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.     

Cellulose-TiO2 nanocomposite with enhanced UV–Vis light absorption

TiO₂/N-cellulose nanocomposite was successfully prepared in the (cyclohexyl)hexyl-dimethylammonium acetate–dimethyl sulfoxide solution. The obtained composite was characterized with various techniques like UV–Vis/DR, FTIR/DRS, X-ray diffraction, thermogravimetric analysis, DLS method and BET SSA measurements. TiO₂/N-cellulose nanocomposite exhibited high UV–Vis light absorption with energy gap shifted to the visible region. Additive of TiO₂/N photocatalyst to cellulose-IL-DMSO solution leads to obtaining the material with higher thermostability and limited photoactivity.     

Facile and green solvothermal synthesis of palladium nanoparticle-nanodiamond-graphene oxide material with improved bifunctional catalytic properties

We developed a selective solvothermal synthesis of palladium nanoparticles on nanodiamond (ND)–graphene oxide (GO) hybrid material in solution. After the GO and ND materials have been added in PdCl₂ solution, the spontaneous redox reaction between the ND–GO and PdCl₂ led to the creation of nanohybrid Pd@ND@GO material. The resulting Pd@ND@GO material was characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared (FTIR) spectrometry, scanning electronic microscopy (SEM), and atomic absorption spectrometry methods. The Pd@ND@GO material has been used for the first time as a catalyst for the reduction for 2-nitrophenol and the degradation of methylene blue in the presence of NaBH₄. GO plays the role of 2D support material for Pd nanoparticles, while NDs act as a nanospacer for partly preventing the re-stacking of the GO. The Pd@ND@GO material can lead to high catalytic activity for the reduction reaction of 2-nitrophenol and degradation of methylene blue with 100% conversion within ~15 s for these two reactions even when the content of Pd in it is as low as 4.6 wt%.     

Preparation of nano-dispersed lithium niobate by mechanochemical route

Interaction in the system of lithium carbonate–niobium pentoxide during mechanochemical treatment in air and water has been studied. Prepared samples have been investigated with the help of DTA–TG, XRD, FTIR, Raman, and UV–Vis spectroscopy, adsorption–desorption of nitrogen and TEM. Activation of reagents and direct mechanochemical synthesis are observed at 600–850 and 1,000 rpm, respectively. Lithium metaniobate samples prepared via milling possess high dispersity, defective structure, and improved photocatalytic activity, including under visible illumination.     

Synthesis of Poly(silyne-co-hydridocarbyne) for Silicon Carbide Production

Pre-ceramic polymers have previously been shown to be polymeric precursors to silicon carbide, diamond and diamond-like carbon. Here, we report the synthesis of a pre-ceramic polymer, poly(silyne-co-hydridocarbyne), which was electrochemically synthesized from one monomer containing both silicon and carbon in its structure. The polymer is soluble in common solvents such as CHCl₃, CH₂Cl₂ and THF. Since the polymer contains both silyne and carbyne on its backbone, it can be easily converted to silicon carbide upon heating under an ambient inert atmosphere, or to SiO₂ under ambient air atmosphere. Poly(silyne-co-hydridocarbyne) was characterized with UV/Vis spectroscopy, FTIR, ¹H-NMR, GPC and Raman spectroscopy. Conversion of the polymer to SiC ceramic was accomplished by heating at 1000 and 750°C under an argon atmosphere and characterized with optical microscopy, SEM, X-Ray and Raman spectroscopies.     

无皂乳液聚合制备光敏聚合物微球及其光响应性

利用红外光谱(IR)和核磁共振(1H NMR)对所制备的光敏可聚合单体重氮萘醌苯磺酸甲基丙烯酸羟乙酯(DNQMA)进行了表征. 采用无皂乳液聚合方法制备DNQMA与甲基丙烯酸叔丁酯(t-BMA)的共聚合光敏微球. 利用紫外光谱(UV/Vis)、动态光散射(DLS)、扫描电镜(SEM)对光敏微球在光照前后形态的变化进行了表征. DLS的研究结果表明在水分散液中, 光敏微球的尺寸随光照时间的增加, 先增大, 然后达到平衡. 这与紫外光谱中DNQMA特征吸收达到饱和的时间相一致. SEM研究结果表明光敏微球的形态在光照后破坏很严重, 并基本解体.     

In Situ Direct Measurement of Vapor Pressures and Thermodynamic Parameters of Volatile Organic Materials in the Vapor Phase: Benzoic Acid,Ferrocene, and Naphthalene

We report the direct determination of vapor pressures and optical and thermodynamic parameters of powders of low‐volatile materials in their vapor phase using a commercial UV/Vis spectrometer. This methodology is based on the linear proportionality between the density of the saturated gas of the material and the absorbance of the gas at different temperatures. The vapor pressure values determined for benzoic acid and ferrocene are in good agreement with those reported in the literature with ～2–7 % uncertainty. Thermodynamic parameters of benzoic acid, ferrocene, and naphthalene are determined in situ at temperatures below their melting points. The sublimation enthalpies of the investigated organic molecules are in excellent agreement with the ICTAC recommended values (less than 1 % difference). This method has been used to measure vapor pressures and thermodynamic parameters of organic volatile materials with vapor pressures of ～0.5–355 Pa in the 50–100 °C temperature range.     

Catalytic Reduction of p‐Nitrophenol and Hexacyanoferrate (III) by Borohydride Using Green Synthesized Gold Nanoparticles

A simple and green approach for the synthesis of well‐stabilized gold nanoparticles (AuNPs) using gum Acacia (GA) is presented here. The gum acacia acts as the reductant and stabilizer. The synthesized gold nanoparticles were characterized by using ultraviolet visible (UV‐Vis), fourier transform infrared spectroscopy (FTIR), x‐ray diffraction (XRD), dynamic light scattering (DLS) and transmission electron microscopy (TEM) techniques. The UV‐Vis study revealed a distinct surface plasmon resonance at 520 – 550 nm, due to the formation of AuNPs. FTIR analysis showed the evidence that –OH groups present in the gum matrix were responsible in reducing the tetra chloroauric acid into AuNPs. XRD studies confirmed the formation of well crystalline nanoparticles with fcc structure and the particle size ranges from 4 – 29 nm, as indicated by TEM analysis. The synthesized gold nanoparticles exhibited homogeneous catalytic activity. The two model reactions studied were the reduction of p‐nitro phenol and the reduction of hexacyanoferrate (III) by borohydride ions. Both the reactions were monitored by UV‐Vis spectroscopy. The kinetic investigations were carried out for the AuNPs‐catalyzed reactions at different temperatures and different amount of catalyst.     

The Preparation and Properties of Polyurethane/Nano-CeO<Subscript>2</Subscript> Hybrid Aqueous Coating

To improve the ultraviolet resistance and thermal stability of waterborne polyurethane, stable waterborne polyurethane/nano-cerium oxide hybrid dispersions were obtained by adding nano-cerium colloids to previously synthesized waterborne polyurethane dispersions. The dried ceria colloid was characterized by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). The XRD results indicated the prepared CeO₂ was a face-centered cubic structure. The prepared polyurethane/CeO₂ dispersions were studied by dynamic light scattering (DLS), transmission electron microscopy (TEM), UV–Vis spectroscopy and accelerated weathering test. The dried polyurethane/CeO₂ films were characterized using thermogravimetric analysis (TGA). The DLS analysis indicated the particles average diameter of hybrids emulsion was bigger than that of the pure waterborne polyurethane dispersion. TG analysis and accelerated weathering test suggested the hybrid latex films had better thermal stability and mechanical properties than those of the pure waterborne polyurethane. The UV–Vis absorption capacity of the dispersions prepared was increasing with the amount of CeO₂ colloid increased.     

Growth, spectral, and thermal characterization of 2-hydroxy-3-methoxybenzaldehyde semicarbazone

2-Hydroxy-3-methoxybenzaldehyde semicarbazone (HMBS) has been synthesized from 2-hydroxy-3-methoxybenzaldehyde and semicarbazide hydrochloride using sodium acetate as catalyst. Good quality single crystals of HMBS were successfully grown by slow evaporation method at room temperature using a mixture of DMF and ethanol as solvent. Fourier transform infrared and Fourier transform Raman spectral studies have been performed to identify the functional groups. Single-crystal XRD study was conducted to obtain the crystal structure and lattice parameters. The grown crystal was subjected to ¹H- and ¹³C-NMR spectral studies in order to confirm its structure and purity. The compound crystallizes into a monoclinic P21/c space group. Intermolecular hydrogen-bonding interactions facilitate unit cell packing in the crystal lattice. The UV–Vis spectrum confirmed the transparency of the compound between the wavelengths 420 and 1,100 nm, which is a characteristic property of a nonlinear optical (NLO) material. The thermal decomposition of the compound under static air atmosphere was investigated by simultaneous TG–DTG at a heating rate of 10 °C min^?1. The NLO property of HMBS was confirmed from the second-harmonic generation by Kurtz–Perry powder test.     

Interaction of naproxen with β-cyclodextrin and its derivatives/polymer: experimental and molecular modeling studies

The interaction of naproxen with β-cyclodextrin and its derivatives (hosts) as well as polymer has been studied using UV Visible (UV–Vis), Fourier Transform Infrared (FTIR), Nuclear Magnetic Resonance (NMR) spectroscopy and Scanning electron microscopy (SEM). In this paper, the solid inclusion complexes were prepared by freeze drying method. The formation constants of the complexes were determined by UV–Vis method. The adsorption properties of naproxen with β-Cyclodextrin bonded silica stationary phase (CDS) were studied for an in-depth understanding of the host–guest interaction. The inclusion process involving naproxen and hosts was investigated by using the PM3 quantum–mechanical semiempirical method. The stabilization energy values obtained from the semiempirical calculation showed the same relation with the formation constant values determined by UV–Vis spectroscopy.     

The Antimicrobial Activities of Silver Nanoparticles from Aqueous Extract of Grape Seeds against Pathogenic Bacteria and Fungi

Grape seed extract (GSE) is a natural source of polyphenolic compounds and secondary metabolites, which have been tested for their possible antimicrobial activities. In the current study, we tested the antibacterial and antifungal activities of aqueous GSE and the biosynthesized silver nanoparticles loaded with GSE (GSE-AgNPs) against different pathogens. The biosynthesized GSE-AgNPs were assessed by UV spectroscopy, dynamic light scattering (DLS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), and gas chromatography/mass spectrometry (GC/MS). The antimicrobial activities were assessed against different bacterial and fungal species. DLS analysis showed that GSE-AgNPs had a Z-Average of 91.89 nm while UV spectroscopy showed that GSE-AgNPs had the highest absorbance at a wavelength of ~415 nm. FTIR analysis revealed that both of GSE and GSE-AgNPs consisted of different functional groups, such as hydroxyl, alkenes, alkyne, and aromatic rings. Both FE-SEM and TEM showed that GSE-AgNPs had larger sizes and rough surfaces than GSE and AgNO₃. The results showed significant antimicrobial activities of GSE-AgNPs against all tested species, unlike GSE, which had weaker and limited effects. More studies are needed to investigate the other antimicrobial activities of GSE.     

Enhanced bactericidal and in vivo wound healing potential of biosynthesized zinc oxide nanoparticles from psyllium mucilage

The multifunctional zinc oxide nanoparticles are synthesized using a cost-effective, efficient, eco-friendly, simple, and clean synthesis approach. Herein, we reported the antibacterial and wound healing potential of zinc oxide nanoparticles (ZnO-NPs) prepared using psyllium gel (PG) as the reducing and stabilizing agent. The PG-mediated zinc oxide nanoparticles (PG-ZnO-NPs) were characterized using UV–Vis, photoluminescence (PL), FTIR, XRD, Raman, and SEM. UV–Vis spectral studies confirmed the surface plasmonic resonance (SPR) band at 364 nm. PL results demonstrated the fluorescent or emission nature of PG-ZnO-NPs. FTIR analysis confirmed characteristic peaks at 873.82 and 619.88 cm⁻¹ due to the tetrahedral coordination of zinc and the formation of the Zn-O bond. XRD and Raman confirm the formation of PG-ZnO-NPs, whereas SEM analysis revealed PG-ZnO-NPs are rod-shaped, having hexagonal prism-like bases, and EDX exhibited the elemental composition of PG-ZnO-NPs. The as-synthesized PG-ZnO-NPs possessed prominent microbicidal potential against gram-positive (Bacillus subtilis and Bacillus licheniformis) and gram-negative (Escherichia coli and Salmonella shigella) bacterial strains in terms of zone of inhibition (ZOI), minimum inhibitory concentration (MIC), and minimum bactericidal concentration (MBC). In vivo biological investigations with mice show that the synthesized PG-ZnO-NPs possess outstanding biocompatibility and wound healing potential. PG-ZnO-NPs dressing significantly speeds up full-thickness wound repair by triggering a decrease in MMP-1 and MMP-2 and escalating the mRNA levels of collagen types (I & III) and fibronectin. Thus, our work validates that the inclusion of PG-ZnO-NPs in dressing shows excellent potential for acute wound management.     

Characterisation of nuclear fuel by spectroscopic evaluation of alpha autoradiographs

New methods for estimation of concentration and distribution of plutonium in (Th,Pu)O₂ MOX fuel samples have been attempted by spectroscopic analysis of SSNTD based alpha images using UV–Vis spectrophotometry and photoluminescence spectroscopy. (Th,Pu)O₂ MOX fuel samples having a large range of PuO₂ concentration, were subjected to this study and found beneficial when compared with the conventional analysis of alpha autoradiographs. UV–Vis absorbance and photoluminescence of the alpha autoradiograph showed linear decrease proportionally to PuO₂% in the fuel sample. Optical band gap was found to proportionally increase with PuO₂% in the fuel sample which was revealed in UV–Vis spectrophotometry.

     

Conformational Polymorphism in N‐(4′‐methoxyphenyl)‐ 3‐bromothiobenzamide

Three conformational polymorphs of N‐(4′‐methoxyphenyl)‐3‐bromothiobenzamide, yellow α, orange β, and yellow γ, have been identified by single‐crystal X‐ray diffraction. The properties and structure of the polymorphs were examined with FT Raman, FTIR (ATR), and UV/Vis spectroscopy, as well as differential scanning calorimetry. Computational data on rotational barriers in the isolated gas‐phase molecule indicate that the molecular conformation found in the α form is energetically preferred, but only by around 2 kJ mol^?1 over the γ conformation. The planar molecular structure found in the β form is destabilized by 10–14 kJ mol^?1, depending on the calculation method. However, experimental evidence suggests that the β polymorph is the most stable crystalline phase at room temperature. This is attributed to the relative planarity of this structure, which allows more and stronger intermolecular interactions, that is, more energetically effective packing. Calculated electronic‐absorption maxima were in agreement with experimental spectra.     

Redox properties of undoped 5 nm diamond nanoparticles

This paper demonstrates the promoting effects of 5 nm undoped detonation diamond nanoparticles on redox reactions in solution. An enhancement in faradaic current for the redox couples Ru(NH(3))(6)(3+/2+) and Fe(CN)(6)(4-/3-) was observed for a gold electrode modified with a drop-coated layer of nanodiamond (ND), in comparison to the bare gold electrode. The ND layer was also found to promote oxygen reduction. Surface modification of the ND powders by heating in air or in a hydrogen flow resulted in oxygenated and hydrogenated forms of the ND, respectively. Oxygenated ND was found to exhibit the greatest electrochemical activity and hydrogenated ND the least. Differential pulse voltammetry of electrode-immobilised ND layers in the absence of solution redox species revealed oxidation and reduction peaks that could be attributed to direct electron transfer (ET) reactions of the ND particles themselves. It is hypothesised that ND consists of an insulating sp(3) diamond core with a surface that has significant delocalised pi character due to unsatisfied surface atoms and C[double bond, length as m-dash]O bond formation. At the nanoscale surface properties of the particles dominate over those of the bulk, allowing ET to occur between these essentially insulating particles and a redox species in solution or an underlying electrode. We speculate that reversible reduction of the ND may occur via electron injection into available surface states at well-defined reduction potentials and allow the ND particles to act as a source and sink of electrons for the promotion of solution redox reactions.     

Functionalization of nanodiamond with epoxy monomer

A novel nanodiamond-epoxy derivative(ND-EP) was synthesized by grafting epoxy monomers onto the surface of nanodiamond(ND),and characterized by FTIR and TGA.The ratio of grafted epoxy groups was determined to be 32.5 wt% by TGA.The developed methodology provides an efficient method for the functionalization of nanodiamond material,which enables a variety of advanced engineering and biomedical applications of ND.     

Synthesis and characterization of magnetite nanoparticles for photocatalysis of nitrobenzene

The present work shows the photocatalytic degradation of nitrobenzene (NB) using Fe₃O₄ magnetic nanoparticles (MNP) as a photocatalyst in the presence of UV light. The MNP were synthesized by an ultrasonic-assisted reverse co-precipitation (US-RP) method using FeSO₄, FeCl₃ and NH₄OH as precursors. The prepared nanoparticles were characterized by UV–vis spectroscopy, attenuated total reflectance Fourier transformed infrared spectroscopy (ATR FT-IR), Raman spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Dynamic light scattering (DLS), Zeta potential, Vibrating sample magnetometer (VSM) and Magnetic thermogravimetric analysis (MTGA). The successive decrement in the absorbance at 265 nm shows the effective decrease in NB concentration measured by UV–vis spectroscopy. The reaction intermediates detected by gas chromatography/mass spectrum (GC/MS) were 2-nitrophenol (2-NPh), 3-nitrophenol (3-NPh) and 4-nitrophenol (4-NPh). The prepared MNP showed an optimal NB degradation at an initial pH of 2 and 100 ppm of the photocatalyst.     

Fabrication of silver nanoparticles in pH responsive polymer microgel dispersion for catalytic reduction of nitrobenzene in aqueous medium

Copolymer microgels based on N-isopropylacrylamide (NIPAM) and methacrylic acid (MAA) have been synthesized by free radical emulsion polymerization using N,N-methylenebisacrylamide (BIS) as a cross-linker. Synthesized microgels were characterized by Fourier transform infrared spectroscopy (FTIR). Then silver nanoparticles were fabricated in the synthesized microgels by in-situ reduction of AgNO₃ with NaBH₄. The formation of silver nanoparticles was confirmed by UV–Vis spectroscopy. The pH sensitivity of the copolymer microgels was investigated using dynamic light scattering technique (DLS). Hydrodynamic radius of P (NIPAM–MAA) microgels increases with increase in pH of the medium at 25°C. Surface plasmon resonance wavelength (λ_SPR) of silver nanoparticles increases with increase in hydrodynamic radius due to change in pH of the medium. The catalytic activity for the reduction of nitrobenzene (NB), an environmental pollutant, into aniline was investigated by UV–Vis spectroscopy in excess of NaBH₄ using hybrid microgels as catalyst. The value of apparent rate constant (k_app) of the reaction was calculated using pseudo first order kinetic model and it was found to be linearly related to the amount of catalyst. The results were compared with literature data. The system was found to be an effective catalyst for conversion of NB into aniline.     

Bio-therapeutic Potential and Cytotoxicity Assessment of Pectin-Mediated Synthesized Nanostructured Cerium Oxide

In the present studies, renewable and nontoxic biopolymer, pectin, was extracted from Indian red pomelo fruit peels and used for the synthesis of cerium oxide nanoparticles (CeO₂-NPs) having bio-therapeutic potential. The structural information of extracted pectin was investigated by FTIR and NMR spectroscopic techniques. Physicochemical characteristics of this pectin suggested its application in the synthesis of metal oxide nanoparticles. Using this pectin as a template, CeO₂-NPs were synthesized by simple, one step and eco-friendly approach. The UV–Vis spectrum of synthesized CeO₂-NPs exhibited a characteristic absorption peak at wavelength 345 nm, which can be assigned to its intrinsic band gap (3.59 eV) absorption. Photoluminescence measurements of CeO₂-NPs revealed that the broad emission was composed of seven different bands. FTIR analysis ensured involvement of pectin in the formation and stabilization of CeO₂-NPs. FT-Raman spectra showed a sharp Raman active mode peak at 461.8 cm^?1 due to a symmetrical stretching mode of Ce–O vibration. DLS, FESEM, EDX, and XRD analysis showed that the CeO₂-NPs prepared were polydispersed, spherical shaped with a cubic fluorite structure and average particle size ≤40 nm. These CeO₂-NPs displayed broad spectrum antimicrobial activity, antioxidant potential, and non-cytotoxic nature.