Comparison of polarizable continuum model and quantum mechanics/molecular mechanics solute electronic polarization: study of the optical and magnetic properties of diazines in water

A combination of the polarizable continuum model (PCM) and the hybrid quantum mechanics/molecular mechanics (QM/MM) methodology, PCM-MM/QM, is used to include the solute electronic polarization and then study the solvent effects on the low-lying n→π(?) excitation energy and the (15)N nuclear magnetic shielding of pyrazine and pyridazine in aqueous environment. The results obtained with PCM-MM/QM are compared with two other procedures, i.e., the conventional PCM and the iterative and sequential QM/MM (I-QM/MM). The QM calculations are made using density functional theory in the three procedures. For the excitation energies, the time-dependent B3LYP/6-311+G(d) model is used. For the magnetic shielding, the B3LYP/aug-pcS2(N)/pcS2(C,O,H) is used with the gauge-including atomic orbitals. In both cases, i.e., PCM-MM/QM and I-QM/MM, that use a discrete model of the solvent, the solute is surrounded by a first shell of explicit water molecules embedded by an electrostatic field of point charges for the outer shells. The best results are obtained including 28 explicit water molecules for the spectral calculations and 9 explicit water molecules for the magnetic shielding. Using the PCM-MM/QM methodology the results for the n→π(?) excitation energies of pyridazine and pyrazine are 32,070 ± 80 cm(-1) and 32,675 ± 60 cm(-1), respectively, in good agreement with the corresponding I-MM/QM results of 32,540 ± 80 cm(-1) and 32,710 ± 60 cm(-1) and the experimental results of 33,450-33,580 cm(-1) and 32,700-33,300 cm(-1). For the (15)N magnetic shielding, the corresponding numbers for the gas-water shifts obtained with PCM-MM/QM are 47.4 ± 1.3 ppm for pyridazine and 19.7 ± 1.1 ppm for pyrazine, compared with the I-QM/MM values of 53.4?±?1.3 ppm and 19.5 ± 1.2 ppm and the experimental results of 42-54 ppm and 17-22 ppm, respectively. The agreement between the two procedures is found to be very good and both are in agreement with the experimental values. PCM-MM/QM approach gives a good solute polarization and could be considered in obtaining reliable results within the expected QM/MM accuracy. With this electronic polarization, the solvent effects on the electronic absorption spectra and the (15)N magnetic shielding of the diazines in water are well described by using only an electrostatic approximation. Finally, it is remarked that the experimental and theoretical results suggest that the (15)N nuclear magnetic shielding of any diazine has a clear dependence with the solvent polarity but not directly with the solute-solvent hydrogen bonds.     

Vertical inventories and fluxes of <Superscript>210</Superscript>Pb, <Superscript>228</Superscript>Ra and <Superscript>226</Superscript>Ra at southern South China Sea and Malacca Straits

Inventories and fluxes of ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra were determined in sediment cores collected at nine stations covering of the southern South China Sea and Malacca Straits with the thickness of water column between 42 and 83 m depth. The inventories of ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra were calculated range from 0.15–2.55 Bq cm⁻², 0.05–0.40 Bq cm⁻² and 6.83–83.63 Bq cm⁻², meanwhile the fluxes ranged from 0.005–0.079 Bq cm⁻² yr⁻¹, 0.009–0.048 Bq cm⁻² yr⁻¹ and 0.003–0.037 Bq cm⁻² yr⁻¹, respectively. The results show that the highest inventories and fluxes for ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra were found at station WC 01 and EC 05. Because there are additional sources of ²¹⁰Pb, ²²⁸Ra and ²²⁶Ra, where water transport will brings more dissolved isotopes, influence of the transportation and deposition of suspended particles, fast rate of regeneration and greater production of those radionuclides and others.     

Structure and electronic properties of hydrated mesityl oxide: a sequential quantum mechanics/molecular mechanics approach

The hydration of mesityl oxide (MOx) was investigated through a sequential quantum mechanics/molecular mechanics approach. Emphasis was placed on the analysis of the role played by water in the MOx syn–anti equilibrium and the electronic absorption spectrum. Results for the structure of the MOx–water solution, free energy of solvation and polarization effects are also reported. Our main conclusion was that in gas-phase and in low-polarity solvents, the MOx exists dominantly in syn-form and in aqueous solution in anti-form. This conclusion was supported by Gibbs free energy calculations in gas phase and in-water by quantum mechanical calculations with polarizable continuum model and thermodynamic perturbation theory in Monte Carlo simulations using a polarized MOx model. The consideration of the in-water polarization of the MOx is very important to correctly describe the solute–solvent electrostatic interaction. Our best estimate for the shift of the π–π^* transition energy of MOx, when it changes from gas-phase to water solvent, shows a red-shift of −2,520 ± 90 cm⁻¹, which is only 110 cm⁻¹ (0.014 eV) below the experimental extrapolation of −2,410 ± 90 cm⁻¹. This red-shift of around −2,500 cm⁻¹ can be divided in two distinct and opposite contributions. One contribution is related to the syn → anti conformational change leading to a blue-shift of ~1,700 cm⁻¹. Other contribution is the solvent effect on the electronic structure of the MOx leading to a red-shift of around −4,200 cm⁻¹. Additionally, this red-shift caused by the solvent effect on the electronic structure can by composed by approximately 60 % due to the electrostatic bulk effect, 10 % due to the explicit inclusion of the hydrogen-bonded water molecules and 30 % due to the explicit inclusion of the nearest water molecules.     

Hydrolysis behavior of a precursor for bridged polysilsesquioxane 1,4-bis(triethoxysilyl)benzene: a <Superscript>29</Superscript>Si NMR study

The hydrolysis behavior of 1,4-bis(triethoxysilyl)benzene (BTB), a precursor of bridged polysilsesquioxane, was investigated with high-resolution ²⁹Si nuclear magnetic resonance (²⁹Si NMR) spectroscopy at ambient temperature in a system with BTB:ethanol:water:HCl = 1:10:x:0.8 × 10⁻⁴ (x = 3, 6 or 9). Signals due to hydrolyzed triethoxysilyl groups as well as unhydrolyzed triethoxysilyl groups [−Si(OEt)₃, −Si(OEt)₂(OH), −Si(OEt)(OH)₂ and −Si(OH)₃ (OEt = OCH₂CH₃)] formed four sub-regions based on the number of hydroxyl groups bound to a silicon atom. In addition, one silicon environment influenced the other silicon environment by an intra-molecular interaction between two silicon atoms, and each sub-region for monomeric species thus contained four signals. Based on the development of signal intensity, it is revealed that one of the two triethoxysilyl groups in BTB is hydrolyzed preferentially. Thus, when a triethoxysilyl group is hydrolyzed, the −Si(OH) _x (OEt)_3−x (x = 1, 2) groups formed undergo further hydrolysis, which is opposite to the tendency expected from the hydrolysis behavior of organotrialkoxysilanes under acidic conditions.     

Ultra low level deep water <Superscript>137</Superscript>Cs activity in the South Pacific Ocean

We determined ¹³⁷Cs concentrations in deep water samples of the subtropical gyre in the South Pacific collected during the BEAGLE2003 cruise. This was done at an underground facility to achieve extremely low background γ-spectrometry, and we, therefore, obtained reliable values of ¹³⁷Cs activity in the deeper layers. ¹³⁷Cs activity in the layers between 2000 and 4500 m ranged from 7 ± 4 mBq m⁻³ to 25 ± 11 mBq m⁻³. The inventory of ¹³⁷Cs in the water column from 2000 m to the sea bottom was estimated to be 20 ± 8 Bq m⁻² to 94 ± 41 Bq m⁻² in this region.     

Application of ICP-QMS for the determination of ultratrace-levels of <Superscript>226</Superscript>Ra in geothermal water and sediment samples

A rapid, accurate and less labor intensive approach to determining ²²⁶Ra in environmental samples was examined; this utilized quadrupole-based inductively coupled plasma mass spectrometry (ICP-QMS). The procedure used chemical separation by ion exchange chromatography to remove most of the matrices after coprecipitation with BaSO₄. The average chemical recovery of the NIST SRM preparation method ranged from 60.5 to 85.9% using ¹³³Ba as internal tracer by gamma counting. This technique was capable of completing a ²²⁶Ra measurement within 3 min. It did not require an in-growth period to allow radon and its progeny to achieve secular equilibrium with the parent ²²⁶Ra as is needed for liquid scintillation analyzer (LSA). The method detection limits for the determination of ²²⁶Ra in geothermal water and sediment samples were 0.02 mBq L⁻¹ (0.558 fg L⁻¹) and 0.10 Bq kg⁻¹ (2.79 fg g⁻¹), respectively. The results obtained with various natural samples and the suitability of the method when applied to various environmental matrices such as geothermal water and sediment are discussed. When ICP-QMS was compared to double-focusing magnetic sector field inductively coupled plasma mass spectrometry (ICP-SFMS), good agreement was obtained with a correlation coefficient, r ² = 0.982.     

Solvent effects on the nπ* transition of pyrimidine in aqueous solution

A hybrid quantum mechanical and molecular mechanical potential is used in Monte Carlo simulations to examine the solvent effects on the electronic excitation energy for the n→π* transition of pyrimidine in aqueous solution. In the present study, the pyrimidine molecule is described by the semi-empirical AM1 model, while the solvent molecules are treated classically. Two sets of calculations are performed: the first involves the use of the pairwise three-point charge TIP3P model for water, and the second computation employs a polarizable many-body potential for the solvent. The latter calculation takes into account the effect of solvent polarization following the solute electronic excitation, and makes a correction to the energies determined using pairwise potentials, which neglects such fast polarization effects and overestimates the solute-solvent interactions on the Franck-Condon excited states. Our simulation studies of pyrimidine in water indicate that the solvent charge redistribution following the solute electronic excitation makes modest corrections (about −130␣cm⁻¹) to the energy predicted by using pairwise potentials. Specific hydrogen bonding interactions between pyrimidine and water are important for the prediction of solvatochromic shifts for pyrimidine. The computed n→π* blue shift is 2275±110 cm⁻¹, which may be compared with the experimental value (2700 cm⁻¹) from isooctane to water. Received: 14 January 1997 / Accepted: 21 February 1997     

Determination of <Superscript>90</Superscript>Sr, <Superscript>129</Superscript>I and gross beta radioactivity concentration in some teas

In this study, ⁹⁰Sr (540 keVβ ⁻), ¹²⁹I (150 keVβ ⁻) and the gross beta radioactivity concentrations were determined for the samples of tea as the most leading consumed hot drink in the markets (processed and packaged for sale) in our country. Furthermore, the obtained data were statistically analyzed. For determination of ¹²⁹I (150 keVβ⁻), ⁹⁰Sr (540 keVβ⁻) and gross radioactivity concentrations in tea samples, a sensor system consisting of scintillation detector with BP4 probe sensitive to beta radiation and a radiation meter (ST7) configurable for windows at desired power was used.     

Distribution of <Superscript>137</Superscript>Cs, <Superscript>40</Superscript>K, <Superscript>232</Superscript>Th and <Superscript>238</Superscript>U in coastal marine sediments of Margarita Island,Venezuela

This work presents the results of ¹³⁷Cs, ⁴⁰K, ²³²Th and ²³⁸U concentration (Bq kg⁻¹) values in coastal marine sediments collected from 38 sites along the coastline of the island of Margarita, Venezuela. The purpose was to determine baseline values for these radionuclides in surface marine sediments and to detect if there were any anomalously high concentration values. Only three of the 38 sediments analyzed had measurable values above the detection limit of 0.9 Bq kg⁻¹ for ¹³⁷Cs and the highest only being 1.4 Bq kg⁻¹. While, the concentration (Bq kg⁻¹) ranges for the primordial radionuclides, ⁴⁰K, ²³²Th and ²³⁸U were as follows: 12.2–211.7, <1.5–9.8 and <4.4–20.7, respectively. These concentration ranges for the primordial radionuclides can be considered as baseline values for surface marine sediments for areas that are considered not polluted by man or contaminated by nature. Finally, the concentration range of ¹³⁷Cs can also be employed as baseline values, which only seem to have been the result of the atmospheric testing of nuclear weapons in the past.     

Determination of HEPES in <Superscript>68</Superscript>Ga-labeled peptide solutions

A practical and reliable HPLC method was used for the determination of 2-[4-N-(2-hydroxyethyl)-1-piperazinyl]-N′-ethanesulfonic acid (HEPES) content in the ⁶⁸Ga-labeled [1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid]-1-Nal3-octreotide (DOTANOC). Linearity of this method was observed in a concentration range of 0.01–10 mg mL⁻¹ and the quantitative limit (signal to noise = 11) was determined as 10 μg mL⁻¹. The HEPES concentration in the final products of ⁶⁸Ga-DOTANOC was typically lower than the detection limit. Pure water and HEPES buffer as reaction medium were investigated using various activities of gallium-68. It was demonstrated that the presence of HEPES buffer consistently furnished very high radiochemical purity of ⁶⁸Ga-DOTANOC, which remained stable for several hours post-labeling. Evidence is provided that in addition to its role as a buffer, HEPES also functions as a radioprotectant agent.     

Levels of <Superscript>232</Superscript>Th activity in the South Adriatic Sea marine environment of Montenegro

²³²Th activities in the South Adriatic Sea-water, surface sediment, mud with detritus, seagrass (Posidonia oceanica) samples, and the mullet (Mugilidae) species Mugil cephalus, as well as soil and sand from the Montenegrin Coast, were measured using the six-crystal spectrometer PRIPYAT-2M, which has relatively high detection efficiency and a good sensitivity, and allows a short acquisition time, and measuring samples of any shape, without preliminary preparation and calibration measurements for different sample geometries. An average ²³²Th activity concentration in surface soil layer is found to be 40.33 Bq kg⁻¹, while in sand—4.7 Bq kg⁻¹. The absorbed dose rate in air due to ²³²Th gamma radiation from surface soil layer ranged from 11.76 to 63.39 nGy h⁻¹, with a mean of 24.06 nGy h⁻¹. Corresponding average annual effective dose rate has been found to be 0.03 mSv y⁻¹. The absorbed dose rates due to the thorium gamma radiation in air at 1 m above sand surface on the Montenegrin beaches have been found to be from 0.41 to 9.08 nGy h⁻¹, while annual effective dose rates ranged from 0.0005 to 0.011 mSv y⁻¹. ²³²Th activity concentration in seawater ranged from 0.06 to 0.22 Bq L⁻¹, as in the mullet (Mugil cephalus) whole individuals from 0.63 to 1.67 Bq kg⁻¹. Annual intake of ²³²Th by human consumers of this fish species has been estimated to provide an effective dose of about 0.003 mSv y⁻¹.     

<Superscript>224</Superscript>Ra and its implications in the East China Sea

The activities of ²²⁴Ra in the East China Sea (ECS) were measured by the Mn-fiber adsorption—emanation method. The horizontal and vertical distributions of ²²⁴Ra in the ECS in summer and winter were studied. The ranges of ²²⁴Ra activities were < lowest limit of detection (LLD)–5.88 Bq/m³ in summer with an average of 0.85 Bq/m³, and < LLD-7.50 Bq/m³ in winter with an average of 0.72 Bq/m³. And the distributions of ²²⁴Ra in the surface water were similar in these two seasons, decreasing rapidly with the increasing distance from the coast. The high ²²⁴Ra area was located within 30–100 km offshore and the lowest activities appeared in the Kuroshio Current. The vertical distributions of ²²⁴Ra showed two different characteristics. The horizontal and vertical eddy diffusion coefficients calculated by the one-dimensional state model of ²²⁴Ra were (7.1–88.9) × 10⁶cm²/s and 2.18–163 cm²/s, respectively. The upwelling rates off Zhejiang Province were calculated from ²²⁴Ra vertical distribution, which varied from 8.4 × 10⁻³cm/s to 13.3 × 10⁻³cm/s in summer and 16.3 × 10⁻³cm/s to 16.8 × 10⁻³cm/s in winter.     

The concentration of <Superscript>238</Superscript>U and the levels of gross radioactivity in surface waters of the Van Lake (Turkey)

Gross α and gross β activities and ²³⁸U concentrations were determined in 18 surface water samples collected from Van Lake. The instrumentations used to count the gross α and gross β activities and to determine the ²³⁸U concentrations were α/β counter of the multi-detector low background system (PIC-MPC-9604) and Inductively Coupled Plasma-Mass Spectrometry (Thermo Scientific Element 2), respectively. Concentrations ranging from 0.001 to 0.021 Bq L⁻¹ and from 0.111 to 2.794 Bq L⁻¹ were observed for the gross α and β activities in surface waters, respectively. For all samples the gross β activities were higher than the corresponding gross α activities. The results indicated that the gross α radioactive contamination in water samples was lower than recommended values for the guideline of drinking waters and most of the gross β activities in water samples were higher than those in the same procedure. The ²³⁸U concentrations ranged from 74.49 to 113.2 μg L⁻¹ in surface waters. The obtained results have showed that ²³⁸U concentrations are higher than guideline values for uranium.     

Radioactivity levels of <Superscript>238</Superscript>U and <Superscript>232</Superscript>Th,the α and β activities and associated dose rates from surface soil in Ulu Tiram,Malaysia

A survey was carried out to determine terrestrial gammaradiation dose rates, the concentration level of ²³⁸U and ²³²Th and α and β activities for the surface soil in Ulu Tiram, Malaysia A 125 measurements were performed using a NaI(T1) gamma-ray detector with crystal size of 1″ × 1″ on 15 soil samples collected from the site area about 102 km^{2 238}U and ²³²Th concentrations were determined in soils by using hyper pure germanium (HPGe) gamma-ray spectrometry. The activity of α and β from the surface soil was counted by using alpha beta counting system. The average value of ²³⁸U and ²³²Th concentrations in soil samples collected are 3.63±0.39 ppm within the range of 1.74±0.20 to 4.58±0.48 and 43.00±2.31 ppm within the range of 10.68±0.76 to 82 10±4.01 ppm, respectively. The average estimate of α and β activity in soil samples collected are 0.65±0.09 Bqg⁻¹ and 0.68±0.08 Bqg⁻¹, respectively. The average of terrestrial gamma-radiation dose rates measured in Ulu Tiram was found to be 200 nGy h⁻¹, within the range of 96 to 409 nGy h⁻¹. The population weighted outdoor annual effective dose was 1.2 mSv.     

Low level detection of <Superscript>135</Superscript>Cs and <Superscript>137</Superscript>Cs in environmental samples by ICP-MS

The measurement of fission product cesium isotopes ¹³⁵Cs and ¹³⁷Cs at low femtogram (fg) 10⁻¹⁵ levels in ground water by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) is reported. To eliminate the natural barium isobaric interference on the cesium isotopes, in-line chromatographic separation of the cesium from barium was performed followed by high sensitivity ICP-MS analysis. A high efficiency desolvating nebulizer system was employed to maximize ICP-MS sensitivity ~10 cps/fg. The three sigma detection limit for ¹³⁵Cs was 2 fg/mL (0.1 μBq/mL) and for ¹³⁷Cs 0.9 fg/mL (0.0027 Bq/mL) measured from the standard with analysis time of less than 30 min/sample. Cesium detection and 135/137 isotope ratio measurement at very low femtogram levels using this method in a spiked ground water matrix is also demonstrated.     

Calculation of <Superscript>15</Superscript>N NMR chemical shifts of amines in the framework of the density functional theory

The ¹⁵N NMR magnetic shielding constants (followed by recalculation into chemical shifts) in a representative series of amines were calculated in the framework of the density functional theory. The results were compared with experiment. The accuracy factors of this calculation (functional, basis set, solvent effects, and multistandard) were studied. Taking into account all the above factors leads to a noticeable decrease in the average absolute error in the calculation of the ¹⁵N NMR chemical shifts (from 13 to 4 ppm) in a range of their changing in the studies series of compounds of ～60 ppm (which is 6—7% in relative units).     

A colorimetric anion receptor containing the <Emphasis Type="Italic">cis</Emphasis>-Ru(bipy)<Subscript>2</Subscript><Superscript>2+</Superscript> group

When one or more nitro groups are incorporated into an anion receptor, intramolecular proton transfer from nearby –NH groups often takes place and is a significant obstacle for the construction of supramolecular systems. In this paper, by employing an intramolecular hydrogen bond between –NH and nitro groups in order to reduce the acidity of the amide group, we were able to construct a receptor that formed stable supramolecular systems. The receptor forms a 1:2 supramolecular compound with fluoride, whereas 1:1 complexes were formed with AcO⁻ and H₂PO₄ ⁻ in DMSO solution. Using this system, an easy-to-prepare test paper for the detection of F⁻ in low concentration at (10⁻⁴ M) in water was developed. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Scalar-relativistic 5f-in-core pseudopotentials and core-polarization potentials for trivalent actinides: calibration calculations for Ac<Superscript>3+</Superscript>, Cm<Superscript>3+</Superscript> and Lr<Superscript>3+</Superscript> complexes

The performance of recently proposed 5f-in-core pseudopotentials for the trivalent actinides was investigated in calculations for model complexes An³⁺L ⁿ⁻ for three selected actinides (An³⁺ = Ac³⁺, Cm³⁺, Lr³⁺) and eight simple ligands with atoms from the first three periods of the table of elements (L ⁿ⁻ = F⁻, Cl⁻, OH⁻, SH⁻, CO, NH₂⁻, H₂O, H₂S, NH₃). Results of Hartree-Fock and Coupled Cluster with singles, doubles and perturbative triples calculations using basis sets of quadruple-zeta quality are compared to corresponding reference data obtained with scalar-relativistic energy-adjusted 5f-in-valence small-core pseudopotentials. The inclusion of core-polarization potentials in the 5f-in-core pseudopotential calculations and corrections of the basis set superposition error by the counterpoise correction leads to very good agreement between the 5f-in-valence and 5f-in-core pseudopotential results for bond lengths, bond angles and binding energies. Results from 5f-in-core pseudopotential calculations using different density functionals also show reasonable agreement with the more rigorous Coupled Cluster results. It is argued that the An 5f rather than the An f population is a useful criterion for the applicability of a specific An 5f-in-core pseudopotential.     

Quantum-chemical calculations of NMR chemical shifts of organic molecules: IV. Effect of intermolecular coordination on <Superscript>31</Superscript>P NMR shielding constants and chemical shifts of molecular complexes of phosphorus pentachloride with azoles

Intermolecular coordination effects on the ³¹P NMR spectra of molecular complexes of N-vinylimidazole and 1-allyl-3,5-dimethylpyrazole with phosphorus pentachloride were studied by theoretical and experimental methods. The formation of intermolecular dative N→P bond was shown to be accompanied by upfield shift of the phosphorus resonance signal by more than 200 ppm. Appreciable contribution of relativistic effects to ³¹P NMR chemical shifts was revealed; the spin-orbital contribution to ³¹P shielding constant was estimated at >210 ppm. Consideration of solvent effect was found to be crucial while studying steric structure of molecular complexes of azoles with phosphorus pentachloride and intermolecular coordination effects on 31P NMR chemical shifts.     

Molecular modeling of hydration properties of hydrophobic ions Li<Superscript>+</Superscript>@C<Subscript>60</Subscript> and K<Superscript>+</Superscript>@C<Subscript>60</Subscript>

The Gibbs free energies of solvation (ΔG _s) and the electronic structures of endohedral metallofullerenes M⁺@C₆₀ (M⁺= Li⁺, K⁺) were calculated within the framework of the density functional theory and the polarizable continuum model. In water environment, the equilibrium position of K⁺ is at the center of the fullerene cavity whereas that of Li⁺ is shifted by 0.14 nm toward the fullerene cage. The Li⁺ cation is stabilized by interactions with both the fullerene and solvent. The equilibrium structures of both endohedral metallofullerenes are characterized by very close ΔG _s values. In particular, the calculated ΔG _s values for K⁺@C₆₀ are in the range from −124 to −149 kJ mol⁻¹ depending on the basis set and on the type of the density functional. Molecular dynamics simulations (TIP3P H₂O, OPLS force field, water sphere of radius 1.9 nm) showed that the radial distribution functions of water density around C₆₀ and M⁺@C₆₀ are very similar, whereas orientations of water dipoles around the endohedral metallofullerenes resemble the hydration pattern of isolated metal ions.