Biocompatible NaYF4:Yb,Er upconversion nanoparticles: Colloidal stability and optical properties

Currently, highly luminescent colloidal upconversion nanoparticles (UCNPs) have expanded an increasing interest of researchers because of their facilitating lability in the biomedical/clinical field. In this study, NaYF₄:Yb,Er UCNPs are prepared by eco-friendly metal complexation-based thermal decomposition method at a lower temperature in aqueous media. The phase structure, crystallinity, phase purity, morphology, colloidal dispersibility, surface structure, surface charge, and optical and luminescent properties were evaluated carefully by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive x-ray analysis (EDX), Thermogravimetric analysis (TGA), zeta potential, Fourier transform infrared (FTIR), UV/visible and photoluminescent spectroscopic techniques. XRD pattern shows a pure single-phase cubic structure with an average grain size of 30–35 nm. TEM and SEM micrographs exhibited irregularly shaped spherical morphologies, porous surface structures highly aggregated UCNPs with the narrow-size distribution. Positive zeta potential has shown value signifying high absorption in the visible region which indicates particle's good colloidal stability in aqueous media. Under NIR-laser light excitation, the UCNPs emit strong UC emission transitions in the visible region. A broad infrared absorption peak of hydroxyl groups (–OH) in FTIR spectrum and mass loss at a lower temperature in TGA verified the surface functionality of UCNPs, with high colloidal stability, and excellent biocompatibility in aqueous media. In terms of their surface characteristics and high luminescent properties, the NaYF₄:Yb,Er UCNPs could be interestingly applied in tagging of biomolecules, drug delivery, proteins labeling, and therapeutic and thermostats applications.     

多壁碳纳米管的纯化及其表面含氧基团的表征

用兼具酸性和氧化性的HNO3水溶液可方便地除去残留在原生态多壁碳纳米管(CNT)上的Ni-MgO催化剂组分,同时在其表面产生某些含氧官能团,使原生态多壁碳纳米管的疏水性表面变为亲水性表面.采用Boehm中和滴定法以及X射线衍射(XRD)、热脱附谱(TPD)、傅里叶变换红外(FTIR)光谱和X射线光电子能谱(XPS)等技术对HNO3处理过的多壁碳纳米管的相组成和表面含氧官能团进行测量和表征.结果表明:所生成表面含氧官能团的总量以经7.0mol·L-1硝酸378K处理24h的CNT为最高;3种主要表面含氧官能团的含量高低顺序为,羧基内酯型羧基酚型羟基.     

Thermal and spectroscopic characterization of nanostructured zirconia–scandia–dysprosia

Zirconia containing 10 mol% scandia and x mol% dysprosia (0 ≤ x ≤ 1.5) gels was synthesized by simultaneous precipitation at room temperature. The aim of this work is to verify the effect of dysprosium on the cubic phase stabilization of the zirconia–scandia solid electrolyte. The gel was characterized by thermogravimetry, differential scanning calorimetry, and differential thermal analyses. The thermally treated powders were analyzed by Fourier transform infrared spectroscopy, thermal analyses, and X-ray diffraction techniques. For comparison purpose, a commercial zirconia–10 mol% scandia powder was subjected to some characterization techniques. The infrared spectrum shows characteristic absorption bands due to residual material from the synthesis on the surface of the powder particles. Nanostructured powders were obtained after thermal treatments at 500 °C for 2 h. Infrared spectroscopy and X-ray diffraction results evidence the stabilization of the cubic phase in zirconia–scandia containing dysprosium. The thermal stability of the cubic phase during thermal cycling was ascertained by thermal analysis.     

Control of sp2/sp3 carbon ratio and surface chemistry of nanodiamond powders by selective oxidation in air

The presence of large amounts of nondiamond carbon in detonation-synthesized nanodiamond (ND) severely limits applications of this exciting nanomaterial. We report on a simple and environmentally friendly route involving oxidation in air to selectively remove sp(2)-bonded carbon from ND. Thermogravimetric analysis and in situ Raman spectroscopy shows that sp(2) and sp(3) carbon species oxidize with different rates at 375-450 degrees C and reveals a narrow temperature range of 400-430 degrees C in which the oxidation of sp(2)-bonded carbon occurs with no or minimal loss of diamond. X-ray absorption near-edge structure spectroscopy detects an increase of up to 2 orders of magnitude in the sp(3)/sp(2) ratio after oxidation. The content of up to 96% of sp(3)-bonded carbon in the oxidized samples is comparable to that found in microcrystalline diamond and is unprecedented for ND powders. Transmission electron microscopy and Fourier transform infrared spectroscopy studies show high purity 5-nm ND particles covered by oxygen-containing surface functional groups. The surface functionalization can be controlled by subsequent treatments (e.g., hydrogenization). In contrast to current purification techniques, the air oxidation process does not require the use of toxic or aggressive chemicals, catalysts, or inhibitors and opens avenues for numerous new applications of nanodiamond.     

Green synthesis of platinum nanoparticles using Atriplex halimus leaves for potential antimicrobial,antioxidant, and catalytic applications

Herein, green platinum nanoparticles (PtNPs) were synthesized using an aqueous extract of Atriplex halimus leaves as a reductant. Atriplex platinum nanoparticles (At-PtNPs) were stable for up to three months. At-PtNPs were characterized by several techniques including UV–Visible spectroscopy, Fourier Transform Infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), Energy Dispersive X-ray spectroscopy (EDX), EDX elemental mapping, High-resolution Transmission electron microscope (HRTEM), Selected Area Electron Diffraction (SAED), and X-ray Photoelectron Spectroscopy (XPS) and Zeta measurements. At-PtNPs were black-colored and mainly spherical with a plasmon peak at 295 nm with ultra-small particle size (1–3 nm) and high surface charge (?25.4 mV). At-PtNPs were verified as a superb catalyst as they were able to catalytically degrade MB dye. At-PtNPs exhibited a high antibacterial efficiency against gram-negative bacteria. At-PtNPs were proved as a highly efficient antioxidant agent. Thus, the attained results offer a promising route of the green synthesis of PtNPs using the aqueous extract of Atriplex halimus.     

Simple and low-temperature synthesis of NiO nanoparticles through solid-state thermal decomposition of the hexa(ammine)Ni(II) nitrate, [Ni(NH3)6](NO3)2, complex

NiO nanoparticles with an average size of about 12 nm were easily prepared via the thermal decomposition of hexa(ammine)Ni(II) nitrate complex, [Ni(NH₃)₆](NO₃)₂, at low temperature of 250 °C. The product was characterized by thermal analysis (TGA/DTA), X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR), UV-Vis spectroscopy, BET specific surface area measurement, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), and magnetic measurement. The magnetic measurement revealed a small hysteresis loop at room temperature, confirming a superparamagnetic (weak ferromagnetic) nature of the synthesized NiO nanoparticles. Indeed, the NiO nanoparticles prepared by this method could be an appropriate semiconductor material due to the optical band gap of 3.35 eV which shows a red shift in comparison with the previous reports. This method is simple, fast, safe, low-cost and also suitable for industrial production of high purity NiO nanoparticles for applied purposes.     

Effect of nitrogen-containing groups on enhanced capacitive behaviors of multi-walled carbon nanotubes

In this work, electrochemical properties of surface treated multi-walled carbon nanotubes (MWNTs) are studied in supercapacitors. Nitrogen and oxygen functional groups containing MWNTs are prepared by urea and acidic treatments, respectively. The surface properties of the MWNTs are confirmed by X-ray photoelectron spectroscopy (XPS) and zeta-potential measurements. The textural properties are characterized by N₂ adsorption/desorption isotherm at 77 K using the BET eqaution, BJH method, and HK method. The electrochemical properties of the MWNTs are accumulated by cyclic voltammetry, impedance spectra, and charge-discharge cycling performance in 1 M H₂SO₄ at room temperature. As a result, the functionalized MWNTs lead to an increase in capacitance as compared with pristine MWNTs. It suggests that the pyridinic and pyridinic-N-oxides nitrogen species have effects on the specific capacitance due to the positive charge, and thus an improved electron transfer at high current loads results, the most important functional groups affecting capacitive behaviors.     

Preparation and characterization of NiO nanoparticles from thermal decomposition of the [Ni(en)3](NO3)2 complex: A facile and low-temperature route

NiO nanoparticles with an average size of 15 nm were easily prepared via the thermal decomposition of the tris(ethylenediamine)Ni(II) nitrate complex [Ni(en)₃](NO₃)₂ as a new precursor at low temperature, and the nanoparticles were characterized by thermal analysis (TGA/DTA), X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR), UV-Vis spectroscopy, BET specific surface area measurement, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM) and magnetic measurements. The magnetic measurements confirm that the product shows a ferromagnetic behavior at room temperature, which may be ascribed to a size confinement effect. The NiO nanoparticles prepared by this method could be an appropriate photocatalytic material due to a strong absorption band at 325 nm. This method is simple, fast, safe, low-cost and also suitable for industrial production of high purity NiO nanoparticles for applied purposes.     

−22-Fold of 1H signal enhancement in-situ low-field liquid NMR using nanodiamond as polarizer of overhauser dynamic nuclear polarization

Nanodiamond (ND) polarizer can be used for dynamic nuclear polarization (DNP), owing to unpaired electrons provided by surface defects. However, ¹H enhancement via Overhauser DNP (ODNP) using ND in-situ liquid has been found much smaller than traditional radicals. Herein, we study the surface properties of ND using electron spin resonance (ESR) and Raman methods firstly. Then the enhancement of ¹H ODNP is explored using ND as polarizer with different nanoparticle sizes and concentrations at home-built 0.06 T DNP spectrometer. The surface of ND with the size of 30 nm is further modification via high temperature air oxidized and the enhancement was measured. The results show that nanoparticle sizes and Raman peak intensity ratio of sp²/sp³ hybridization are approximate negative correlation and positive correlation to enhancement, respectively. Furthermore, there is no significant enhancement in the oxidation group, and a −22.5-fold ¹H ODNP enhancement is achieved in-situ liquid at room temperature, which demonstrate the ND can be used as an efficient enhancer. We expect ND to play a greater role in biomedical research, especially for multimodal imaging with improving the performance of ND surface.     

Surface modification of carbon black by thiol-ene click reaction for improving dispersibility in aqueous phase

Carbon black (CB) particles were firstly encapsulated by γ-Methacryloxypropyltrimethoxysilane (MEMO) using a sol-gel method and then grafted with sodium 3-Mercapto-1-propanesulfonate (MPS) via thiol-ene click reaction. Morphology characterization reveals that modified CB particles have a core-shell structure. Element composition and chemical status derived from X-ray photoelectron spectroscopy (XPS) results prove the grafting of MPS molecules. Moreover, the crystal structure and thermal behavior of modified CB particles were characterized by Raman spectra and Thermogravimetric analysis (TGA) curves, respectively. The modified CB particles exhibit excellent self-dispersing ability in aqueous media and the dispersion has high thermal and centrifugal stability. This research provides a new insight into the preparation of inkjet printing ink with excellent stability.     

Synthesis and characterization of sulfonated single-walled carbon nanotubes and their performance as solid acid catalyst

Single-walled carbon nanotubes (SWCNTs) were treated with sulfuric acid at 300 °C to synthesize sulfonated SWCNTs (s-SWCNTs), which were characterized by electron microscopy, infrared, Raman and X-ray photoelectron spectroscopy, and thermo analysis. Compared with activated carbon, more sulfonic acid groups can be introduced onto the surfaces of SWCNTs. The high degree (∼20 wt%) of surface sulfonation led to hydrophilic sidewalls that allows the SWCNTs to be uniformly dispersed in water and organic solvents. The high surface acidity of s-SWCNTs was demonstrated by NH₃ temperature-programmed desorption technique and tested by an acetic acid esterification reaction catalyzed by s-SWCNTs. The results show that the water-dispersive s-SWCNTs are an excellent solid acid catalyst and demonstrate the potential of SWCNTs in catalysis applications.     

Green synthesis of silver nanoparticles using olive leaf extract and its antibacterial activity

The silver nanoparticles (AgNPs) synthesized using hot water olive leaf extracts (OLE) as reducing and stabilizing agent are reported and evaluated for antibacterial activity against drug resistant bacterial isolates. The effect of extract concentration, contact time, pH and temperature on the reaction rate and the shape of the Ag nanoparticles are investigated. The data revealed that the rate of formation of the nanosilver increased significantly in the basic medium with increasing temperature. The nature of AgNPs synthesized was analyzed by UV–vis spectroscopy, X-ray diffraction, scanning electron microscopy and thermal gravimetric analysis (TGA). The silver nanoparticles were with an average size of 20–25 nm and mostly spherical. The antibacterial potential of synthesized AgNPs was compared with that of aqueous OLE by well diffusion method. The AgNPs at 0.03–0.07 mg/ml concentration significantly inhibited bacterial growth against multi drug resistant Staphylococcus aureus (S. aureus), Pseudomonas aeruginosa (P. aeruginosa) and Escherichia coli (E. coli). This study revealed that the aqueous olive leaf extract has no effect at the concentrations used for preparation of the Ag nanoparticles. Thus AgNPs showed broad spectrum antibacterial activity at lower concentration and may be a good alternative therapeutic approach in future.     

Microporous membranes obtained from polypropylene blend films by stretching

Blends of two linear polypropylenes (PP, having different molecular weights) were prepared to develop microporous membranes through melt extrusion followed by stretching. The role of high molecular weight chains on the row-nucleated lamellar crystallization was investigated. The orientation of crystalline and amorphous phases was measured by wide angle X-ray diffraction (WAXD) and Fourier transform infrared (FTIR). Long period spacing was obtained using small angle X-ray scattering (SAXS). The effects of annealing temperature and applied elongation during annealing on the crystallinity of the films were studied using differential scanning calorimetry (DSC). It was found that annealing at 140 °C contributed significantly to the perfection of the crystalline phase. Scanning electron microscopy (SEM) images of the membrane surface showed more pore density and uniform pore size as the amount of high molecular weight component increased. The addition of the high M_w PP improved the water vapor transmission rate (WVTR) of the membranes, indicating increased interconnectivity of the pores, which was also confirmed from cross-section SEM micrographs of the membranes. The surface area and pore dimensions of the microporous membranes were measured using the BET nitrogen absorption technique and mercury porosimetry, respectively. The influences of temperature and amount of stretching during cold and hot stretching on WVTR were also explored. Tensile properties in the machine and transverse directions (MD and TD, respectively) as well as puncture resistance in the normal direction (ND) were evaluated. As the high M_w PP was added, a slight reduction in the mechanical properties along MD and TD and no changes in ND were observed.     

Designing of luminescent GdPO4:Eu@LaPO4@SiO2 core/shell nanorods: Synthesis,structural and luminescence properties

GdPO₄:Eu³⁺ (core) and GdPO₄:Eu@LaPO₄ (core/shell) nanorods (NRs) were successfully prepared by urea based co-precipitation process at ambient conditions which was followed by coating with amorphous silica shell via the sol-gel chemical route. The role of surface coating on the crystal structure, crystallinity, morphology, solubility, surface chemistry and luminescence properties were well investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, Fourier Transform Infrared (FTIR), UV-Vis, and photoluminescence spectroscopy. XRD pattern revealed highly purified, well-crystalline, single phase-hexagonal-rhabdophane structure of GdPO₄ crystal. The TEM micrographs exhibited highly crystalline and narrow size distributed rod-shaped GdPO₄:Eu³⁺ nanostructures with average width 14–16 nm and typical length 190–220 nm. FTIR spectra revealed characteristic infrared absorption bands of amorphous silica. High absorbance in a visible region of silica modified core/shell/Si NRs in aqueous environment suggests the high solubility along with colloidal stability. The photoluminescence properties were remarkably enhanced after growth of undoped LaPO₄ layers due to the reduction of nonradiative transition rate. The advantages of presented high emission intensity and high solubility of core/shell and core/shell/Si NRs indicated the potential applications in monitoring biological events.     

Influences of temperature and atmosphere on thermal stability of BaCrO4

In this article, the influences of temperature and atmosphere on thermal stability of BaCrO₄ were investigated. BaCrO₄ powders with an orthorhombic structure were synthesized by a facile aqueous solution route. The synthesized BaCrO₄ products were then heat treated at different atmospheres to evaluate their thermal stability by differential thermal analysis–thermogravimetry (DTA–TG), X-ray photoelectron spectroscopy and X-ray diffraction. BaCrO₄ has a good thermal stability and does not decompose in air up to 1,400 °C. However, the decomposition of BaCrO₄ in vacuum depends mainly upon a two-stage chemical reaction. BaCrO₄ is finally decomposed into BaCr₂O₄ with trivalent Cr³⁺ cations and Ba₃(Cr⁶⁺ Cr⁵⁺)₂O_9?x with both pentavalent Cr⁵⁺ and hexavalent Cr⁶⁺ cations after heat treatments in vacuum.     

Microstructures and photocatalytic properties of Ag and La surface codoped TiO2 films prepared by sol–gel method

Ag⁺ and La³⁺ surface codoped TiO₂ films were successfully prepared by the improved sol–gel and doping processes. The as-prepared specimens were characterized using differential thermal analysis-thermogravimetry (DTA–TG), X-ray diffraction (XRD), high-resolution field emission scanning electron microscopy (FE-SEM), X-ray energy dispersive spectroscopy (EDS), Brunauer–Emmett–Teller (BET) surface area, Photoluminescence spectrum (PL) and UV–vis diffuse reflectance spectroscopy. The photocatalytic activities of the films were evaluated by degradation of an organic dye in aqueous solution. The results of XRD, FE-SEM and BET analyses indicated that the TiO₂ films were composed of nano-particles or aggregates with a size of less than 10 nm. With the codoping of Ag⁺ and La³⁺, TiO₂ films with high photocatalytic activity and clearly responsive to the visible light were obtained. The improvement mechanism by ions doping was also discussed.     

Removal of heavy metals and bacteria from aqueous solution by novel hydroxyapatite/zeolite nanocomposite,preparation, and characterization

In this study, a HAp/NaP nanocomposite was prepared by adding a synthesized nano-hydroxyapatite to zeolite NaP gel in the hydrothermal condition and used for the removal of lead(II) and cadmium(II) ions from aqueous solution. HAp/zeolite nanocomposite was then characterized by Fourier transform infrared spectroscopy, X-ray diffraction and Rietveld method, scanning electron microscope, energy-dispersive X-ray analysis, and surface area and thermal analyses. Results suggested that the nanocomposite crystals of HAp were dispersed onto the zeolite external surface and/or encapsulated within the zeolite channels and pores. The potential of the composite in adsorption of heavy metals was investigated by using batch experiment. The metal concentration in the equilibrium C _e (mg/g) after adsorption with nanocomposite of HAp/NaP was analyzed using flame atomic adsorption spectrometry. The adsorption experiments were carried out at pH of 3–9. The influences of contact time, initial concentration, dose, and temperature on the adsorption of lead and cadmium ions were also studied. Results show that these nanocomposites have further adsorption related to NaP and HAp. They have great potential (about 95 %) for Pb(II) and Cd(II) adsorption at room temperature. The equilibrium process was described by Frendlich, Langmuir, Temkin, and Dubinin–Radushkevich (D-R) models. The kinetics data were successfully fitted by a pseudo-second-order model. The in vitro antibacterial activity of these composites was evaluated against Bacillus subtilis (as Gram-positive bacteria) and Pseudomonas aeruginosa (as Gram-negative bacteria) and compared with standard drugs that show inhibition on bacterial growth.     

Saccharide‐Modified Nanodiamond Conjugates for the Efficient Detection and Removal of Pathogenic Bacteria

The detection and removal of bacteria, such as E. coli in aqueous environments by using safe and readily available means is of high importance. Here we report on the synthesis of nanodiamonds (ND) covalently modified with specific carbohydrates (glyco–ND) for the precipitation of type 1 fimbriated uropathogenic E. coli in solution by mechanically stable agglutination. The surface of the diamond nanoparticles was modified by using a Diels–Alder reaction followed by the covalent grafting of the respective glycosides. The resulting glyco–ND samples are fully dispersible in aqueous media and show a surface loading of typically 0.1 mmol g^?1. To probe the adhesive properties of various ND samples we have developed a new sandwich assay employing layers of two bacterial strains in an array format. Agglutination experiments in solution were used to distinguish unspecific interactions of glyco–ND with bacteria from specific ones. Two types of precipitates in solution were observed and characterized in detail by light and electron microscopy. Only by specific interactions mechanically stable agglutinates were formed. Bacteria could be removed from water by filtration of these stable agglutinates through 10 μm pore‐size filters and the ND conjugate could eventually be recovered by addition of the appropriate carbohydrate. The application of glycosylated ND allows versatile and facile detection of bacteria and their efficient removal by using an environmentally and biomedically benign material.     

Synthesis and characterization of surface modified SBA-15 silica materials and their application in chromatography

Hexagonally ordered SBA-15 mesoporous silica spheres with large uniform pore diameters are obtained using the triblock copolymer, Pluronic P123, as template with a cosurfactant cetyltrimethylammonium bromide (CTAB) and the cosolvent ethanol in acidic media. A series of surface modified SBA-15 silica materials is prepared in the present work using mono- and trifunctional alkyl chains of various lengths which improves the hydrothermal and mechanical stability. Several techniques, such as element analysis, nitrogen sorption analysis, small angle X-ray diffraction, scanning electron microscopy (SEM), FTIR, solid-state (29)Si and (13)C NMR spectroscopy are employed to characterize the SBA-15 materials before and after surface modification with the organic components. Nitrogen sorption analysis is performed to calculate specific surface area, pore volume and pore size distribution. By surface modification with organic groups, the mesoporous SBA-15 silica spheres are potential materials for stationary phases in HPLC separation of small aromatic molecules and biomolecules. The HPLC performance of the present SBA-15 samples is therefore tested by means of a suitable test mixture.     

A simple selenium source to synthesize CdSe via the two-phase thermal approach

A novel selenium source was developed to synthesize the size-controlled CdSe nanocrystals with relatively narrow size distribution successfully in a two-phase thermal approach. A highly reactive and aqueous soluble selenium source was provided by the reduction of selenite, and in this route the size of the nanocrystals can be adjusted by the reaction temperature and time. The size, crystalline structure and optical characteristics of these nanocrystals were investigated by transmission electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, UV–vis spectroscopy, and photoluminescence spectroscopy. The influence factors for this approach were also discussed.