"iDoctor – Medical Blog"

Stephanie L. Brooke: Creative Arts Therapies Manual: A Guide to the History, Theoretical Approaches, Assessment, and Work with Special Populations of Art, Play, Dance, Music, Drama, and Poetry Therapies

• Content Type Journal Article
• Category Book Review
• Pages 1-3
• DOI 10.1007/s10465-012-9127-9
• Authors
  • Enid G. Wolf-Schein, University of Alberta, 1703 Andros Isle #j-2, Coconut Creek, FL 33066, USA

• Journal American Journal of Dance Therapy
• Online ISSN 1573-3262
• Print ISSN 0146-3721

Sharon Chaiklin and Hilda Wengrower (eds.): The Art and Science of Dance/Movement Therapy: Life is Dance

• Content Type Journal Article
• Category Book Review
• Pages 1-3
• DOI 10.1007/s10465-012-9126-x
• Authors
  • Julie Miller, Pratt Institute Brooklyn, New York, USA

• Journal American Journal of Dance Therapy
• Online ISSN 1573-3262
• Print ISSN 0146-3721

Publication year: 2012
Source: Journal of Molecular Structure, Available online 18 February 2012

Hao-Hong Li, Yun-Jie Wang, Zhao-Xun Lian, Yong-Fu Xu, Min Wang, …

Three new haloplumbates(II)/aromatic N-heterocyclic organic hybrids, [(nmp)(PbI3)]n(nmp=N-methylpyrazine)(1), [(dhpp)(Pb2Cl6)]n(dhpp=6,12-dihydrodipyrido[1,2-a:1’,2’-d] pyrazinium)(2), [(dedp)3(Pb6I18)]n(dedp=N,N’-diethyl-4,4’-dipyridinium)(3) have been synthesized and structurally determined. These polymeric haloplumbates exhibit different model type structures, including one-dimensional linear chain (for1), ribbonlike arrangement based on face- and edge-sharing PbXntetagonal pyramids or octahedra(for2and3), and N-heterocyclic organic cations weakly interact with inorganic haloplumbates to present 3-D supramolecular networks. Three compounds posses semiconducting properties with Egranging among 2.07-2.71eV. Photoluminescence and third-order nonlinear optical (NLO) activity of3were also discussed.

Highlights

► Hybrid haloplumbate solids containing aromatic N-heterocyclic molecules. ► Semiconducting properties with Egranging among 2.07-2.71eV. ► Photoluminescence, third-order nonlinear optical (NLO) activity of3.

Publication year: 2012
Source: Journal of Molecular Structure, Available online 18 February 2012

Krzysztof Marciniec, Andrzej Maślankiewicz, Maria J. Maślankiewicz, Rafał Kurczab

The one-step synthesis of positional isomers ofN,N-dimethylsulfamoylquinoline are presented. Seven newly synthesized compounds have been characterized by elemental analyses, MS,H andN NMR spectral data. The long-range correlations between the ring protons and the endocyclic nitrogen atoms were observed in the gHMBC experiments. The spectral positions of the nitrogen atoms from the sulfonamide groups were drawn from the 1D spectra of theN-labeled sulfonamide isotopomers. Correlations between the experimentally determined chemical shifts and GIAO calculated isotropic shielding constants were found. The GIAO calculations were based on HF-, MP2-, and B3LYP-optimized geometries and were performed at the HF, BLYP, and B3LYP levels of theory.

Publication year: 2012
Source: Journal of Molecular Structure, Available online 18 February 2012

Valia Nikolova, Diana Cheshmedzhieva, Sonia Ilieva, Boris Galabov

Density functional theory computations at the B3LYP/6-311+G(2d,2p) level for a series of 25 para-subsituted phenoxide ions were performed in analyzing the intramolecular effects determining the σreactivity constants for aromatic systems. Very good linear relationships were established between the electrostatic potential at nuclei values, NBO and Hirshfeld atomic charges at the phenoxide oxygen in p-substituted phenolates and the σconstants. Comparisons of the charge shifts induced by polar groups at para position in the phenoxides and in substituted at position 4 bicyclo[2.2.2]octan-1-olates reveals that very strong conjugative effects determine the high values of σconstants for electron-withdrawing substituents. Inversely, low charge transfer between substituents and the negatively charged reaction center in the case of electron donating groups is in harmony with the low values for the σconstants for such moieties. The unusual resonance interactions between substituents and the negatively charged reaction center were quantitatively assessed.

Publication year: 2012
Source: Journal of Molecular Structure, Available online 18 February 2012

C. Gruian, A. Vulpoi, H.-J. Steinhoff, S. Simon

Functional protein adsorption at liquid-solid interfaces has been intensively studied in the last years, however it is difficult to evidence directly conformational changes of the protein which are likely to appear upon adsorption. Spin labeling in combination with Electron Paramagnetic Resonance (EPR) spectroscopy was applied in this study to investigate adsorption of horse methemoglobin to bioactive glass (BG) similar in composition with 45S5 Bioglass®. X-band cw-EPR spectra of spin labeled methemoglobin in solution were compared to those obtained after adsorption on bioactive glass surface (functionalized and non-functionalized with glutaraldehyde), to extract information of the structure and dynamics in the vicinity of position β-93. The concentration of methemoglobin adsorbed on BG substrate was determined from the intensity of cw-EPR spectra and correlated with images obtained by Scanning Electron Microscopy (SEM). Line shape analysis of the EPR spectra revealed that ionic strength does not induce significant conformational changes in the protein structure upon adsorption, however, the chemical treatment applied to the bioactive glass surface positively influences protein adsorption.

Highlights

► The study is focused on less investigated interaction of a bioactive glass (BG) with methemoglobin and MnmE (5-methyl-aminomethyl-uridine forming enzyme) proteins. ► EPR analysis revealed structural changes of the protein in the adsorbed state and confirmed that, upon adsorption on BG, the use of glutaraldehyde (GA) helps in maintaining the surroundings of β-93 position close to the native state. ► SEM analysis revealed that GA leads to the cross-linking of hemoglobin, resulting in chain formation of macromolecules consisting of 8-10 proteins; while protein coverage is more dense when the adsorption is made in a low salt concentration medium.

Publication year: 2012
Source: Journal of Molecular Structure, Available online 18 February 2012

Xiang Zhang

On the basis of the tandem mass spectrometry (MS/MS) technique and density functional theory (DFT) calculations, we have studied the decarboxylation reactions of several anionic lithium complexes of the doubly deprotonated dicarboxylic acids, which include succinic acid,L-malic acid,L-mercaptosuccinic acid,L-aspartic acid and oxalacetic acid et al. Tandem mass spectrometry experiments indicate that the decarboxylation reactions of these complexes in the gas phase can all take place. DFT calculations show that the α-substituted groups in the dicarboxylic acids, such as -OH, -NH2and -SH et al, can advance the decarboxylation of the corresponding anionic lithium complexes. Meanwhile, the decarboxylation generally happens at the carboxylate group that is away from the substituent. This opinion is also supported by the bond angle analyses of the carboxylate groups.

Highlights

► Using MS/MS technique and DFT to study the decarboxylation of several anionic lithium complexes. ► The α-substituted groups in the dicarboxylic acids can advance the decarboxylation. ► The decarboxylation generally happens to the carboxylate group away from the substituent.

Publication year: 2012
Source: Journal of Molecular Structure, Available online 17 February 2012

Peter Klaeboe, Valdemaras Aleksa, Claus J. Nielsen, Anne Horn, Gamil A. Guirgis, …

Raman spectra of 1-fluoro-1-silacyclohexane as a liquid were recorded at 293 K and polarization data obtained. Additional Raman spectra were recorded at various temperatures between 293 and 143 K, and intensity changes of certain bands with temperature were investigated. An apparently plastic phase was observed around 170 K, but no definite crystallization was ever obtained on cooling. The infrared spectra have been studied of the vapour, of an amorphous solid at 78 K and of the liquid in the range 600-100 cm. No infrared bands present in the vapour or liquid vanished upon cooling.The compound existsa prioriin two conformers,equatorial (e)andaxial (a), and the experimental results suggest an equilibrium in which thea-conformer has 1.2 kJ mollower enthalpy than thee-conformer in the liquid, leading to 60%a-conformer at ambient temperature.B3LYP calculations with various basis sets and the G3 model chemistry gave conformational enthalpy difference ΔH(e-a) in the range 0.6 and 1.8 kJ mol. Infrared and Raman intensities, polarization ratios and vibrational frequencies for theeandaconformers were calculated. The wavenumbers of the vibrational modes were derived in the anharmonic approximation in B3LYP/cc-pVTZ calculations. An average relative deviation of ca. 1% between the observed and calculated wavenumbers for the 48 modes of theeandaconformers was found.

Highlights

► Infrared and Raman spectra were recorded in different phases. ► The enthalpy difference ΔH(e-a) was observed by Raman spectroscopy. ► DFT calculations made in the anharmonic approximation (B3LYP/cc-pVTZ). ► The vibrational modes of the and a conformers were observed and calculated. ► 1-fluoro-1-silacyclohexane was prepared and purified.

Publication year: 2012
Source: Journal of Molecular Structure, Available online 17 February 2012

Desislava Staneva, Paula Bosch, Ivo Grabchev

A poly(propyleneamine) dendrimer, comprising four 4-(N,N-dimethylaminoethyloxy)-1,8-naphthalimide units in the dendrimer periphery has been synthesized for the first time. The new blue fluorescent dendrimer has been obtained by nucleophilic substitution of the nitro groups at C-4 position of 1,8-naphthalimide units byN,N-dimethylaminoethyloxy moiety under ultrasonic conditions. Its photophysical characteristics have been investigated in organic solvents of different polarity. The influence of different metal cations on the dendrimer fluorescence has been also investigated viewing its sensor potential.

Highlights

► New blue fluorescent poly(propyleneamine) dendrimer has been synthesized under ultrasonic conditions. ► Photophysical properties have been investigated in organic solvents with different polarity. ► The new dendrimer is selective for Feions.

Publication year: 2012
Source: Journal of Molecular Structure, Available online 17 February 2012

Beata Morak-Młodawska, Kinga Suwińska, Krystian Pluta, Małgorzata Jeleń

The modification of the phenothiazine structure via the substitution of the benzene ring with the pyridine ring may proceed through the Ullmann cyclization or the Smiles rearrangement of the appropriate sulfide followed by cyclization. Reaction of dipyridyl sulfide (4) with 4-chloro-3-nitropyridine (5) in DMF can lead to one of the isomeric nitropyridyldiazaphenothiazines (7,9or10). Two-dimensionalH NMR experiments (COSY and ROESY) and a single crystal X-ray diffraction study were used to reveal the right product structure10, being the result of an uncommon reaction mechanism involving the double Smiles rearrangement of the S-N type. The tricyclic diazaphenothiazine system is not planar, folded along the S-N axis with the butterfly angle of 149.38(7)° between two pyridine rings. The central thiazine ring is in boat conformation with the nitropyridyl substituent located in equatorial position with the S5···N10–C11 angle of 162.3(2)°. The pyridyl substituent plane bisects the tricyclic ring system showing the dihedral angle between this plane and the C4a/C5a/C9a/C10a plane of 70.7(7)°. The nitro group is located intra the dipyridothiazine system and is tilted from the pyridine ring by 30.4(2)°.

Highlights

► Reaction of dipyridyl sulfide with chloronitropyridine led to a new phenothiazine type. ► The reaction may lead to 3 possible isomeric 10-nitropyridyldipyridothiazines. ► The reaction proceeded through a very rare double Smiles rearrangement. ► Only X-ray study showed the right structure and folding ring system along N-S axis. ► The central ring is in boat conformation with the equatorial nitropyridyl group.