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At least 19 records

Effect of pH value on particle morphology and electrochemical properties of LiFePO{sub 4} by hydrothermal method

Graphical abstract: The pH value of system is adjusted in the range of 2.5-8.8 by using dilute sulfuric acid and ammonia water. The results indicated that the particle exhibits acute angle diamond flake-like morphology at pH = 2.5. With increase of pH value, the particle gradually becomes to round flake-like and irregular flake-like morphology. The optimal sample synthesized at pH = 6.4 exhibits discharge capacities of 151.8 mAh g{sup -1} at 0.2 C rate and 129.3 mAh g{sup -1} at 3 C rate. Highlights: {yields} The pH value of solution affects greatly on particle morphology. {yields} The solubility product determined the transition of interphases. {yields} The disorder of atoms in crystal is affected by pH value. {yields} LiFePO{sub 4} with high capacity could be synthesized at slight acid or neutral conditions. -- Abstract: Lithium iron phosphate was prepared by hydrothermal synthesis using LiOH.H{sub 2}O, FeSO{sub 4}.7H{sub 2}O and H{sub 3}PO{sub 4} as raw materials. The effects of pH value of reaction solution on particle morphology and electrochemical property were investigated. The pH value of the reaction solution was adjusted in the range of 2.5-8.8 by dilute sulfuric acid and ammonia water. The samples were characterized by field-emission scanning electronic microscope (FE-SEM), X-ray powder diffraction (XRD), constant-current charge/discharge cycling tests and chemical analysis. The results indicated that the particles exhibited acute angle diamond flake-like morphology at pH = 2.5, and as the pH value increased, the particle became hexagon flake-like, round flake-like and irregular flake-like morphology gradually. The optimal sample synthesized at pH = 6.4 exhibited discharge capacities of 151.8 mAh g{sup -1} at 0.2 C rate and 129.3 mAh g{sup -1} at 3 C rate. It was found that pH value affected the morphologies and properties of the product by means of different crystal growth rates.

36 MATERIALS SCIENCE↗

Tumor‐pH‐value responsive non‐peripheral substituted phthalocyanines: Synthesis, investigation of photophysical and photochemical properties

Cancer is one of the diseases with the highest mortality rate worldwide. Although PDT has recently produced encouraging outcomes, there are still many areas that need to be improved. The first of these is the negative consequences faced by patients treated with the PDT method when exposed to sunlight. For this reason, a new PDT method has been developed in recent years, and it is aimed at using photosensitizer molecules that can be active in acidic conditions. Since the pH values of tumor tissues are more acidic than normal tissues, preparing molecules that act effectively in acidic conditions will allow for more effective results in treating cancer with PDT. In this context, within the scope of this study, 3‐(4‐propionylphenoxy)phthalonitrile ( 1 ) and its non‐peripheral tetra‐substituted phthalocyanine derivatives [( 2 ), ( 3 ), and ( 4 )] were prepared. With these phthalocyanine derivatives, the novel compounds ( 5 ), ( 6 ), and ( 7 ) were synthesized for the first time. The aggregation tendencies of newly synthesized phthalocyanines ( 5–7 ) were investigated in solvent media. The effects of pH changes upon UV–Vis and fluorescence spectra were performed. The electronic and emission spectra of synthesized phthalocyanine derivatives are highly sensitive to pH changes. Formation constant (Log K) values of mono‐ and di‐protonated phthalocyanine forms were calculated by the Henderson–Hasselback equation. The mono‐ and di‐protonated species' equilibrium constants (logK 1 and logK 2 ) were calculated as ~5.0. This value may be promising for pH‐sensitizing photosensitizers. Also, the photophysical and photochemical properties of synthesized metallophthalocyanine derivatives ( 2 ) and ( 5 ) were studied at different pH values. The singlet oxygen quantum yield of ( 2 ) and ( 5 ) was calculated to be 0.78 and 0.81 in DMSO, respectively. When pH = 6.4, that is, tumor‐pH‐values, this value for ( 5 ) has increased to 0.92. The newly synthesized phthalocyanines are suitable photosensitizers for PDT applications, especially with high singlet oxygen quantum yield at pH 6.4.

Genc Bilgicli, Hayriye↗

Visible light absorption of TiO{sub 2} materials impregnated with tungstophosphoric acid ethanol–aqueous solution at different pH values. Evidence about the formation of a surface complex between Keggin anion and TiO{sub 2} surfaces

Graphical abstract: - Highlights: • TPA impregnation on TiO{sub 2} particles was done at different initial pH values. • Powders characterization evidenced the possible existence of TPA–TiO{sub 2} complexes. • Keggin anion complexed on TiO{sub 2} would be responsible of visible light absorption. - Abstract: TiO{sub 2} particles prepared by the sol–gel method were impregnated at different pH values (1.0, 2.0, 5.0 and 10.0) with a water–ethanol solution (50% V/V) of tungstophosphoric acid (TPA) (0.012 M). Similar preparation was carried out to synthesize TiO{sub 2} impregnated with [WO{sub 4}]{sup 2−} (TiW). These materials were characterized by different techniques such as UV–vis diffuse reflectance spectroscopy (UV–vis DRS), magic angle spinning nuclear magnetic resonance of {sup 31}P ({sup 31}P MAS NMR), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Fourier transform Raman spectroscopy (FT-Raman). Results revealed that TPA–TiO{sub 2} materials exhibit visible light absorption only when impregnation was done at pH 1.0 (TiTPA1) and 2.0 (TiTPA2). TiW powder did not show visible light absorption. XRD patterns show the presence of peaks at 2θ = 25.4° (1 0 1), 37.9° (0 0 4), 47.8° (2 0 0) and 54.3° associated to the anatase phase. Solid NMR, FT-IR and FT-Raman characterization showed that TiTPA1 and TiTPA2 samples contain Keggin ([PW{sub 12}O{sub 40}]{sup 3−}) and lacunary anions ([PW{sub 11}O{sub 39}]{sup 7−}) respectively. On the other hand, FT-Raman results revealed a blue shifting and broadening of the band at 141 cm{sup −1} corresponding to anatase TiO{sub 2} and moreover, a broadening of bands at 900–1100 cm{sup −1} attributed to Keggin structures of TPA. Both spectral changes could be related to the formation of a surface complex between the Keggin anion of TPA and TiO{sub 2} surfaces. This interaction should be responsible for visible light absorption.

36 MATERIALS SCIENCE↗

Physical Properties of Mn{sub 2}O{sub 3} Nanoparticles Synthesized by Co-precipitation Method at Different pH Values

Mn{sub 2}O{sub 3} nanoparticles were synthesized at different pH values ranging from 10 to 13 by co-precipitation technique. The characterization of all samples were completed by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), ultraviolet-absorption spectroscopy (UV), Raman spectroscopy, and M–H loop measurements. The XRD spectra show that the structure of Mn{sub 2}O{sub 3} is cubic, and the lattice parameter a decreases as pH increases. Crystalline size, determined from TEM and XRD analyses, decreases as pH increases. TGA curves show that a mass loss is significantly affected as pH increases, indicating the decomposition of organic species besides the oxidation of Mn{sub 2}O{sub 3} to Mn{sub 3}O{sub 4}. FTIR spectra indicate that the absorption peaks at 593.73 and 519.09 cm{sup − 11} referred to the stretching vibration of Mn–O and Mn–O–Mn bonds during the synthesis of Mn{sub 2}O{sub 3} nanoparticles. UV-visible spectroscopy is measured in the range 250–800 nm and showed a deviation to the lower wavelength in addition to an increase in the band-gap energy (E{sub g}) values from 1.012 to 1.370 eV is obtained. Raman spectra shows a slight deviation to the left which is conversely proportional to the crystalline size. M–H loops for the prepared samples were measured and the results of retentivity (M{sub s}) and coercivity (H{sub c}) were discussed.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Thermoluminescence Characteristics of Nanocrystalline LiF Phosphors Synthesized at Different pH Values

Nanocrystalline lithium fluoride (LiF) phosphors have been prepared by the chemical co-precipitation method at different pH values (7.0, 8.0, 9.0). The formation of nanocrystalline structure has been confirmed by X-ray diffraction and transmission electron microscope. The thermolumniscence (TL) properties of LiF phosphors irradiated with gamma rays at different doses have been studied. The analysis of TL glow curve has revealed the existence of two well resolved glow peaks, one low temperature peak at around 145 deg. C and other one at higher temperature around 375 deg. C. The LiF nano-crystallites synthesized at 8.00 pH have been found to show maximum TL intensity at studied gamma doses (0.1 Gy-15 Gy).

36 MATERIALS SCIENCE↗

Influence of the pH value of a colloidal gold solution on the absorption spectra of an LSPR-assisted sensor

The localized surface plasmon resonances (LSPRs) of gold particles assembled on a crystal plate are a powerful tool for biological sensors. Here, we prepare gold colloids in different pH solutions. We monitor the effects of the particle radius and particle coverage on the absorption spectra of AT-cut (r-face dihedral angle of about 3°) crystal plates supporting gold nanoparticles. The surface morphologies were monitored on silicon dioxide substrates using ultraviolet and visible (UV-vis) spectroscopy, and atomic force microscopy (AFM). The results showed that the gold particle coverage decreases with increasing pH value of the gold colloid solution. This phenomenon demonstrates that self-assembled gold surfaces were formed via the electrostatic adsorption of gold particles on the positively charged, ionized amino groups on the crystal plates in the acidic solution. The spectrum of gold nanoparticles with different coverage degree on the crystal plates showed that the LSPR properties are highly dependent on pH.

36 MATERIALS SCIENCE↗

Rare earth enrichment process by contacting raw material with a base at specific pH values

Disclosed herein are methods for preparing a hydraulic pre-concentrate enriched in rare earth elements and critical minerals, the method comprising: (a) contacting a raw material with a first base in an amount sufficient to adjust the pH to a value from about 4.0 to about 6.0, thereby forming a mixture comprising a first aqueous phase and a first solid concentrate; (b) separating the first aqueous phase from the first solid concentrate; (c) contacting the first aqueous phase with a second base in an amount sufficient to adjust the pH to a value from about 7.0 to about 9.0, thereby forming a mixture comprising a second aqueous phase and the hydraulic pre-concentrate; (d) removing the second aqueous phase and collecting the hydraulic pre-concentrate; wherein the raw material comprises rare earth elements; and wherein the hydraulic pre-concentrate is enriched in rare earth elements.

Ziemkiewicz, Paul F.↗

Structural and degradation studies of a biocompatible Zn-L-tartrate metal–organic framework

New anhydrous Zn-L-tratrate was synthesized under hydrothermal conditions. Crystal structure which was solved by powder X-ray diffraction data from monoclinic unit cell (I{sub 2}, a=11.7557(1), b=9.0319(1), c=5.0750(1), β=91.920(1)) consists of the three-dimensional framework where each Zn atom coordinates four tartrate ligands in distorted octahedral geometry. Due to its biocompatible components, the degradation of material was studied in aqueous media under different pH values (pH=1–7) and in the simulated body fluid (pH=7.4) performed by the measurement of the released Zn{sup 2+} concentrations at thermostatic conditions (37 °C). The results showed that under acidic conditions approximately 60% of Zn{sup 2+} is released from the investigated material after 6 h of degradation process. With the increase of the solution’s pH, the rate of degradation gradually decreases. XRD and SEM analyses indicate that in aqueous media the compound slowly disintegrates and does not undergo hydrolysis process regardless of pH. Biocompatibility of the compound and its controllable rate of degradation even in acid conditions open its potential use in the fields of bio-applications. - Graphical abstract: The degradation kinetics of Zn-L-tar MOF material in aqueous media at different pH conditions. - Highlights: • Anhydrous chiral Zn-L-tratrate was synthesized under hydrothermal conditions. • 3-D framework consists of Zn atoms, each chelating four tartrate ligands. • Degradation of material was studied in aqueous media at different pH values. • The compound disintegrates in controllable manner in aqueous solutions. • The rate compound degradation is increasing with increased acidity of solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pyrolytic oil of banana (Musa spp.) pseudo-stem via fast process

This study was an attempt to produce bio-oil from banana pseudo-stem, a waste of banana cultivation, using fast pyrolysis technology. The compositions were determined and the thermal degradation behaviour of the raw material was analyzed using Perkin-Elmer Simultaneous Thermal Analyzer (STA) 6000. A 300 g/h fluidized bed bench scale fast pyrolysis unit, assembled with double screw feeders and cyclones, operating at atmospheric pressure, was used to obtain the pyrolysis liquid. The study involves the impact of the following key variables; the reactor temperature in the range of 450–650 °C, and the residence time in the range of 1.00–3.00 s. The particle size was set at 224-400 µm. The properties of the liquid product were analyzed for calorific heating value, pH value, conductivity, water and char content. The basic functional groups of the compositions were also determined using FTIR. The properties of the liquid product were compared with other wood derived bio-oil. The pyrolysis liquids derived from banana pseudo-stem were found to be in an aqueous phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computer simulation of immobilized pH gradients at acidic and alkaline extremes - A quest for extended pH intervals

Computer simulations of the concentration profiles of simple biprotic ampholytes with Delta pKs 1, 2, and 3, on immobilized pH gradients (IPG) at extreme pH values (pH 3-4 and pH 10-11) show markedly skewed steady-state profiles with increasing kurtosis at higher Delta pK values. Across neutrality, all the peaks are symmetric irrespective of their Delta pK values, but they show very high contribution to the conductivity of the background gel and significant alteration of the local buffering capacity. The problems of skewness, due to the exponential conductivity profiles at low and high pHs, and of gel burning due to a strong electroosmotic flow generated by the net charges in the gel matrix, also at low and high pHs, are solved by incorporating in the IPG gel a strong viscosity gradient. This is generated by a gradient of linear polyacrylamide which is trapped in the gel by the polymerization process.

Mosher, Richard A.↗

Mycobacterium tuberculosis acyl carrier protein synthase adopts two different pH-dependent structural conformations

The crystal structures of acyl carrier protein synthase (AcpS) from Mycobacterium tuberculosis (Mtb) and Corynebacterium ammoniagenes determined at pH 5.3 and pH 6.5, respectively, are reported. Comparison of the Mtb apo-AcpS structure with the recently reported structure of the Mtb AcpS-ADP complex revealed that AcpS adopts two different conformations: the orthorhombic and trigonal space-group structures show structural differences in the {alpha}2 helix and in the conformation of the {alpha}3-{alpha}4 connecting loop, which is in a closed conformation. The apo-AcpS structure shows electron density for the entire model and was obtained at lower pH values (4.4-6.0). In contrast, at a higher pH value (6.5) AcpS undergoes significant conformational changes, resulting in disordered regions that show no electron density in the AcpS model. The solved structures also reveal that C. ammoniagenes AcpS undergoes structural rearrangement in two regions, similar to the recently reported Mtb AcpS-ADP complex structure. In vitro reconstitution experiments show that AcpS has a higher post-translational modification activity between pH 4.4 and 6.0 than at pH values above 6.5, where the activity drops owing to the change in conformation. The results show that apo-AcpS and AcpS-ADP adopt different conformations depending upon the pH conditions of the crystallization solution.

59 BASIC BIOLOGICAL SCIENCES↗

Influence of pH on the physical and electromagnetic properties of Mg–Mn ferrite synthesized by a solution combustion method

The synthesis of nano-crystalline Mg–Mn ferrites by a solution combustion method using citric acid and ammonia was investigated by varying the pH of the precursor solution, which played an important role in controlling the morphology of the synthesized powders. The phase formation, microstructure and electromagnetic properties were studied using X-ray diffraction, scanning electron microscopy, impedance analyzer and vibrating sample magnetometer. Single phase pure spinel Mg–Mn ferrite powders were obtained for all the samples at different pH (< 1, 3, 5, 7, 9). The results showed that an increase of pH improves the crystallinity of the Mg–Mn ferrite nanoparticles. The average grain size of sintered samples was found to decrease from 2 μm to 0.5 μm with increasing pH values from pH < 1 to pH 9, respectively. The dielectric constant of the samples with different pH is in the range of 7–12 from frequencies of 1 MHz to 1 GHz. The highest saturation magnetization (30.04 emu/g) was obtained for the sample with pH < 1. - Highlights: • Mg–Mn ferrites were synthesized by a solution combustion method with different pH. • Auto-combustion process resulted in the formation of single phase spinel ferrite. • An increase of pH improves the crystallinity of the Mg–Mn ferrite nanoparticles. • pH variation has influence on phase formation and morphology of the ferrite.

36 MATERIALS SCIENCE↗

Transmission Electron Microscopy Study of Eu-Doped Y2O3 Nanosheets and Nanotubes

A hydrothermal method was used to synthesize high-purity Eu-doped Y{sub 2}O{sub 3} nanosheets and nanotubes with an approximate molar ratio of (0.1):(1.0) for Eu:Y. High-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy analysis and synchrotron X-ray diffraction were used to characterize these nanomaterials. A body-centered cubic structure was confirmed for the nanotubes. The lattice parameter of Eu-doped Y{sub 2}O{sub 3} nanotubes were 0.12% larger as compared to that of pure Y{sub 2}O{sub 3} which was attributed to the larger ionic radius of Eu{sup 3+} (0.947 {angstrom}) than that of Y{sup 3+} (0.900 {angstrom}). The nanosheets had a similar structure. Nanosheets of approximate dimensions 600 to 800 nm length and width were obtained using a slightly lower pH value, and they were highly textured. The high resolution transmission electron microscopy images showed that the nanotubes are fully crystalline. The nanotubes were typically 1.5-3 {micro}m in length and 50-200 nm in diameter. Using a pH value of approximately 10, stable nanotubes were obtained. It is anticipated that nanosheets might have rolled to form more stable nanotubes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Synthesis, morphology, optical and photocatalytic performance of nanostructured β-Ga{sub 2}O{sub 3}

Highlights: ► Nanostructures of β-Ga{sub 2}O{sub 3} were prepared using facile reflux condensation process. ► The pH of the reaction mixture shows evident influence on the size and shape of the nanostructures formed. ► The nanostructures exhibited good photocatalytic activity toward Rhodamine B and was found to be superior for higher pH value. - Abstract: Fine powders of β-Ga{sub 2}O{sub 3} nanostructures were prepared via low temperature reflux condensation method by varying the pH value without using any surfactant. The pH value of reaction mixture had great influence on the morphology of final products. High crystalline single phase β-Ga{sub 2}O{sub 3} nanostructures were obtained by thermal treatment at 900 °C which was confirmed by X-ray diffraction and Raman spectroscopy. The morphological analysis revealed rod like nanostructures at lower and higher pH values of 6 and 10, while spindle like structures were obtained at pH = 8. The phase purity and presence of vibrational bands were identified using Fourier transform infrared spectroscopy. The optical absorbance spectrum showed intense absorption features in the UV spectral region. A broad blue emission peak centered at 441 nm due to donor–acceptor gallium–oxygen vacancy pair recombination appeared. The photocatalytic activity toward Rhodamine B under visible light irradiation was higher for nanorods at pH 10.

36 MATERIALS SCIENCE↗