A new family of sterically hindered alkyl(tri-tert-butyl) phosphonium salts (n-CnH2n+1 with n = 2, 4, 6, 8, 10, 12, 14, 16, 18, 20) was synthesized and evaluated as stabilizers for the formation of palladium nanoparticles (PdNPs), and the prepared PdNPs, stabilized by a series of phosphonium salts, were applied as catalysts of the Suzuki cross-coupling reaction. All investigated phosphonium salts were found to be excellent stabilizers of metal nanoparticles of small catalytically active size with a narrow size distribution. In addition, palladium nanoparticles exhibited exceptional stability: the presence of phosphonium salts prevented agglomeration and precipitation during the catalytic reaction.

The creation of mitochondria-targeted vector systems is a new tool for the treatment of socially significant diseases. Phosphonium groups provide targeted delivery of drugs through biological barriers to organelles. For this purpose, a new class of alkyl(diethylAmino)(Phenyl) Phosphonium halides (APPs) containing one, two, or three diethylamino groups was obtained by the reaction of alkyl iodides (bromides) with (diethylamino)(phenyl)phosphines under mild conditions (20 °C) and high yields (93-98%). The structure of APP was established by NMR and XRD. A high in vitro cytotoxicity of APPs against M-HeLa, HuTu 80, PC3, DU-145, PANC-1, and MCF-7 lines was found. The selectivity index is in the range of 0.06-4.0 μM (SI 17-277) for the most active APPs. The effect of APPs on cancer cells is characterized by hyperproduction of ROS and depolarization of the mitochondrial membrane. APPs induce apoptosis, proceeding along the mitochondrial pathway. Incorporation of APPs into lipid systems (liposomes and solid lipid nanoparticles) improves cytotoxicity toward tumor cells and decrease toxicity against normal cell lines. The IC50s of lipid systems are lower than for the reference drug DOX, with a high SI (30-56) toward MCF-7 and DU-145. APPs exhibit high selective activity against Gram-positive bacteria S. aureus 209P and B. segeus 8035, including methicillin-resistant S. aureus (MRSA-1, MRSA-2), comparable to the activity of the fluoroquinolone antibiotic norfloxacin. A moderate in vivo toxicity in CD-1 mice was established for the lead APP.

We previously described the manufacture and characterization of hydrogel forming, thin film, anti-infective wound dressings made from Poly Vinyl Alcohol (PVA) and silver nanoparticles, crosslinked by heat. However, these films were designed to be inexpensive for simple manufacture locally in Africa. In this new study, we have further developed PVA dressings by manufacturing films or electrospun membranes, made from blends of PVA with different degrees of hydrolyzation, that contain silver salts and degrade in a controlled manner to release silver in a sustained manner over 12 days.

Single walled carbon nanotubes (SWCNT) were functionalized using the 1,3-dipolar cycloaddition reaction of an azomethine ylide under solvent-free conditions, a one-pot procedure that yields pyrrolidine type of groups at the nanotubes surface. The functionalized SWCNT were further decorated with Ag and Cu nanoparticles by reduction of the corresponding metal salts in dimethylformamide. The extensive reduction of silver from its nitrate was observed, as well as the partial reduction of copper from its acetate. X-ray photoelectron spectroscopy (XPS) confirmed the functionalization of SWCNT with pyrrolidine that provided anchoring sites for the metal nanoparticles. Metal nanoparticles (NP) were formed at the surface of the organically functionalized SWCNT in higher yields as compared to the same procedure carried out with pristine SWCNT. This was observed using scanning electron microscopy (SEM) and quantified by XPS. Raman spectroscopy demonstrated that functionalization and metal decoration of the SWCNT did not induce structural damage to the SWCNT.

The direct use of ethanol in fuel cells presents unprecedented economic, technical, and environmental opportunities in energy conversion. However, complex challenges need to be resolved. For instance, ethanol oxidation reaction (EOR) requires breaking the rigid C-C bond and results in the generation of poisoning carbonaceous species. Therefore, new designs of the catalyst electrode are necessary. In this work, two trimetallic PdxAgyNiz/C samples are prepared using a facile borohydride reduction route. The catalysts are characterized by X-ray diffraction (XRD), Energy-Dispersive X-ray spectroscopy (EDX), X-ray photoelectron Spectroscopy (XPS), and Transmission Electron Microscopy (TEM) and evaluated for EOR through cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). The XRD patterns have shown a weak alloying potential between Pd, and Ag prepared through co-reduction technique. The catalysts prepared have generally shown enhanced performance compared to previously reported ones, suggesting that the applied synthesis may be suitable for catalyst mass production. Moreover, the addition of Ag and Ni has improved the Pd physiochemical properties and electrocatalytic performance towards EOR in addition to reducing cell fabrication costs. In addition to containing less Pd, The PdAgNi/C is the higher performing of the two trimetallic samples presenting a 2.7 A/mgPd oxidation current peak. The Pd4Ag2Ni1/C is higher performing in terms of its steady-state current density and electrochemical active surface area.

In view of a simple after-use separation, the potentiality of producing magnetic activated carbon (MAC) by intercalation of ferromagnetic metal oxide nanoparticles in the framework of a powder activated carbon (PAC) produced from primary paper sludge was explored in this work. The synthesis conditions to produce cost effective and efficient MACs for the adsorptive removal of pharmaceuticals (amoxicillin, carbamazepine, and diclofenac) from aqueous media were evaluated. For this purpose, a fractional factorial design (FFD) was applied to assess the effect of the most significant variables (Fe3+ to Fe2+ salts ratio, PAC to iron salts ratio, temperature, and pH), on the following responses concerning the resulting MACs: Specific surface area (SBET), saturation magnetization (Ms), and adsorption percentage of amoxicillin, carbamazepine, and diclofenac. The statistical analysis revealed that the PAC to iron salts mass ratio was the main factor affecting the considered responses. A quadratic linear regression model A = f(SBET, Ms) was adjusted to the FFD data, allowing to differentiate four of the eighteen MACs produced. These MACs were distinguished by being easily recovered from aqueous phase using a permanent magnet (Ms of 22-27 emu g-1), and their high SBET (741-795 m2 g-1) were responsible for individual adsorption percentages ranging between 61% and 84% using small MAC doses (35 mg L-1).

Surface-enhanced Raman scattering (SERS) is a powerful technique for decoding of 2-5-component mixes of analytes. Low concentrations of analytes and complex biological media are usually non-decodable with SERS. Recognition molecules, such as antibodies and aptamers, provide an opportunity for a specific binding of ultra-low contents of analyte dissolved in complex biological media. Different approaches have been proposed to provide changes in SERS intensity of an external label upon binding of ultra-low contents of the analytes. In this paper, we propose a SERS-based sensor for the rapid and sensitive detection of botulinum toxin type A. The silver nanoisland SERS substrate was functionalized using an aptamer conjugated with a Raman label. The binding of the target affects the orientation of the label, providing changes in an analytical signal. This trick allowed detecting botulinum toxin type A in a one-stage manner without additional staining with a monotonous dose dependence and a limit of detection of 2.4 ng/mL. The proposed sensor architecture is consistent with the multiarray detection systems for multiplex analyses.

Grouping approaches of nanomaterials have the potential to facilitate high throughput and cost effective nanomaterial screening. However, an effective grouping of nanomaterials hinges on the application of suitable physicochemical descriptors to identify similarities. To address the problem, we developed an integrated testing approach coupling acellular and cellular phases, to study the full life cycle of ingested silver nanoparticles (NPs) and silver salts in the oro-gastrointestinal (OGI) tract including their impact on cellular uptake and integrity. This approach enables the derivation of exposure-dependent physical descriptors (EDPDs) upon biotransformation of undigested nanoparticles, digested nanoparticles and digested silver salts. These descriptors are identified in: size, crystallinity, chemistry of the core material, dissolution, high and low molecular weight Ag-biomolecule soluble complexes, and are compared in terms of similarities in a grouping hypothesis. Experimental results indicate that digested silver nanoparticles are neither similar to pristine nanoparticles nor completely similar to digested silver salts, due to the presence of different chemical nanoforms (silver and silver chloride nanocrystals), which were characterized in terms of their interactions with the digestive matrices. Interestingly, the cellular responses observed in the cellular phase of the integrated assay (uptake and inflammation) are also similar for the digested samples, clearly indicating a possible role of the soluble fraction of silver complexes. This study highlights the importance of quantifying exposure-related physical descriptors to advance grouping of NPs based on structural similarities.

Kraft lignin was catalytically graphitized to graphene-based nanostructures at 1000 °C under argon atmosphere with four iron catalysts, iron(III) nitrate (Fe-N); iron(II) chloride (Fe-Cl₂); iron(III) chloride (Fe-Cl₃); and iron(II) sulfate (Fe-S). The catalytic decomposition process of iron-promoted lignin materials was examined using thermalgravimetric analysis and temperature-programmed decomposition methods. The crystal structure, morphology and surface area of produced materials were characterized by means of X-ray diffraction, Raman, scanning electron microscopy, high resolution transmission electron microscopy and N₂ adsorption-desorption techniques. Experimental results indicated that iron nitrate catalyst had better iron dispersion three other iron salts. Iron nitrate was the most active catalyst among four iron salts. The low activity of iron in iron chloride-promoted samples was because the residual chlorine over iron surfaces prevent iron interaction with lignin functional groups.

In the recent era, carbon dots (C-dots) have been extensively considered as a potential tool in drug delivery analysis. However, there have been fewer reports in the literature on their application in the sensing of amino acids. As part of our ongoing research on coconut-husk-derived C-dots, we synthesized C-dots under different temperature conditions and utilized them in the field of amino acid sensing and found them to be highly selective and sensitive towards tyrosine. The detailed characterization of the prepared C-dots was carried out. The developed C-dots exhibit good values of quantum yield. BSA, HSA and glutamic acid were utilized to explore the binding efficiency of C-dots with biologically active components. Hemolysis, blood clotting index activity and cell viability assays using the prepared C-dots were evaluated and they were found to be biocompatible. Therefore, the C-dots described in this work have high potential to be utilized in the field of amino acid sensing, especially L-tyrosine. The limit of detection and the binding constant for the developed C-dots in the presence of tyrosine were found to be 0.96 nM and 296.38 nM-1, respectively. The efficiency of the developed C-dots was also investigated in the presence of various other amino acids and different water mediums in order to enhance the working scope of the developed sensors.

This paper demonstrates the in situ sinter bonding of Ag microparticle pastes to a Si substrate via the temporal formation and decomposition of Ag carboxylate on the surface of Ag microparticles. This was proposed via the investigation of Ag sinter bonding using the redox reaction between Ag2O and ethylene glycol, which achieved a bonding strength above 30 MPa even for the bonding temperature at 220 °C. Thermal analysis was used to identify the product of the redox reaction between Ag2O and ethylene glycol and determine the bonding temperature because the final reaction facilitates the interfacial sinter bonding with the substrate. Fourier-transform infrared spectroscopy and nuclear magnetic resonance results indicated the in situ formation of Ag salts of carboxylic acids, such as Ag oxalate on the surface of Ag microparticles. Therefore, the sinter bonding process enabled by the in situ formation and subsequent decomposition of these Ag salts was investigated using Ag microparticles and oxalic acid. Observations of the surface and interfacial morphology of the Ag particles after heating revealed the formation of Ag nanoparticles on the surfaces of the microparticles and the formation of sintering necks between the particles. The bonding experiments demonstrated a significant increase in strength with the addition of oxalic acid to the Ag paste due to the enhanced interfacial sinter bonding with the substrate. The in situ formation and decomposition of Ag salts are promising strategies for improving sintered bonds in electronic devices because they can provide enhanced localized sinter bonding using stable insert materials.

Graphene oxide (GO) nanosheets were utilized as a selective layer on a highly porous polyvinyl alcohol (PVA) nanofiber support via a pressure-assisted self-assembly technique to synthesize composite nanofiltration membranes. The GO layer was rendered stable by cross-linking the nanosheets (GO-to-GO) and by linking them onto the support surface (GO-to-PVA) using glutaraldehyde (GA). The amounts of GO and GA deposited on the PVA substrate were varied to determine the optimum nanofiltration membrane both in terms of water flux and salt rejection performances. The successful GA cross-linking of GO interlayers and GO-PVA via acetalization was confirmed by FTIR and XPS analyses, which corroborated with other characterization results from contact angle and zeta potential measurements. Morphologies of the most effective membrane (CGOPVA-50) featured a defect-free GA cross-linked GO layer with a thickness of ~67 nm. The best solute rejections of the CGOPVA-50 membrane were 91.01% for Na2SO4 (20 mM), 98.12% for Eosin Y (10 mg/L), 76.92% for Methylene blue (10 mg/L), and 49.62% for NaCl (20 mM). These findings may provide one of the promising approaches in synthesizing mechanically stable GO-based thin-film composite membranes that are effective for solute separation via nanofiltration.

ZnFe2O4 (ZFO) nanospheres with complex structures have been synthesized by a one-step simple solvothermal method using two different types of precursors-metal chlorides and nitrates -and were fully characterized by XRD, SEM, XPS, and EDS. The ZFO nanospheres synthesized from chloride salts (ZFO_C) were loose with a size range of 100-200 nm, while the ZFO nanospheres synthesized from nitrate salts (ZFO_N) were dense with a size range of 300-500 nm but consisted of smaller nanoplates. The different morphologies may be caused by the different hydrolysis rates and different stabilizing effects of chloride and nitrate ions interacting with the facets of forming nanoparticles. Electrochemical tests of nitrate-based ZFO nanospheres as anode materials for lithium-ion batteries demonstrated their higher cyclic stability. The ZFO_C and ZFO_N samples have initial specific discharge/charge capacities of 1354/1020 and 1357/954 mAh∙g-1, respectively, with coulombic efficiencies of 75% and 71%. By the 100th cycle, ZFO_N has a capacity of 276 mAh∙g-1, and for ZFO_C, only 210 mAh∙g-1 remains after 100 cycles.

We report on the construction of functionalized nanotubes based on tail sheath protein 041 from vB_KleM-RaK2 bacteriophage. The truncated 041 protein (041Δ200) was fused with fluorescent proteins GFP and mCherry or amidohydrolase YqfB. The generated chimeric proteins were successfully synthesized in E. coli BL21 (DE3) cells and self-assembled into tubular structures. We detected the fluorescence of the structures, which was confirmed by stimulated emission depletion microscopy. When 041Δ200GFP and 041Δ200mCherry were coexpressed in E. coli BL21 (DE3) cells, the formed nanotubes generated Förster resonance energy transfer, indicating that both fluorescent proteins assemble into a single nanotube. Chimeric 041Δ200YqfB nanotubes possessed an enzymatic activity, which was confirmed by hydrolysis of N4-acetyl-2'-deoxycytidine. The enzymatic properties of 041Δ200YqfB were similar to those of a free wild-type YqfB. Hence, we conclude that 041-based chimeric nanotubes have the potential for the development of delivery vehicles and targeted imaging and are applicable as scaffolds for biocatalysts.

The CO2-assisted oxidative dehydrogenation of propane (ODP) was investigated over titania based composite metal oxides, 10% MxOy-TiO2 (M: Zr, Ce, Ca, Cr, Ga). It was found that the surface basicity of composite metal oxides was significantly higher than that of bare TiO2 and varied in a manner which depended strongly on the nature of the MxOy modifier. The addition of metal oxides on the TiO2 surface resulted in a significant improvement of catalytic performance induced by a synergetic interaction between MxOy and TiO2 support. Propane conversion and propylene yield were strongly influenced by the nature of the metal oxide additive and were found to be superior for the Cr2O3-TiO2 and Ga2O3-TiO2 catalysts characterized by moderate basicity. The reducibility of the latter catalysts was significantly increased, contributing to the improved catalytic performance. This was also the case for the surface acidity of Ga2O3-TiO2 which was found to be higher compared with Cr2O3-TiO2 and TiO2. A general trend was observed whereby catalytic performance increased significantly with decreasing the primary crystallite size of TiO2. DRIFTS studies conducted under reaction conditions showed that the adsorption/activation of CO2 was favored on the surface of composite metal oxides. This may be induced by the improved surface basicity observed with the MxOy addition on the TiO2 surface. The Ga2O3 containing sample exhibited sufficient stability for about 30 h on stream, indicating that it is suitable for the production of propylene through ODP with CO2 reaction.

This study involves environmentally friendly synthesis of copper nanoparticles in aqueous medium without inert gas protection, using ranolazine as a capping material. UV-Visible (UV-Vis) spectrometry showed that ranolazine-derived copper nanoparticles (Rano-Cu NPs) demonstrate a localized surface plasmon resonance (LSPR) band at 573 nm with brick-red color under optimized parameters, including pH, reaction time, and concentrations of copper salt, hydrazine hydrate, and ranolazine. The coating of ranolazine on the surface of Cu NPs was studied via Fourier transform infrared (FTIR) spectroscopy. Scanning electron microscopy (SEM) revealed that Rano-Cu NPs consist of spherical particles. X-ray diffraction (XRD) verified that Rano-Cu NPs are crystalline in nature. Atomic force microscopy (AFM) showed that the average size of Rano-Cu NPs was 40 ± 2 nm in the range of 22⁻95 nm. Rano-Cu NPs proved to be highly sensitive as a selective colorimetric sensor for As3+ via color change from brick red to dark green, in the linear range of 3.0 × 10-7 to 8.3 × 10-6 M, with an R² value of 0.9979. The developed sensor is simple, cost effective, highly sensitive, and extremely selective for As3+ detection, showing a low detection limit (LDL) of 1.6 × 10-8 M. The developed sensor was effectively tested for detection of As3+ in some water samples.

Copper nanoparticles (CuNPs) stabilized by quaternary ammonium salts are well known as antimicrobial agents. The aim of this work was to study the feasibility of the inclusion of CuNPs in nanovesicular systems. Liposomes are nanovesicles (NVs) made with phospholipids and are traditionally used as delivery vehicles because phospholipids favor cellular uptake. Their capacity for hydrophilic/hydrophobic balance and carrier capacity could be advantageous to prepare novel hybrid nanostructures based on metal NPs (Me-NPs). In this work, NVs were loaded with CuNPs, which have been reported to have a biofilm inhibition effect. These hybrid materials could improve the effect of conventional antibacterial agents. CuNPs were electro-synthesized by the sacrificial anode electrolysis technique in organic media and characterized in terms of morphology through transmission electron microscopy (TEM). The NVs were prepared by the thin film hydration method in aqueous media, using phosphatidylcholine (PC) and cholesterol as a membrane stabilizer. The nanohybrid systems were purified to remove non-encapsulated NPs. The size distribution, morphology and stability of the NV systems were studied. Different quaternary ammonium salts in vesicular systems made of PC were tested as stabilizing surfactants for the synthesis and inclusion of CuNPs. The entrapment of charged metal NPs was demonstrated. NPs attached preferably to the membrane, probably due to the attraction of their hydrophobic shell to the phospholipid bilayers. The high affinity between benzyl-dimethyl-hexadecyl-ammonium chloride (BDHAC) and PC allowed us to obtain stable hybrid NVs c.a. 700 nm in diameter. The stability of liposomes increased with NP loading, suggesting a charge-stabilization effect in a novel antibiofilm nanohybrid material.

Aiming to improve the treatment outcomes of current daily tuberculosis (TB) chemotherapy over several months, we investigated whether nanoencapsulation of existing drugs would allow decreasing the treatment frequency to weekly, thereby ultimately improving patient compliance. Nanoencapsulation of three first-line anti-TB drugs was achieved by a unique, scalable spray-drying technology forming free-flowing powders in the nanometer range with encapsulation efficiencies of 82, 75, and 62% respectively for rifampicin, pyrazinamide, and isoniazid. In a pre-clinical study on TB infected mice, we demonstrate that the encapsulated drugs, administered once weekly for nine weeks, showed comparable efficacy to daily treatment with free drugs over the same experimental period. Both treatment approaches had equivalent outcomes for resolution of inflammation associated with the infection of lungs and spleens. These results demonstrate how scalable technology could be used to manufacture nanoencapsulated drugs. The formulations may be used to reduce the oral dose frequency from daily to once weekly in order to treat uncomplicated TB.

In the present study, Ni/Ce-Sm-xCu (x = 5, 7, 10 at.%) catalysts were prepared using microwave radiation coupled with sol-gel and followed by wetness impregnation method for the Ni incorporation. Highly dispersed nanocrystallites of CuO and NiO on the Ce-Sm-Cu support were found. Increase of Cu content seems to facilitate the reducibility of the catalyst according to the H₂ temperature-programmed reduction (H₂-TPR). All the catalysts had a variety of weak, medium and strong acid/basic sites that regulate the reaction products. All the catalysts had very high XC3H8O3 for the entire temperature (400⁻750 °C) range; from ≈84% at 400 °C to ≈94% at 750 °C. Ni/Ce-Sm-10Cu catalyst showed the lowest XC3H8O3-gas implying the Cu content has a detrimental effect on performance, especially between 450⁻650 °C. In terms of H₂ selectivity (SH2) and H₂ yield (YH2), both appeared to vary in the following order: Ni/Ce-Sm-10Cu > Ni/Ce-Sm-7Cu > Ni/Ce-Sm-5Cu, demonstrating the high impact of Cu content. Following stability tests, all the catalysts accumulated high amounts of carbon, following the order Ni/Ce-Sm-5Cu < Ni/Ce-Sm-7Cu < Ni/Ce-Sm-10Cu (52, 65 and 79 wt.%, respectively) based on the thermogravimetric analysis (TGA) studies. Raman studies showed that the incorporation of Cu in the support matrix controls the extent of carbon graphitization deposited during the reaction at hand.

This paper presents an experimental study about the preparation, by electrospinning, of uranium carbide fibers with nanometric grain size. Viscous solutions of cellulose acetate and uranyl salts (acetate, acetylacetonate, and formate) on acetic acid and 2,4-pentanedione, adjusted to three different polymer concentrations, 10, 12.5, and 15 weight %, were used for electrospinning. Good quality precursor fibers were obtained from solutions with a 15% cellulose acetate concentration, the best ones being produced from the uranyl acetate solution. As-spun precursor fibers were then decomposed by slow heating until 823 K under argon, resulting in a mixture of nano-grained UO2 and C fibers. A last carboreduction was then carried out under vacuum at 2073 K for 2 h. The final material displayed UC2-y as the major phase, with grain sizes in the 4 nm-10 nm range. UO2+x was still present in moderate concentrations (~30 vol.%). This is due to uncomplete carboreduction that can be explained by the fiber morphology, limiting the effective contact between C and UO2 grains.