Synthesis and Raman spectroscopic characterisation of hydrotalcite with CO32− and VO3− anions in the interlayer

Infrared and Raman spectroscopy were used to characterise synthetic mixed carbonate and vanadate hydrotalcites of formula Mg₆Al₂(OH)₁₆(CO₃)²⁻, (VO₄)³⁻·4H₂ O. The spectra were used to assess the molecular assembly of the cations and anions in the hydrotalcite structure. The spectra may be conveniently subdivided into spectral features based on (1) the carbonate anion (2) the hydroxyl units and (3) water units. Bands were assigned to the hydroxyl stretching vibrations of water. Three types of carbonate anions were identified: (1) carbonate hydrogen‐bonded to water in the interlayer, (2) carbonate hydrogen‐bonded to the hydrotalcite hydroxyl surface and (3) free carbonate anions. It is proposed that the water is highly structured in the hydrotalcite, as it is hydrogen‐bonded to both the carbonate and the hydroxyl surface. The spectra were used to assess the contamination of carbonate in an open reacting vessel in the synthesis of vanadate hydrotalcites of formula Mg₆Al₂(OH)₁₆(CO₃)²⁻, (VO₄)³⁻·4H₂ O. Bands have been assigned to vanadate anions in the infrared and Raman spectra associated with V O bonds. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and Raman spectroscopic characterisation of hydrotalcites based on the formula Ca6Al2(CO3)(OH)16· 4H2O

We have successfully synthesised hydrotalcites (HTs) containing calcium, which are naturally occurring minerals. Insight into the unique structure of HTs has been obtained using a combination of X‐ray diffraction (XRD) as well as infrared and Raman spectroscopies. Calcium‐containing hydrotalcites (Ca‐HTs) of the formula Ca₄Al₂(CO₃)(OH)₁₂·4H₂O (2:1 Ca‐HT) to Ca₈Al₂(CO₃)(OH)₂₀· 4H₂O (4:1 Ca‐HT) have been successfully synthesised and characterised by XRD and Raman spectroscopy. XRD has shown that 3:1 calcium HTs have the largest interlayer distance. Raman spectroscopy complemented with selected infrared data has been used to characterise the synthesised Ca‐HTs. The Raman bands observed at around 1086 and 1077 cm⁻¹ were attributed to the ν₁ symmetric stretching modes of the (CO₃²⁻) units of calcite and carbonate intercalated into the HT interlayer. The corresponding ν₃ CO₃²⁻ antisymmetric stretching modes are found at around 1410 and 1475 cm⁻¹. Copyright © 2010 John Wiley & Sons, Ltd.     

钼、钒的单一及混合溶液中离子存在形态的拉曼光谱研究

利用拉曼光谱研究了钼、钒单一及混合溶液在pH=10.0~1.0时的离子分布行为. 钼、钒离子在存在形式上存在着差异：当pH=9.0~7.5时钒主要以(VO₃)_n^n-形式存在,而钼主要为MoO₄^2-. 这一差异是目前现有的许多钼钒分离方法的基本原理. 通过将混合溶液体系的拉曼光谱与单一体系进行对比,分析得出了混合体系中离子的存在形式. 当pH低于6.5时,部分V-O-V基团中的V原子会被Mo原子取代,从而形成了钼钒杂多酸离子. 当pH=6.0~2.0时,钒主要以十聚钒酸盐形式存在;当pH=2.0~1.0时,混合溶液中的钼主要以具有七钼酸盐结构的杂多酸离子存在,而在相同pH的单一溶液中,钼的存在形式主要为Mo₈O₂₆^4-和Mo₃₆O₁₁₂^8-.     

Synthesis and Raman spectroscopic study of Mg/Al,Fe hydrotalcites with variable cationic ratios

Hydrotalcites of formula Mg₆(Al,Fe)₂(OH)₁₆(CO₃)·4H₂O formed by intercalation with the carbonate anion as a function of divalent/trivalent cationic ratio have been successfully synthesised. The XRD patterns show variation in the d‐spacing attributed to the size of the cation. Raman and infrared bands in the OH stretching region are assigned to (1) brucite layer OH stretching vibrations, (2) water stretching bands and (3) water strongly hydrogen bonded to the carbonate anion. Multiple (CO₃)²⁻ symmetric stretching bands suggest that different types of (CO₃)²⁻ exist in the hydrotalcite interlayer. Increasing the cation ratio (Mg/Al,Fe) resulted in an increase in the combined intensity of the two Raman bands at around 3600 cm⁻¹, attributed to Mg OH stretching modes, and a shift of the overall band profile to higher wavenumbers. These observations are believed to be a result of the increase in magnesium in the structure. Raman spectroscopy shows a reduction in the symmetry of the carbonate, leading to the conclusion that the anions are bonded to the brucite‐like hydroxyl surface and to the water in the interlayer. Water bending modes are identified in the infrared spectra at positions greater than 1630 cm⁻¹, indicating that water is strongly hydrogen bonded to both interlayer anions and the brucite‐like surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Intermediate range order in concentrated aqueous solutions of copper nitrate. X-ray diffraction and Raman investigations

Concentrated aqueous solutions of copper nitrate of different concentrations (0.66 mol dm⁻³ up to 4.84 mol dm⁻³) have been investigated by X-ray diffraction at room temperature. In these solutions a maximum of intensity (prepeak) is observed at low values of Q (approx. 0.6 to 1 Å⁻¹) suggesting the existence of an intermediate range order in their structure, in agreement with previous investigations on different electrolytes. In order to get information on the solvation shell of the copper cation, Raman spectroscopy experiments have been performed for the more concentrated solution. Polarization observations, isotopic substitution of the solvent and the comparison with a Raman spectrum of a concentrated aqueous solution of aluminum nitrate were performed in order to improve the interpretation of the obtained results with these convergent observations.     

Synthesis and Raman spectroscopic characterisation of hydrotalcite with CO32− and (MoO4)2− anions in the interlayer

Raman spectroscopy has been used to characterise synthetic mixed carbonate and molybdate hydrotalcites of formula Mg₆Al₂(OH)₁₆((CO₃)²⁻,(MoO₄)²⁻)·4H₂O. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structure. The spectra may be conveniently subdivided into spectral features on the basis of the carbonate anion, the molybdate anion, the hydroxyl units and water units. Bands are assigned to the hydroxyl stretching vibrations of water. Three types of carbonate anions are identified: (1) carbonate hydrogen‐bonded to water in the interlayer, (2) carbonate hydrogen‐bonded to the hydrotalcite hydroxyl surface, (3) free carbonate anions. It is proposed that the water is highly structured in the hydrotalcite, as it is hydrogen bonded to both the carbonate and the hydroxyl surface. The spectra have been used to assess the contamination of carbonate in an open reaction vessel in the synthesis of a molybdate hydrotalcite of formula Mg₆Al₂(OH)₁₆((CO₃)²⁻, (MoO₄)²⁻)·4H₂O. Bands are assigned to carbonate and molybdate anions in the Raman spectra. Importantly, the synthesis of hydrotalcites from solutions containing molybdate provides a mechanism for the removal of this oxy‐anion. Copyright © 2007 John Wiley & Sons, Ltd.     

Spectral and fluorescent indication of the acid-base properties of biopolymer solutions

Methods of absorption and fluorescent spectroscopy and fluorescent chronoscopy are used to investigate aqueous fluorescein solutions with pH values increasing from 1.79 to 11.67. For each method, the calibration curves are drawn for the fraction of dianion fluorescein species, quantum fluorescence yield, and amplitude dianion contribution to the fluorescence intensity on the pH values of aqueous solutions. The calibration curves allow the pH values of aqueous fluorescein solutions with gelatin (pH = 6.4 ± 0.1, 6.6 ± 0.2, and 6.6 ± 0.1), starch (pH = 6.3 ± 0.1, 6.3 ± 0.2, and 6.4 ± 0.1), and acid-soluble chitosan additions (pH = 5.4 ± 0.1, 5.6 ± 02, and 5.8 ± 0.1) to be estimated by these three methods. The pH values of biopolymer solutions obtained by the potentiometer method for starch (6.51) and gelatin (6.69) and by the three spectral and fluorescent methods are close; they are significantly underestimated (3.85) for chitosan solutions.     

Raman spectroscopy of gallium‐based hydrotalcites of formula Mg6Ga2(CO3)(OH)16· 4H2O

Insight into the unique structure of hydrotalcites has been obtained using Raman spectroscopy. Gallium‐containing hydrotalcites of formula Mg₄Ga₂(CO₃)(OH)₁₂· 4H₂O (2:1 Ga‐HT) to Mg₈Ga₂(CO₃)(OH)₂₀· 4H₂O (4:1 Ga‐HT) have been successfully synthesized and characterized by X‐ray diffraction and Raman spectroscopy. The d(003) spacing varied from 7.83 Å for the 2:1 hydrotalcite to 8.15 Å for the 3:1 gallium‐containing hydrotalcite. Raman spectroscopy complemented with selected infrared data has been used to characterize the synthesized gallium‐containing hydrotalcites of formula Mg₆Ga₂(CO₃)(OH)₁₆· 4H₂O. Raman bands observed at around 1046, 1048 and 1058 cm⁻¹ are attributed to the symmetric stretching modes of the CO₃²⁻ units. Multiple ν₃ CO₃²⁻ antisymmetric stretching modes are found at around 1346, 1378, 1446, 1464 and 1494 cm⁻¹. The splitting of this mode indicates that the carbonate anion is in a perturbed state. Raman bands observed at 710 and 717 cm⁻¹ assigned to the ν₄ (CO₃²⁻) modes support the concept of multiple carbonate species in the interlayer. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopy of the sampleite group of minerals

Raman and infrared spectroscopy enabled insights into the molecular structure of the sampleite group of minerals. These minerals are based upon the incorporation of either phosphate or arsenate with chloride anion into the structure, and as a consequence the spectra reflect the bands attributable to these anions, namely, phosphate or arsenate with chloride. The sampleite vibrational spectrum reflects the spectrum of the phosphate anion and consists of ν₁ at 964 cm⁻¹, ν₂ at 451 cm⁻¹, ν₃ at 1016 and 1088 cm⁻¹ and ν₄ at 643, 604, 591 and 557 cm⁻¹. The lavendulan spectrum consists of ν₁ at 854 cm⁻¹, ν₂ at 345 cm⁻¹, ν₃ at 878 cm⁻¹ and ν₄ at 545 cm⁻¹. The Raman spectrum of lemanskiite is different from that of lavendulan consistent with a different structure. Low wavenumber bands at 227 and 210 cm⁻¹ may be assigned to CuCl transverse/longitudinal (TO/LO) optic vibrations. Raman spectroscopy identified the substitution of arsenate by phosphate in zdenekite and lavendulan. Copyright © 2007 John Wiley & Sons, Ltd.     

The analysis of pH‐dependent protonated conformers of 1‐hydroxyethylidene‐1,1‐diphosphonic acid by means of FT‐Raman spectroscopy,multivariate curve resolution and DFT modelling

1‐Hydroxyethylidene‐1,1‐diphosphonic acid (HEDP) solutions in the pH range 0.98–13.00 were analysed using FT‐Raman spectroscopy and ³¹P and ²³Na NMR spectroscopy. Vibrational bands for different protonated species were observed in the Raman spectra, whereas only a single NMR signal that shifted with pH was observed for all samples over the entire pH range. No significant shift in the ²³Na NMR signal was observed, confirming that formation of Na⁺(aq) complexes did not take place; hence, no interference with the different protonated forms of HEDP occurred. Vibrational bands were assigned using density functional theory(DFT)‐calculated spectra of the most likely conformers in solution. Multivariate curve resolution was performed on the Raman spectra in the region containing the PO stretching vibrations to determine the number of protonated species formed over the entire pH range. Chemometric analysis compares very favourably with the experimental species distribution diagram which was generated using the reported log K_H values. Copyright © 2009 John Wiley & Sons, Ltd.     

Computation and conversion of brain pH values obtained with two algorithms of phosphorus magnetic resonance spectroscopy data analysis

The intracellular brain pH in phosphorus magnetic resonance spectroscopy is calculated using the chemical shift between the inorganic phosphate and phosphocreatine with the Henderson–Hasselbalch equations. Researchers use various mathematical formulas that have different parameters and get various results for the same input data as a consequence. Thus, the aim of this article was to determine the mathematical formulas that allow the conversion of the pH values obtained by the most popular analysis methods to each other. To determine the relationships between pH results and the applied mathematical formula, the pH values were calculated using two algorithms for the theoretical chemical shift values. The pH results were compared with each other using the appropriate t-tests. Mathematical formulas were designed to simplify the conversion of pH values obtained by two data analysis methods to each other. The pH values with were obtained this way did not differ significantly from the pH values calculated directly from the given formula. The computed mathematical formulas will make it possible to simplify pH conversions without knowing the chemical shift between inorganic phosphate and phosphocreatine but only basing on the final pH values obtained by one of the formulas.     

Raman spectroscopy of gallium‐ and zinc‐based hydrotalcites

Insight into the unique structure of hydrotalcites (HTs) has been obtained using Raman spectroscopy. Gallium‐containing HTs of formula Zn₄ Ga₂(CO₃)(OH)₁₂ · xH₂O (2:1 ZnGa‐HT), Zn₆ Ga₂(CO₃)(OH)₁₆ · xH₂O (3:1 ZnGa‐HT) and Zn₈ Ga₂(CO₃)(OH)₁₈ · xH₂O (4:1 ZnGa‐HT) have been successfully synthesised and characterised by X‐ray diffraction (XRD) and Raman spectroscopy. The d(003) spacing varies from 7.62 Å for the 2:1 ZnGa‐HT to 7.64 Å for the 3:1 ZnGa‐HT. The 4:1 ZnGa‐HT showed a decrease in the d(003) spacing, compared to the 2:1 and 3:1 compounds. Raman spectroscopy complemented with selected infrared data has been used to characterise the synthesised gallium‐containing HTs. Raman bands observed at around 1050, 1060 and 1067 cm⁻¹ are attributed to the symmetric stretching modes of the (CO₃²⁻) units. Multiple ν₃ (CO₃²⁻) antisymmetric stretching modes are found between 1350 and 1520 cm⁻¹, confirming multiple carbonate species in the HT structure. The splitting of this mode indicates that the carbonate anion is in a perturbed state. Raman bands observed at 710 and 717 cm⁻¹ and assigned to the ν₄ (CO₃²⁻) modes support the concept of multiple carbonate species in the interlayer. Copyright © 2010 John Wiley & Sons, Ltd.     

Monitoring deprotonation of gallic acid by Raman spectroscopy

Gallic acid (GA) is involved in many biochemical processes and reactions and is of great importance in environment thanks to its antioxidant and pro‐oxidant properties. We present in this paper a comprehensive study of GA deprotonation by means of Raman spectroscopy. In the Raman spectra, we identified the characteristic bands that were sensitive to the five pH‐dependent GA forms. From these results, we extracted the GA pKa values that are consistent with the reference values. These results permit the monitoring of GA forms for applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and Raman spectroscopic characterisation of the oxalate mineral wheatleyite Na2Cu2+(C2O4)2·2H2O

The mineral wheatleyite has been synthesised and characterised by Raman spectroscopy complimented with infrared spectroscopy. Two Raman bands at 1434 and 1470 cm⁻¹ are assigned to the ν_{(C O)} stretching mode and implies two independent oxalate anions. Two intense Raman bands observed at 904 and 860 cm⁻¹ are assigned to the ν(C C) stretching mode and support the concept of two non‐equivalent oxalate units in the wheatleyite structure. Two strong bands observed at 565 and 585 cm⁻¹ are assigned to the symmetric CCO in plane bending modes. The Raman band at 387 cm⁻¹ is attributed to the CuO stretching vibration and the bands at 127 and 173 cm⁻¹ to OCuO bending vibrations. A comparison is made with Raman spectra of selected natural oxalate bearing minerals. Oxalates are markers or indicators of environmental events. Oxalates are readily determined by Raman spectroscopy. Thus, deterioration of works of art, biogeochemical cycles, plant metal complexation, the presence of pigments and minerals formed in caves can be analysed. Copyright © 2008 John Wiley & Sons, Ltd.     

大亚湾土壤胡敏酸的荧光光谱特征

本文较详细地研究了大亚湾土壤胡敏酸（Ｈｕｍｉｃ，Ａｃｉｄ，ＨＡ）的荧光光谱特征，对常规荧光光谱和同步荧光光谱进行了比较分析。     

SiC表面C 1s谱最优拟合参数的研究

提出了一种新的,用未限定拟合峰位置、半高宽和峰面积的X射线光电子谱拟合方法,研究了拟合峰的数目、函数类型及背景对SiC表面C 1s谱拟合结果的影响,并与样品表面宽扫描X射线光电子谱和红外掠反射吸收谱相对照,确定了SiC表面C 1s谱的最优拟合参数,获得了与文献中数值相同的 C 1s束缚能. 为SiC及其他材料表面元素窄扫描X射线光电子谱的拟合和化学态结构的鉴定奠定了基础. 关键词： SiC X射线光电子谱 C 1s谱     

Influence of Solution Acidity on Structure of Actinocin Derivatives and Their Affinity to DNA Studied as a Function of pH by Raman Spectroscopy

An important problem of molecular biophysics is the influence of pH and ionic strength of a solution on chemical structures and charge of biologically active substances. By means of pH titration and Raman spectroscopy methods, the influence of solution acidity on structural changes of actinocin derivatives was investigated, analogues to antitumor antibiotic actinomycin D. It has been shown that these ligands have different values of cation charges in neutral solutions. From analysis of Raman spectra, it was concluded that protonation of nitrogen atom and amino group of the phenoxazone ring starts only at pH < 3.5. It was shown that protonation of actinocin derivative with two amide groups (diaminoactinocin) occurred in two steps. Corresponding protonation constants for diaminoactinocin (log k ₁ = 6.9 ± 0.5 and log k ₂ = 5.3 ± 0.1) and for partially protonated actinocin derivative with three methylene groups in the side chains (log k = 5.3 ± 0.1) were obtained. Characteristic frequencies of Raman spectra for the basic functional C=O, C2–NH₂, C–C=C, and –N=C groups of phenoxazone chromophore of actinocin derivatives in protonated and nonprotonated states were determined. The different affinities of binding of variously charged ligands to DNA have also been demonstrated.     

Electrochemical characterization of surface complexes formed on Cu and Ta in succinic acid based solutions used for chemical mechanical planarization

Open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu lines and Ta barriers in the fabrication of semiconductor devices. It is shown that in non-alkaline solutions of H₂O₂, the SA-promoted surface complexes of Cu and Ta can potentially support chemically enhanced material removal in low-pressure CMP of surface topographies overlying fragile low-k dielectrics. ADS can suppress Cu dissolution without significantly affecting the surface chemistry of Ta. The data analysis steps are discussed in detail to demonstrate how the D.C. and A.C. electrochemical probes can be combined in the framework of the RDE technique to design and test CMP slurry solutions.     

Optical properties of serum albumin water solutions,containing mesoporous silicon particles

The interaction of molecules of bovine serum albumin (BSA) with silicon nanoparticles (SiNPs) was studied in water solutions of them at different pH values. The data of photon correlation spectroscopy and IR spectroscopy of studied solutions indicate the absence of interaction between BSA and SiNPs in the pH range 3–7, which is attested to by the experimentally obtained character of the pH dependence of the translational diffusion coefficient D _t and by the absence of hydrogen bonds between the protein carbonyl groups and the OH groups on the surface of mesoporous silicon nanoparticles. The obtained data may play a leading role in further in vivo application of silicon nanoparticles.     

Effect of dilute gelatine on the ultrasonic thermally assisted synthesis of nano hydroxyapatite

A series of nano hydroxyapatite-gelatine composites with different dilute solutions of gelatine concentrations were synthesized by a thermally assisted low-power ultrasonic irradiation method. The gelatine hydroxyapatite, (Gel-HAP) nanoparticles were prepared using Ca(NO(3))(2) and KH(2)PO(4) in the presence of gelatine in an aqueous solution. The synthesised products were heat treated between 100 and 400°C. The effect of the addition of gelatine on the nucleation and growth of synthesised nano HAP was investigated. Characterisation was performed using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and Fourier transform infrared spectroscopy (FT-IR). The characterisation results indicate that gelatine has been appended to the nano HAP forming regular spherical shaped crystals of nano sized Gel-HAP.