Optimization and comparison of ultrasound/microwave assisted extraction (UMAE) and ultrasonic assisted extraction (UAE) of lycopene from tomatoes

The extracting technology including ultrasonic and microwave assisted extraction (UMAE) and ultrasonic assisted extraction (UAE) of lycopene from tomato paste were optimized and compared. The results showed that the optimal conditions for UMAE were 98 W microwave power together with 40 KHz ultrasonic processing, the ratio of solvents to tomato paste was 10.6:1 (V/W) and the extracting time should be 367 s; as for UAE, the extracting temperature was 86.4 °C, the ratio of the solvents to tomato paste was 8.0:1 (V/W) and the extracting time should be 29.1 min, while the percentage of lycopene yield was 97.4% and 89.4% for UMAE and UAE, respectively. These results implied that UMAE was far more efficient extracting method than UAE.     

Ultrasound assisted combined molecularly imprinted polymer for selective extraction of nicotinamide in human urine and milk samples: Spectrophotometric determination and optimization study

Ultrasound-assisted dispersive solid phase microextraction followed by UV–vis spectrophotometer (UA-DSPME-UV–vis) was designed for extraction and preconcentration of nicotinamide (vitamin B₃) by HKUST-1 metal organic framework (MOF) based molecularly imprinted polymer (MIP). This new material was characterized by FTIR and FE-SEM techniques. The preliminary Plackett–Burman design was used for screening and subsequently the central composite design justifies significant terms and possible construction of mathematical equation which give the individual and cooperative contribution of variables like HKUST-1-MOF-NA-MIP mass, sonication time, temperature, eluent volume, pH and vortex time. Accordingly the optimum condition was set as: 2.0 mg HKUST-1-MOF-NA-MIP, 200 μL eluent and 5.0 min sonication time in center points other variables were determined as the best conditions to reach the maximum recovery of the analyte. The UA-DSPME-UV–vis method performances like excellent linearity (LR), limits of detection (LOD), limits of quantification of 10–5000 μg L⁻¹ with R² of 0.99, LOD (1.96 ng mL⁻¹), LOQ (6.53 μg L⁻¹), respectively show successful and accurate applicability of the present method for monitoring analytes with within- and between-day precision of 0.96–3.38%. The average absolute recoveries of the nicotinamide extracted from the urine, milk and water samples were 95.85–101.27%.     

Cu@SnS/SnO2 nanoparticles as novel sorbent for dispersive micro solid phase extraction of atorvastatin in human plasma and urine samples by high-performance liquid chromatography with UV detection: Application of central composite design (CCD)

Separation and detection of residual drug in biological fluids has directly related to human health in term of their beneficial or side effects. In biological fluid samples (complex matrix which containing drug at very low level) conduction of preliminary efficient technique as good choice for pre-concentration and clean-up of real sample before their instrumental analysis is highly recommended. In this result technique, based on nano-structure material which poses higher available surface area and larger member of reactive sites led to significant improvement in characteristic performance of analytical method. This paper focused on the synthesis and application of novel nano-sorbent for pre-concentration and extraction of atorvastatin (AT) from different biological fluids. Influence of various variables including sorbent dosage, eluent volume and sonication time on present method response was studied and optimized by central composite design under response surface methodology and accordingly an acceptable calibration curves over wide linear ranges (0.3–2000 μg L⁻¹) with high coefficient of determination higher than 0.999 strongly confirm high applicability of present method for quantification of analyte while limit of detection and quantification in plasma sample were 0.0608 and 0.2033 μg L⁻¹, respectively.     

Ultrasonically synthesis of Mn- and Cu- @ ZnS-NPs-AC based ultrasound assisted extraction procedure and validation of a spectrophotometric method for a rapid preconcentration of Allura Red AC (E129) in food and water samples

This study is devoted on Allura Red as food colorant preconcentration and determination in beverage, fruit juice and drink water samples is based on usage of Mn- and Cu- @ ZnS-NPs-AC as new sorbent for ultrasound-assisted-dispersive solid-phase microextraction (UA-DSPME) combined with ultraviolet–visible spectrophotometric based method (UV–Vis). Contribution of volume of eluent, pH, sorbent mass and sonication time on response following conduction of 28 experiments were optimized and investigated while their significantly justified according to p-value. Values of “Prob > F” less than 0.0500 is proportional with their significant influence on recovery of analyte. Under the optimum conditions 0.14 mL of THF; pH of 2.5; 8 mg of sorbent and 3 min sonication time guide and help achievement of limit of quantification (LOQ) and limit of detection (LOD) of 6.08 and 20.26 ng mL⁻¹, respectively. The accuracy of method was validated according to calculation of recovery following spiking 400 and 600 ng mL⁻¹ to blank solution and recovery as more reliable indication of accuracy 93.41 and 102.17% recoveries with RSD < 3.5%, which demonstrate the successful applicability of present method for real sample analysis. The maximum sorbent capacity was 50.0 mg g⁻¹ based on Langmuir isotherm as best model with high correlation coefficient. Combination of UA-DSPME and UV–Vis lead to higher sensitivity and lower cost for accurate and repeatable monitoring of Allura Red level in beverage, fruit juice and drink water samples with acceptable recovery and reasonable RSD%.     

Extraction of phenolics and anthocyanins from purple eggplant peels by multi-frequency ultrasound: Effects of different extraction factors and optimization using uniform design

In this work, multi-frequency ultrasound (working modes for the single-, dual- and tri-frequency in simultaneous ways) was applied to extract bioactive compounds from purple eggplant peels. The single-factor experiments were performed by varying six independent variables. A six-level-five-factor uniform design (UD) was further employed to evaluate the interaction effects between different factors. It was found that extraction temperature and extraction time significantly affected the total phenolic content (TPC), whereas the total monomeric anthocyanins (TMA) was mainly influenced by ethanol concentration, extraction temperature and solid-liquid ratio. Based on partial least-squares (PLS) regression analysis, the optimal conditions for TPC extraction were: 53.6 % ethanol concentration, 0.336 mm particle size, 44.5 °C extraction temperature, 35.2 min extraction time, 1:43 g/mL solid-liquid ratio, and similar optimal conditions were also obtained for TMA. Furthermore, the TPC and TMA extraction were investigated by ultrasound in different frequencies and power levels. Compared with single-frequency (40 kHz) and dual-frequency ultrasound (25 + 40 kHz), the extraction yield of TPC and TMA with tri-frequency ultrasound (25 + 40 + 70 kHz) increased by 23.65 % and 18.76 % respectively, which suggested the use of multi-frequency ultrasound, especially tri-frequency ultrasound, is an efficient strategy to improve the TPC and TMA extracts in purple eggplant peels.     

Comparisons between conventional,ultrasound-assisted and microwave-assisted methods for extraction of anthraquinones from Heterophyllaea pustulata Hook f. (Rubiaceae)

This work reports a comparative study about extraction methods used to obtain anthraquinones (AQs) from stems and leaves of Heterophyllae pustulata Hook (Rubiáceae). One of the conventional procedures used to extract these metabolites from a vegetable matrix is by successive Soxhlet extractions with solvents of increasing polarity: starting with hexane to eliminate chlorophylls and fatty components, following by benzene and finally ethyl acetate. However, this technique shows a low extraction yield of total AQs, and consumes large quantities of solvent and time. Ultrasound-assisted extraction (UAE) and microwave-assisted extraction (MAE) have been investigated as alternative methods to extract these compounds, using the same sequence of solvents. It was found that UAE increases the extraction yield of total AQs and reduces the time and amount of solvent used. Nevertheless, the combination UAE with benzene, plus MAE with ethyl acetate at a constant power of 900 W showed the best results. A higher yield of total AQs was obtained in less time and using the same amount of solvent that UAE. The optimal conditions for this latter procedure were UAE with benzene at 50 °C during 60 min, followed by MAE at 900 W during 15 min using ethyl acetate as extraction solvent.     

Ultrasound assisted extraction of Maxilon Red GRL dye from water samples using cobalt ferrite nanoparticles loaded on activated carbon as sorbent: Optimization and modeling

In this research, a selective, simple and rapid ultrasound assisted dispersive solid-phase micro-microextraction (UA-DSPME) was developed using cobalt ferrite nanoparticles loaded on activated carbon (CoFe₂O₄-NPs-AC) as an efficient sorbent for the preconcentration and determination of Maxilon Red GRL (MR-GRL) dye. The properties of sorbent are characterized by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Vibrating sample magnetometers (VSM), Fourier transform infrared spectroscopy (FTIR), Particle size distribution (PSD) and Scanning Electron Microscope (SEM) techniques. The factors affecting on the determination of MR-GRL dye were investigated and optimized by central composite design (CCD) and artificial neural networks based on genetic algorithm (ANN-GA). CCD and ANN-GA were used for optimization. Using ANN-GA, optimum conditions were set at 6.70, 1.2 mg, 5.5 min and 174 μL for pH, sorbent amount, sonication time and volume of eluent, respectively. Under the optimized conditions obtained from ANN-GA, the method exhibited a linear dynamic range of 30–3000 ng mL⁻¹ with a detection limit of 5.70 ng mL⁻¹. The preconcentration factor and enrichment factor were 57.47 and 93.54, respectively with relative standard deviations (RSDs) less than 4.0% (N = 6). The interference effect of some ions and dyes was also investigated and the results show a good selectivity for this method. Finally, the method was successfully applied to the preconcentration and determination of Maxilon Red GRL in water and wastewater samples.     

Multivariate optimization and comparison between conventional extraction (CE) and ultrasonic-assisted extraction (UAE) of carotenoid extraction from cashew apple

Carotenoids are an essential component of cashew and can be used in pharmaceuticals, cosmetics, natural pigment, food additives, among other applications. The present work focuses on optimizing and comparing conventional and ultrasound-assisted extraction methods. Every optimization step took place with a 1:1 (w:w) mixture of yellow and red cashew apples lyophilized and ground in a cryogenic mill. A Simplex-centroid design was applied for both methods, and the solvents acetone, methanol, ethanol, and petroleum ether were evaluated. After choosing the extractor solvent, a central composite design was applied to optimize the sample mass (59–201 mg) and extraction time (6–34 min). The optimum conditions for the extractor solvent were 38% acetone, 30% ethanol, and 32% petroleum ether for CE and a mixture of 44% acetone and 56% methanol for UAE. The best experimental conditions for UAE were a sonication time of 19 min and a sample mass of 153 mg, while the CE was 23 min and 136 mg. Comparing red and yellow cashews, red cashews showed a higher carotenoid content in both methodologies. The UAE methodology was ca. 21% faster, presented a more straightforward composition of extracting solution, showed an average yield of superior carotenoid content in all samples compared to CE. Therefore, UAE has demonstrated a simple, efficient, fast, low-cost adjustment methodology and a reliable alternative for other applications involving these bioactive compounds in the studied or similar matrix.     

Statistical optimization of process parameters for improvement of phycobiliproteins (PBPs) yield using ultrasound-assisted extraction and its kinetic study

The present study is mainly concerned for the development of an optimal ultrasound-assisted extraction (UAE) condition for phycobiliproteins (PBPs) from Oscillatoria sp. (BTA 170) using Taguchi methodology. Four process parameters viz. solid to liquid ratio, duty cycle, electrical acoustic intensity, and pH, for UAE were optimized using Taguchi methodology for enhanced PBPs extraction. The ratio of signal to noise (S/N) was used to compute the optimized condition required to attain a higher yield of PBPs, the average performance of individual parameter and corresponding interactive effects. The statistically significant parameters with their contribution were assessed using Analysis of variance (ANOVA). Results showed that duty cycle contributed the maximum influence (30.81%) on phycocyanin (PC) extraction followed by a solid liquid ratio (28.62%), pH (22.46%) and electrical acoustic intensity (18.10%). The highest contribution on the extraction of phycoerythrin (PE) was found from pH (33.16%), followed by duty cycle (31.57%), solid to liquid ratio (22.83%) and electrical acoustic intensity (12.45%). For extraction of allophycocyanin (APC), the duty cycle, solid to liquid ratio, pH and electrical acoustic intensity contributed 29.47, 29.07, 29.03, and 12.43% respectively. Results obtained from Taguchi methodology indicated that enhanced PC (94.10%), PE (95.20%) and APC (90.54%) can be achieved with solid–liquid ratio (0.2 g/ml), electrical acoustic intensity (16.99 w/cm²), duty cycle (75%), and pH 7 than the yield of PBPs obtained under unoptimized condition. In the present study, higher yield of PC (38.99%), PE (20.84%), and APC (11.93%) were attained with UAE compared to yield obtained from homogenized Oscillatoria sp. BTA 170 using 0.05 M phosphate buffer. Batch extraction data of PBPs under UAE was fitted well with the second order model. The values of second-order rate constant (k) were computed as 6.66 × 10⁻⁴, 64.09 × 10⁻⁴ and 1.49 × 10⁻⁴ L/mg/min for extraction of PC, PE and APC respectively. The PBPs exhibited significant antioxidant property and hydrogen peroxide scavenging activity, which were increased with the enhancement of PBPs concentration.     

Ultrasound-assisted extraction of highly nutritious date sugar from date palm (Phoenix dactylifera) fruit powder: Parametric optimization and kinetic modeling

Alternative sweeteners to white sugar with a lower calorie content and glycemic index obtained through date palm fruits is of great interest to the food industry. In this study, ultrasound-assisted extraction of nutritive sugar from date fruit powder was investigated through Box-Behnken design. A maximum total sugar content (TSC) of 812 mg glucose eq./g of DFP was obtained with a sugar extraction yield (SEY) of 81.40 ± 0.27 % under the following optimal extraction conditions: extraction temperature of 60 °C, extraction time of 30 min, and L/S ratio of 7.6 mL/g. Various modern techniques were used to characterize the obtained extracts and associated residues. The results showed that the extract contained fructose, glucose, and sucrose and had good thermal stability. Furthermore, SEM and TSC analysis revealed that ultrasonic treatment of the biomass improved mass transfer diffusion due to acoustic or ultrasonic cavitation, resulting in a higher sugar yield.     

A sonochemical assisted synthesis of hollow sphere structured tin (IV) oxide on graphene oxide sheets for the low-level detection of environmental pollutant mercury in biological samples and foodstuffs

In modern approaches for nanomaterials synthesis, ultrasonication plays an important role in providing the larger surface area and smaller crystalline size properties that are favorable to electrochemical techniques. Herein, we report the tin (IV) oxide on graphene oxide nanoparticles were synthesized (SnO₂@GO NPs) by ultrasonic methodology (UZ SONOPULS HD 3400 Ultrasonic homogenizer) with the total power of 400 W and the (frequency of 20 kHz; 140 W/dm³). The formation of as-prepared SnO₂@GO NPs and its surface morphology were scrutinized over XRD, XPS, TEM, and FESEM. Besides, the sonochemically prepared SnO₂@GO NPs were employed for the determination of environmental hazardous mercury (Hg). As a result, the modified electrode acquired a very low-level detection limit of 1.2 nM with a wider range of 0.01–10.41-µM and 14.52–225.4-µM for the detection of Hg. Finally, the practical applicability of SnO₂@GO NPs in spiked human blood serum and tuna fish samples shows appreciable found and recovery values..     

Utilization of natural deep eutectic solvents and ultrasound-assisted extraction as green extraction technique for the recovery of bioactive compounds from date palm (Phoenix dactylifera L.) seeds: An investigation into optimization of process parameters

The green extraction of bioactive compounds from date seeds was investigated using seven natural deep eutectic solvents (NADES) coupled with ultrasound-assisted extraction (UAE). The seven NADESs mainly consisted of choline chloride as hydrogen bond acceptors (HBA) and four sugars, two organic acids, and one polyalcohol as hydrogen bond donors (HBD) were utilized in this study. When the extraction efficiency of the NADESs was compared to that of the conventional solvents, all the NADESs showed superior bioactive compounds recovery efficacy. The lactic acid-based NADES had the highest extraction efficiency and was further optimized using the response surface method and Box-Behnken design. A four-factors including extraction time (10, 20, and 30 min), ultrasound amplitude (70, 80, and 90 %), % NADES content (30 %, 50 %, and 70 %) and solid-to-solvent ratio (1:30, 1.5:30, and 2:30 g/ml) each at three levels (−1, 0 and 1) using Box-Behnken design was applied. The % NADES content and the solid-to-solvent ratio were the major factors influencing the extraction efficiency of the total phenolic content (TPC) and the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity. The optimum extraction conditions included an extraction time of 15 min, ultrasound amplitude of 90 %, % NADES content of 70 % and solid-to-liquid ratio of 1:30 g/ml. The experimental values for TPC and DPPH at optimum extraction conditions were 145.54 ± 1.54 (mg GAE/g powder) and 719.19 ± 2.09 (mmol TE/g powder), respectively. The major phenolic compounds observed in the date seeds extracted using ChCl-LA were 3,4-dihydroxybenzoic acid, catechin and caffeic acid. This study reveals that the extraction of date seeds with NADES in combination with UAE technique was able to recover significantly higher amounts of phenolic compounds which could find useful applications in the food, pharmaceutical, and cosmetics industries.     

Ultrasound-alkaline combined extraction improves the release of bound polyphenols from pitahaya (Hylocereus undatus 'Foo-Lon') peel: Composition,antioxidant activities and enzyme inhibitory activity

In this study, ultrasound-assisted alkaline hydrolysis was used to extract polyphenols from pitahaya peel. The effects of sonication time, ultrasonic density, NaOH concentration and the liquid–material ratio on the total phenolic content (TPC), total flavonoid content (TFC) and antioxidant activity of the extracts were studied. The composition and content difference of the extracts were analyzed and the inhibitory effect of α-amylase and α-glucosidase was measured. The results of single-factor analysis showed that when the sonication time was 45 min, the ultrasonic density was 32 W/L, the NaOH solution concentration was 6 M and the liquid–material ratio was 30 mL/g, the release of phenolic compounds was the largest and the antioxidant activity was the strongest. An UPLC-QTOF-MS/MS method was used to analyze the components and contents of the extracts. We found that there was a great difference in the component content of the free polyphenol extract and the bound polyphenol extract. From the results, we concluded that there was a strong correlation between the type and content of phenolic compounds and antioxidant activities, indicating that phenolic compounds were the main compounds of these biological activities. Moreover, the bound polyphenol extracts showed a significant inhibitory effect on α-amylase and α-glucosidase was stronger than that of the free polyphenol extracts. In addition, scanning electron microscopy showed that ultrasound-assisted extraction is crucial to the destruction of the cell wall and the release of bound polyphenols. Therefore, the pitahaya peel has the potential for therapeutic, nutritional, and functional food applications, and ultrasound-assisted alkaline hydrolysis is an effective means to release phenolic compounds.     

Ultrasonic-assisted synthesis of polyacrylamide/bentonite hydrogel nanocomposite for the sequestration of lead and cadmium from aqueous phase: Equilibrium,kinetics and thermodynamic studies

Clay-hydrogel nanocomposites are suitable material for mitigating the pollution/environmental impact because of their high adsorption capacity. In this study, the synthesis of polyacrylamide/bentonite hydrogel nanocomposite was assisted by ultrasound through successful incorporation of nanobentonite as filler and cross-linker into polyacrylamide framework. The adsorbent was characterized by FTIR, XRD, BET, SEM-EDX, and TEM in order to observe structural changes and sorption interactions. The effect of adsorbent dose, contact time, initial metal ion concentration and pH on the sequestration of Pb²⁺ and Cd²⁺ was analyzed. The adsorbent removed more than 95% Pb²⁺ and Cd²⁺ within first 20 min, which corresponds to relatively high pseudo-first order rate constant, k₁ (0.240 for Pb²⁺ and 0.253 1/min for Cd²⁺) and pseudo-second order rate constant, k₂ (0.031 for Pb²⁺ and 0.033 g/mg/min for Cd²⁺). The isotherm and kinetics modeling data were best described by Freundlich isotherm over the entire concentration range and pseudo-second order rate equation, respectively. The thermodynamic studies implied spontaneous and endothermic nature of adsorption process. The maximum adsorption capacity (138.33 for Pb²⁺ and 200.41 mg/g for Cd²⁺) determined using Langmuir model along with a good regeneration potential depicts that polyacrylamide/bentonite hydrogel nanocomposite could be used effectively for Pb²⁺ and Cd²⁺ uptake from aqueous solution.     

Synthesis and application of molecularly imprinted nanoparticles combined ultrasonic assisted for highly selective solid phase extraction trace amount of celecoxib from human plasma samples using design expert (DXB) software

In this work molecular imprinted nanoparticles (MINPs) was synthesized and applied for ultrasonic assisted solid phase extraction of celecoxib (CEL) from human plasma sample following its combination by HPLC–UV. The MINPs were prepared in a non-covalent approach using methacrylic acid as monomer, CEL as template, ethylene glycol dimethacrylate as cross-linker, and 2,2-azobisisobutyronitrile (AIBN) as the initiator of polymerization. pH, volume of rinsing and eluent solvent and amount of sorbent influence on response were investigated using factorial experimental design, while optimum point was achieved and set as 250 mg sorbent, pH 7.0, 1.5 mL washing solvent and 2 mL eluent by analysis of results according to design expert (DX) software. At above specified conditions, CEL in human plasma with complicated matrices with acceptable high recoveries (96%) and RSD% lower than 10% was quantified and estimated.The proposed MISPE-HPLC–UV method has linear responses among peak area and concentrations of CEL in the range of 0.2–2000 μg L⁻¹, with regression coefficient of 0.98. The limit of detection (LOD) and quantification (LOQ) based on three and ten times of the noise of HPLC peaks correspond to blank solution were 0.08 and 0.18 μg L⁻¹, respectively.     

Comparison of hydrodistillation and ultrasonic solvent extraction for the isolation of volatile compounds from two unifloral honeys of Robinia pseudoacacia L. and Castanea sativa L

A comparative study of ultrasound-assisted extraction (USE) with the mixture pentane:ether (1:2) and hydrodistillation (HD) with the same trapping mixture is presented for the isolation of volatile compounds from two unifloral honeys of Robinia pseudoacacia L. and Castanea sativa L. All HD isolates contained many thermally derived artefacts (especially phenylacetaldehyde with lower percentages of furfural, cis- and trans-linalool oxides and others). USE method gave the most representative profile of all honey volatiles (without artefacts). In addition, USE enabled extraction of low molecular weight semivolatile markers (especially benzoic, vanillic and phenylacetic acids) that were not extracted by HD. In this regard, low percentage of benzoic acid (0.7–7.4%), vanillic acid (0.0–1.6%) and phenylacetic acid (0.5–4.1%) was determined in Rp USE extracts, while Cs USE extracts contained phenylacetic acid (20.2–23.5%) as the major constituent with low percentage of benzoic acid (2.5–5.5%).     

Poly(4-vinylpyridinium)hydrogen sulfate: a novel and efficient catalyst for the synthesis of 14-aryl-14H-dibenzo[a,j]xanthenes under conventional heating and ultrasound irradiation

A simple and convenient procedure for the synthesis of 14-aryl-14H-dibenzo[a,j]xanthenes is described through a one-pot condensation of 2-naphthol with aryl aldehydes in the presence of poly(4-vinylpyridinium)hydrogen sulfate as an efficient, cheap, readily synthesized and eco-friendly catalyst in a solvent free media using conventional heating and ultrasound irradiation.     

Dinuclear Zn(II) catalysts as biomimics of RNA and DNA phosphoryl transfer enzymes: changing the medium from water to alcohol provides enzyme‐like rate enhancements

Phosphodiesters are notoriously hydrolytically inert compounds that are demonstrated to have large accelerations of P‐OR cleavage promoted by transition and lanthanide metal ions in methanol and ethanol media. This review commentary describes recent findings of how a simple mononuclear and a dinuclear Zn(II) complex promote the cleavage of a series of RNA models and DNA models in alcohol media. The discussion centers on the analysis of the mechanisms of cleavage, energetics of the catalytic process, on recent findings of electrophilic assistance of leaving group departure, and the observation of a rapid hydrolytic reaction of a DNA model promoted by the dinuclear Zn(II) complex in ethanol containing less than 2% water. Copyright © 2009 John Wiley & Sons, Ltd.     

Gaussian basis set of triple zeta valence quality for the atoms from K to Kr: Application in DFT and CCSD(T) calculations of molecular properties

A contracted basis set of triple zeta (TZ) valence quality for the atoms from K to Kr was constructed from fully-optimized Gaussian basis sets generated in this work. Gaussian polarization functions (d, f, and g symmetries), which were optimized at the second-order Mφller–Plesset level, were added to the TZ set. This extends earlier work on segmented contracted TZ basis set for atoms H-Ar. This set along with the BP86 non-hybrid and B3LYP hybrid functionals were used to calculate geometric parameters, dissociation energy, harmonic vibrational frequency, and electric dipole moment of a sample of molecules and, then, comparison with results obtained with other basis sets and with experimental data reported in the literature is done. CCSD(T) atomic excitation energies and bond lengths, dissociation energies, and harmonic vibrational frequencies of some diatomics were also evaluated. Using density functional theory and gauge-including atomic orbitals, ⁵⁷Fe and ⁷⁷Se nuclear magnetic resonance chemical shifts in Fe(C₅H₅)₂, H₂Se, (CH₃)SeH, CSe₂, SeCO, H₂CSe, and SeF₆ were calculated. Comparison with theoretical and experimental values previously published in the literature was done. It is verified that in general these results give good agreement with experimental and benchmark values.     

Raman spectroscopic study of the hydrogen and arsenate bonding environment in isostructural synthetic arsenates of the variscite group—M3+ AsO4·2H2O (M3+ = Fe,Al, In and Ga): implications for arsenic release in water

The Raman spectra of synthetic compounds equivalent to the variscite group: FeAsO₄·2H₂O AlAsO₄·2H₂O, GaAsO₄·2H₂O, and InAsO₄·2H₂O are reported. In particular, upon comparison of FeAsO₄·2H₂O to AlAsO₄·2H₂O, it is observed that the Type II (weak) H‐bond lengths in the latter are slightly longer, which is postulated to affect the stability (As release) in water at pH 5 and 7. Arsenate stretching and bending vibrations were found to be distinct in terms of spectral structure and therefore well suited for fingerprinting. The calculated As O bond strengths from existing crystallographic data showed no significant variations. The strongest ν₁ (AsO₄³⁻) stretch was used to monitor the As O bonding interactions in the four As O M units, where a shift of 114 cm⁻¹ was observed in the order FeAsO₄·2H₂O (lowest) < InAsO₄·2H₂O < GaAsO₄·2H₂O < AlAsO₄·2H₂O (highest); this order also followed exactly the measured arsenic release of these phases. This shift in ν₁ (AsO₄³⁻) position was rationalized to stem from the differences in the electronegativities of the M³⁺ cations. The trends mentioned above were verified and found to also hold for the isostructural phosphate analogues strengite (FePO₄·2H₂O) and variscite (AlPO₄·2H₂O) using published data. Therefore, it is postulated that, as observed with the stability of solution complexes, there may be a correlation between the electronegativity of the M³⁺ cation in these isostructural phases and their stability (As or P release) in water. Copyright © 2010 John Wiley & Sons, Ltd.