituted(X) bicyclo[1.1.1]pent‐1‐yl cations (3) and 4‐substituted(X) bicyclo[2.2.1]hept‐1‐yl cations (4), for a set of substituents (X = H, NO₂, CN, NC, CF₃, CHO, COOH , F, Cl, HO, NH₂, CH₃, SiH₃, Si(CH₃)₃, Li, O^?, and NH₃⁺) covering a wide range of electronic substituent effects were calculated using the DFT theoretical model at the B3LYP/6‐311 + G(2d,p) and B3LYP/6‐31 + G (d) levels of theory, respectively. Linear regression analysis was employed to explore the relationship between the calculated relative hydride affinities (ΔE, kcal/mol) of the appropriate isodesmic reactions for 3/4 and polar field/group electronegativity substituent constants (σ_F and σ_χ, respectively). The analysis reveals that the ΔE values for both systems are best described by a combination of both substituent constants. The result highlights the importance of the σ_χ dependency of charge delocalization in these systems. Copyright © 2012 John Wiley & Sons, Ltd.     

FTIR investigation of the effects of ultra-strong static magnetic field on the secondary structures of protein in bacteria

Secondary structures of protein in Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) exposed to the ultra-strong static magnetic field (SMF) were investigated by Fourier transformation infrared spectroscopy (FTIR). Difference index D value of amide I (1600–1700 cm⁻¹) showed that the ultra-strong magnetic field had little impact on S. aureus, but had strong impact on E. coli. The results indicated that 3.46–9.92% of the disorder coils in the secondary structures of protein in E. coli were turned into α-helices under SMF while applying deconvolution and curve fitting to amide I. At the same time, intermolecular β-sheets transforming into intramolecular ones suggested that cohesion among protein molecules had been destroyed and intramolecular hydrogen bonds strengthened. All the differences among the compositions of protein’s secondary structures in E. coli were mostly due to the varying degrees of various proteins affected by the magnetic field. The results may provide new insights into the structural changes of proteins induced by the SMF.     

Electrochemical in situ surface enhanced Raman spectroscopic characterization of a trinuclear ruthenium complex,Ru‐red

To study the fate of a molecular di‐μ‐oxo‐bridged trinuclear ruthenium complex, [(NH₃)₅Ru–O–Ru(NH₃)₄–O–Ru(NH₃)₅]⁶⁺, also known as Ru‐red, during the electro‐driven water oxidation reaction, electrochemical in situ surface enhanced Raman spectroscopy (SERS) investigations have been conducted on an electrochemically roughened gold surface in acidic condition. It was previously described that on a basal plane pyrolitic graphite electrode in 0.1 M H₂SO₄ aqueous solution, Ru‐red undergoes one electron oxidative conversion into a stable higher oxidation state ruthenium complex, Ru‐brown, at <1.0 V (vs normal hydrogen electrode (NHE)), and this leads to water oxidation and dioxygen release, but the fate of Ru‐red during electrochemistry was not studied in much detail. In this investigation, Ru‐red dispersed in acid electrolyte and immobilized on a roughened gold electrode without Ru‐red in solution has been subjected to anodic controlled potential experiments, and in situ SERS was carried out at various potentials in succession. The electrochemical SERS data obtained for Ru‐red are also compared with in situ SERS results of an electrodeposited ruthenium oxide thin film on the Au disk. Our study suggests that on a gold electrode in sulfuric acid solution containing Ru‐red, one electron oxidative conversion of Ru‐red to a higher oxidation state ruthenium compound, Ru‐brown, occurs at ca. 0.74 V (vs NHE), as supported by the electrochemical in situ SERS experiments. Moreover, at higher potentials and on Au disk, the Ru‐red / Ru‐brown are not stable and slowly decompose or electro‐oxidize leading to deactivation of the tri‐ruthenium catalytic system in acidic medium. Copyright © 2013 John Wiley & Sons, Ltd.     

Detection of bacteria aided by immuno‐nanoparticles

Magnetic immuno‐nanorice particles were used for the capture and detection of Escherichia coli (E. coli) bacteria. The selectivity of the method was attained by attaching a specific anti‐E. coli antibody on the surface of the nanorice, binding exclusively to E. coli. The antibody attachment to the nanorice (60% sorption efficiency) took place through protein‐A molecules (82% uptake). Once E. coli was captured, the immuno‐nanorice‐bacteria complex was separated from the solution using the magnetic property of the nanorice. The detection of bacteria sorbed onto the immuno‐nanorice was accomplished using the ultra‐violet resonance Raman (UVRR) method, detecting single bacterial cells. Specific information concerning the aromatic residues tyrosine (Tyr), phenylalanine (Phe) and tryptophan (Trp) was derived. The discriminant function and cluster hierarchical analysis confirmed the specific and reliable bacteria‐detection capabilities. Copyright © 2007 John Wiley & Sons, Ltd.     

Highly bacterial resistant silver nanoparticles: synthesis and antibacterial activities

In this article, we describe a simple one-pot rapid synthesis route to produce uniform silver nanoparticles by thermal reduction of AgNO₃ using oleylamine as reducing and capping agent. To enhance the dispersal ability of as-synthesized hydrophobic silver nanoparticles in water, while maintaining their unique properties, a facile phase transfer mechanism has been developed using biocompatible block co-polymer pluronic F-127. Formation of silver nanoparticles is confirmed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV–vis spectroscopy. Hydrodynamic size and its distribution are obtained from dynamic light scattering (DLS). Hydrodynamic size and size distribution of as-synthesized and phase transferred silver nanoparticles are 8.2 ± 1.5 nm (σ = 18.3%) and 31.1 ± 4.5 nm (σ = 14.5%), respectively. Antimicrobial activities of hydrophilic silver nanoparticles is tested against two Gram positive (Bacillus megaterium and Staphylococcus aureus), and three Gram negative (Escherichia coli, Proteus vulgaris and Shigella sonnei) bacteria. Minimum inhibitory concentration (MIC) values obtained in the present study for the tested microorganisms are found much better than those reported for commercially available antibacterial agents.     

Characterization of the unstability of 4-mercaptoaniline capped platinum nanoparticles solution by combining LB technique and X-ray photoelectron spectroscopy

This paper reports on the study of the evolution of 4-mercaptoaniline (p-HSC₆H₄NH₂) functionalized platinum nanoparticles in solution by coupling the Langmuir-Blodgett technique and X-ray photoelectron spectroscopy (XPS). The spectra are recorded on mixed LB films containing fatty acid and platinum particles in proportion 50/50. Several samples built from fresh and aged solutions of particles are analyzed. Comparison of the Pt 4f, S 2p and N 1s regions in each case points to the time dependant chemical evolution of the functionalized particles involving at once platinum, thiolate and amine components. The particle aging in solution is reported during several months, until the complete flocculation of the functionalized platinum nanoparticles. Using the compared XPS analysis of the LB layers obtained from the different particle solutions, unstability of the storage looks then clearly related to the chemical evolution of the bifunctional organic crown.