Lanthanide-Connecting and Lone-Electron-Pair Active Trigonal-Pyramidal-AsO3 Inducing Nanosized Poly(polyoxotungstate) Aggregates and Their Anticancer Activities

NASA Astrophysics Data System (ADS)

Zhao, Jun-Wei; Li, Hai-Lou; Ma, Xing; Xie, Zhigang; Chen, Li-Juan; Zhu, Yongsheng

2016-05-01

By virtue of the stereochemical effect of the lone-electron pair located on the trigonal-pyramidal-AsO3 groups and the one-pot self-assembly strategy in the conventional aqueous solution, a series of novel lanthanide-bridging and lone-electron-pair active trigonal-pyramidal-AsO3 inducing nanosized poly(polyoxotungstate) aggregates [H2N(CH3)2]6 Na24H16{[Ln10W16(H2O)30O50](B-α-AsW9O33)8}·97H2O [Ln = EuIII (1), SmIII (2), GdIII (3), TbIII (4), DyIII (5), HoIII (6), ErIII (7), TmIII (8)] were prepared and further characterized by elemental analyses, IR spectra, UV spectra, thermogravimetric (TG) analyses and single-crystal X-ray diffraction. The most remarkable structural feature is that the polyanionic skeleton of {[Ln10W16(H2O)30O50](B-α-AsW9O33)8}46- is constructed from eight trivacant Keggin [B-α-AsW9O33]9- fragments through ten Ln centers and sixteen bridging W atoms in the participation of fifty extraneous oxygen atoms. Notably, 4 and 8 can be stable in the aqueous solution not only for eight days but also in the range of pH = 3.9-7.5. Moreover, the cytotoxicity tests of 4 and 8 toward human cervical cancer (HeLa) cells, human breast cancer (MCF-7) cells and mouse fibroblast (L929) cells were performed by the 3-(4,5-cimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay and the cell apoptosis processes were characterized by calcein AM/PI staining experiments, annexin V-FITC/PI staining experiments and morphological changes.

Dominance of broken bonds and nonbonding electrons at the nanoscale

NASA Astrophysics Data System (ADS)

Sun, Chang Q.

2010-10-01

Although they exist ubiquitously in human bodies and our surroundings, the impact of nonbonding lone electrons and lone electron pairs has long been underestimated. Recent progress demonstrates that: (i) in addition to the shorter and stronger bonds between under-coordinated atoms that initiate the size trends of the otherwise constant bulk properties when a substance turns into the nanoscale, the presence of lone electrons near to broken bonds generates fascinating phenomena that bulk materials do not demonstrate; (ii) the lone electron pairs and the lone pair-induced dipoles associated with C, N, O, and F tetrahedral coordination bonding form functional groups in biological, organic, and inorganic specimens. By taking examples of surface vacancy, atomic chain end and terrace edge states, catalytic enhancement, conducting-insulating transitions of metal clusters, defect magnetism, Coulomb repulsion at nanoscale contacts, Cu3C2H2 and Cu3O2 surface dipole formation, lone pair neutralized interface stress, etc, this article will focus on the development and applications of theory regarding the energetics and dynamics of nonbonding electrons, aiming to raise the awareness of their revolutionary impact to the society. Discussion will also extend to the prospective impacts of nonbonding electrons on mysteries such as catalytic enhancement and catalysts design, the density anomalies of ice and negative thermal expansion, high critical temperature superconductivity induced by B, C, N, O, and F, the molecular structures and functionalities of CF4 in anti-coagulation of synthetic blood, NO signaling, and enzyme telomeres, etc. Meanwhile, an emphasis is placed on the necessity and effectiveness of understanding the properties of substances from the perspective of bond and nonbond formation, dissociation, relaxation and vibration, and the associated energetics and dynamics of charge repopulation, polarization, densification, and localization. Finding and grasping the factors controlling the nonbonding states and making them of use in functional materials design and identifying their limitations will form, in the near future, a subject area of ``nonbonding electronics and energetics'', which could be even more challenging, fascinating, promising, and rewarding than dealing with core or valence electrons alone.

Quantitative analysis of harmonic convergence in mosquito auditory interactions

PubMed Central

Aldersley, Andrew; Champneys, Alan; Robert, Daniel

2016-01-01

This article analyses the hearing and behaviour of mosquitoes in the context of inter-individual acoustic interactions. The acoustic interactions of tethered live pairs of Aedes aegypti mosquitoes, from same and opposite sex mosquitoes of the species, are recorded on independent and unique audio channels, together with the response of tethered individual mosquitoes to playbacks of pre-recorded flight tones of lone or paired individuals. A time-dependent representation of each mosquito's non-stationary wing beat frequency signature is constructed, based on Hilbert spectral analysis. A range of algorithmic tools is developed to automatically analyse these data, and used to perform a robust quantitative identification of the ‘harmonic convergence’ phenomenon. The results suggest that harmonic convergence is an active phenomenon, which does not occur by chance. It occurs for live pairs, as well as for lone individuals responding to playback recordings, whether from the same or opposite sex. Male–female behaviour is dominated by frequency convergence at a wider range of harmonic combinations than previously reported, and requires participation from both partners in the duet. New evidence is found to show that male–male interactions are more varied than strict frequency avoidance. Rather, they can be divided into two groups: convergent pairs, typified by tightly bound wing beat frequencies, and divergent pairs, that remain widely spaced in the frequency domain. Overall, the results reveal that mosquito acoustic interaction is a delicate and intricate time-dependent active process that involves both individuals, takes place at many different frequencies, and which merits further enquiry. PMID:27053654

Rationalizing the structural variability of the exocyclic amino groups in nucleobases and their metal complexes: cytosine and adenine.

PubMed

Fonseca Guerra, Célia; Sanz Miguel, Pablo J; Cebollada, Andrea; Bickelhaupt, F Matthias; Lippert, Bernhard

2014-07-28

The exocyclic amino groups of cytosine and adenine nucleobases are normally almost flat, with the N atoms essentially sp(2) hybridized and the lone pair largely delocalized into the heterocyclic rings. However, a change to marked pyramidality of the amino group (N then sp(3) hybridized, lone pair essentially localized at N) occurs during i) involvement of an amino proton in strong hydrogen bonding donor conditions or ii) with monofunctional metal coordination following removal of one of the two protons. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Sb content on the physical properties of Ge-Se-Te chalcogenide glasses

NASA Astrophysics Data System (ADS)

Vashist, Priyanka; Anjali, Patial, Balbir Singh; Thakur, Nagesh

2018-05-01

In the present study, the bulk as-(Se80Te20)94-xGe6Sbx (x = 0, 1, 2, 4, 6, 8) glasses were synthesized using melt quenching technique. The physical properties viz coordination number, lone pair of electrons, number of constraints, glass transition temperature, mean bond energy, cohesive energy, electro-negativity and average heat of atomization of the investigated composition are reported and discussed. It is inferred that on increasing Sb content; average coordination number, average number of constraints, mean bond energy, cohesive energy and glass transition temperature increases but lone pair of electrons, average heat of atomization and deviation of stoichiometry decreases.

Rabbit-Ears Hybrids, VSEPR Sterics, and Other Orbital Anachronisms

ERIC Educational Resources Information Center

Clauss, Allen D.; Nelsen, Stephen F.; Ayoub, Mohamed; Moore, John W.; Landis, Clark R.; Weinhold, Frank

2014-01-01

We describe the logical flaws, experimental contradictions, and unfortunate educational repercussions of common student misconceptions regarding the shapes and properties of lone pairs, inspired by overemphasis on ''valence shell electron pair repulsion'' (VSEPR) rationalizations in current freshmanlevel chemistry textbooks. VSEPR-style…

Selectivity assessment of DB-200 and DB-VRX open-tubular capillary columns.

PubMed

Kiridena, W; Koziola, W W; Poole, C F

2001-10-12

The solvation parameter model is used to study the influence of composition and temperature on the selectivity of two poly(siloxane) stationary phases used for open-tubular capillary column gas chromatography. The poly(methyltrifluoropropyldimethylsiloxane) stationary phase, DB-200, has low cohesion, intermediate dipolarity/polarizability, low hydrogen-bond basicity, no hydrogen-bond acidity, and repulsive electron lone pair interactions. The DB-VRX stationary phase has low cohesion, low dipolarity/polarizability, low hydrogen-bond basicity and no hydrogen-bond acidity and no capacity for electron lone pair interactions. The selectivity of the two stationary phases is complementary to those in a database of 11 stationary phase chemistries determined under the same experimental conditions.

Water Lone Pair Delocalization in Classical and Quantum Descriptions of the Hydration of Model Ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Remsing, Richard C.; Duignan, Timothy T.; Baer, Marcel D.

Understanding the nature of ionic hydration at a fundamental level has eluded scientists despite intense interest for nearly a century. In particular, the microscopic origins of the asymmetry of ion solvation thermodynamics with respect to the sign of the ionic charge remains a mystery. Here, we determine the response of accurate quantum mechanical water models to strong nanoscale solvation forces arising from excluded volumes and ionic electrostatic fields. This is compared to the predictions of two important limiting classes of classical models of water with fixed point changes, differing in their treatment of "lone-pair" electrons. Using the quantum water modelmore » as our standard of accuracy, we find that a single fixed classical treatment of lone pair electrons cannot accurately describe solvation of both apolar and cationic solutes, underlining the need for a more flexible description of local electronic effects in solvation processes. However, we explicitly show that all water models studied respond to weak long-ranged electrostatic perturbations in a manner that follows macroscopic dielectric continuum models, as would be expected. We emphasize the importance of these findings in the context of realistic ion models, using density functional theory and empirical models, and discuss the implications of our results for quantitatively accurate reduced descriptions of solvation in dielectric media.« less

Divalent carbon(0) chemistry, part 1: Parent compounds.

PubMed

Tonner, Ralf; Frenking, Gernot

2008-01-01

Quantum-chemical calculations with DFT (BP86) and ab initio methods [MP2, SCS-MP2, CCSD(T)] have been carried out for the molecules C(PH(3))(2) (1), C(PMe(3))(2) (2), C(PPh(3))(2) (3), C(PPh(3))(CO) (4), C(CO)(2) (5), C(NHC(H))(2) (6), C(NHC(Me))(2) (7) (Me(2)N)(2)C=C=C(NMe(2))(2) (8), and NHC (9), where NHC=N-heterocyclic carbene and NHC(Me)=N-methyl-substituted NHC. The electronic structure in 1-9 was analyzed with charge- and energy-partitioning methods. The results show that the bonding situations in L(2)C compounds 1-8 can be interpreted in terms of donor-acceptor interactions between closed-shell ligands L and a carbon atom which has two lone-pair orbitals L-->C<--L. This holds particularly for the carbodiphosphoranes 1-3 where L=PR(3), which therefore are classified as divalent carbon(0) compounds. The NBO analysis suggests that the best Lewis structures for the carbodicarbenes 6 and 7 where L is a NHC ligand have C==C==C double bonds as in the tetraaminoallene 8. However, the Lewis structures of 6-8, in which two lone-pair orbitals at the central carbon atom are enforced, have only a slightly higher residual density. Visual inspection of the frontier orbitals of the latter species reveals their pronounced lone-pair character, which suggests that even the quasi-linear tetraaminoallene 8 is a "masked" divalent carbon(0) compound. This explains the very shallow bending potential of 8. The same conclusion is drawn for phosphoranylketene 4 and for carbon suboxide (5), which according to the bonding analysis have hidden double-lone-pair character. The AIM analysis and the EDA calculations support the assignment of carbodiphosphoranes as divalent carbon(0) compounds, while NHC 9 is characterized as a divalent carbon(II) compound. The L-->C((1)D) donor-acceptor bonds are roughly twice as strong as the respective L-->BH(3) bond.

Impact of Pb content on the physical parameters of Se-Te-Pb system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anjali,; Sharma, Raman; Thakur, Nagesh

2015-05-15

In the present study, we have investigated the impact of Pb content on the physical parameters in Se-Te-Pb system via average coordination number, constraints, the fraction of floppy modes, cross-linking density, lone pairs electrons, heat of atomization, mean bond energy, cohesive energy and electronegativity. The bulk samples have been prepared by using melt quenching technique. X-ray diffraction pattern of various samples indicates the amorphous nature of investigated glassy alloys. It is observed that average coordination number, average number of constraints and cross-linking density increase with Pb content. However, lone-pair electrons, floppy modes, average heat of atomization, cohesive energy and meanmore » bond energy are found to decrease with Pb atomic percentage.« less

Influence of polyhedron distortions on calculated bond-valence sums for cations with one lone electron pair.

PubMed

Wang, X; Liebau, F

2007-04-01

In the present bond-valence model (BVM), the bond-valence parameters r(0) and b are, in general, supposed to be constant for each A-X pair and equal to 0.37 A for all A-X pairs, respectively. For [A(i)(X(j))(n)] coordination polyhedra that do not deviate strongly from regularity, these suppositions are well fulfilled and calculated values for the bond-valence sums (BVS)(i) are nearly equal to the whole-number values of the stoichiometric valence. However, application of the BVM to 2591 [L(i)(X(j))(n)] polyhedra, where L are p-block cations, i.e. cations of the 13th to 17th group of the periodic system of elements, with one lone electron pair and X = O(-II), S(-II) and Se(-II), shows that r(0i) values of individual [LX(n)] polyhedra are correlated with the absolute value /Phi(i)/ of an eccentricity parameter, Phi(i), which is higher for more distorted [LX(n)] polyhedra. As a consequence, calculated (BVS)(i) values for these polyhedra are also correlated with /Phi(i)/, rather than being numerically equal to the stoichiometric valence of L. This is interpreted as the stereochemical influence of the lone electron pair of L. It is shown that the values of the correlation parameters and the R(2) values of the correlation equations depend on the position of the L cation in the periodic system of elements, if the correlations are assumed to be linear. This observation suggests that (BVS)(L) describes a chemical quantity that is different from the stoichiometric valence of L.

Bombing Alone: Tracing the Motivations and Antecedent Behaviors of Lone-Actor Terrorists*,†,‡

PubMed Central

Gill, Paul; Horgan, John; Deckert, Paige

2014-01-01

This article analyzes the sociodemographic network characteristics and antecedent behaviors of 119 lone-actor terrorists. This marks a departure from existing analyses by largely focusing upon behavioral aspects of each offender. This article also examines whether lone-actor terrorists differ based on their ideologies or network connectivity. The analysis leads to seven conclusions. There was no uniform profile identified. In the time leading up to most lone-actor terrorist events, other people generally knew about the offender’s grievance, extremist ideology, views, and/or intent to engage in violence. A wide range of activities and experiences preceded lone actors’ plots or events. Many but not all lone-actor terrorists were socially isolated. Lone-actor terrorists regularly engaged in a detectable and observable range of activities with a wider pressure group, social movement, or terrorist organization. Lone-actor terrorist events were rarely sudden and impulsive. There were distinguishable behavioral differences between subgroups. The implications for policy conclude this article. PMID:24313297

Bombing alone: tracing the motivations and antecedent behaviors of lone-actor terrorists,.

PubMed

Gill, Paul; Horgan, John; Deckert, Paige

2014-03-01

This article analyzes the sociodemographic network characteristics and antecedent behaviors of 119 lone-actor terrorists. This marks a departure from existing analyses by largely focusing upon behavioral aspects of each offender. This article also examines whether lone-actor terrorists differ based on their ideologies or network connectivity. The analysis leads to seven conclusions. There was no uniform profile identified. In the time leading up to most lone-actor terrorist events, other people generally knew about the offender's grievance, extremist ideology, views, and/or intent to engage in violence. A wide range of activities and experiences preceded lone actors' plots or events. Many but not all lone-actor terrorists were socially isolated. Lone-actor terrorists regularly engaged in a detectable and observable range of activities with a wider pressure group, social movement, or terrorist organization. Lone-actor terrorist events were rarely sudden and impulsive. There were distinguishable behavioral differences between subgroups. The implications for policy conclude this article. © 2013 American Academy of Forensic Sciences.

Charge disproportionation of mixed-valent Cr triggered by Bi lone-pair effect in the A -site-ordered perovskite BiC u3C r4O12

NASA Astrophysics Data System (ADS)

Etter, Martin; Isobe, Masahiko; Sakurai, Hiroya; Yaresko, Alexander; Dinnebier, Robert E.; Takagi, Hidenori

2018-05-01

A new A -site-ordered perovskite BiC u3C r4O12 is synthesized under a high pressure of 7.7 GPa. A phase transition from a paramagnetic metal to a ferrimagnetic metal is observed at Tc=190 K accompanied with a structural change from cubic to monoclinic. Structural analysis of the low-temperature monoclinic phase reveals that this transition represents a charge disproportionation of C r3.75 + into C r4 + and C r3.5 + . We argue that the asymmetric displacement of Bi caused by a lone-pair effect triggers the formation of a dimeric Cr4+2O5 unit and leads to an ordering of C r4 + and C r3.5 + below the transition.

ns2np4 (n = 4, 5) lone pair triplets whirling in M*F2E3 (M* = Kr, Xe): Stereochemistry and ab initio analyses

NASA Astrophysics Data System (ADS)

Galy, Jean; Matar, Samir F.

2017-02-01

The stereochemistry of ns2np4 (n = 4, 5) lone pair LP characterizing noble gas Kr and Xe (labeled M*) in M*F2 difluorides is examined within coherent crystal chemistry and ab initio visualizations. M*2+ in such oxidation state brings three lone pairs (E) and difluorides are formulated M*F2E3. The analyses use electron localization function (ELF) obtained within density functional theory calculations showing the development of the LP triplets whirling {E3} quantified in the relevant chemical systems. Detailed ELF data analyses allowed showing that in α KrF2E3 and isostructural XeF2E3 difluorides the three E electronic clouds merge or hybridize into a torus and adopt a perfect gyration circle with an elliptical section, while in β KrF2 the network architecture deforms the whole torus into an ellipsoid shape. Original precise metrics are provided for the torus in the different compounds under study. In KrF2 the geometric changes upon β → α phase transition is schematized and mechanisms for the transformation with temperature or pressure are proposed. The results are further highlighted by electronic band structure calculations which show similar features of equal band gaps of 3 eV in both α and β KrF2 and a reorganization of frontier orbitals due to the different orientations of the F-Kr-F linear molecule in the two tetragonal structures.

Atom-bond electronegativity equalization method fused into molecular mechanics. I. A seven-site fluctuating charge and flexible body water potential function for water clusters.

PubMed

Yang, Zhong-Zhi; Wu, Yang; Zhao, Dong-Xia

2004-02-08

Recently, experimental and theoretical studies on the water system are very active and noticeable. A transferable intermolecular potential seven points approach including fluctuation charges and flexible body (ABEEM-7P) based on a combination of the atom-bond electronegativity equalization and molecular mechanics (ABEEM/MM), and its application to small water clusters are explored and tested in this paper. The consistent combination of ABEEM and molecular mechanics (MM) is to take the ABEEM charges of atoms, bonds, and lone-pair electrons into the intermolecular electrostatic interaction term in molecular mechanics. To examine the charge transfer we have used two models coming from the charge constraint types: one is a charge neutrality constraint on whole water system and the other is on each water molecule. Compared with previous water force fields, the ABEEM-7P model has two characters: (1) the ABEEM-7P model not only presents the electrostatic interaction of atoms, bonds and lone-pair electrons and their changing in respond to different ambient environment but also introduces "the hydrogen bond interaction region" in which a new parameter k(lp,H)(R(lp,H)) is used to describe the electrostatic interaction of the lone-pair electron and the hydrogen atom which can form the hydrogen bond; (2) nonrigid but flexible water body permitting the vibration of the bond length and angle is allowed due to the combination of ABEEM and molecular mechanics, and for van der Waals interaction the ABEEM-7P model takes an all atom-atom interaction, i.e., oxygen-oxygen, hydrogen-hydrogen, oxygen-hydrogen interaction into account. The ABEEM-7P model based on ABEEM/MM gives quite accurate predictions for gas-phase state properties of the small water clusters (H(2)O)(n) (n=2-6), such as optimized geometries, monomer dipole moments, vibrational frequencies, and cluster interaction energies. Due to its explicit description of charges and the hydrogen bond, the ABEEM-7P model will be applied to discuss properties of liquid water, ice, aqueous solutions, and biological systems.

Ab initio molecular orbital and density functional studies on the ring-opening reaction of oxetene.

PubMed

Jayaprakash, S; Jeevanandam, Jebakumar; Subramani, K

2014-11-01

Electrocyclic ring opening (ERO) reaction of 2H-Oxete (oxetene) has been carried out computationally in the gas phase and ring opening barrier has been computed. When comparing the ERO reaction of oxetene with the parent hydrocarbon (cyclobutene), the ring opening of cyclobutene is found to exhibit pericyclic behavior while oxetene shows mild pseudopericyclic nature. Computation of the nucleus-independent chemical shift (NICS) of oxetene adds evidence for pseudopericyclic behavior of oxetene. By locking of lone pair of electrons by hydrogen bonding, it is seen that the pseudopericyclic nature of the ring opening of oxetene is converted into a pericyclic one. CASSCF(5,6)/6-311+G** computation was carried out to understand the extent of involvement of lone pair of electrons during the course of the reaction. CR-CCSD(T)/6-311+G** computation was performed to assess the energies of the reactant, transition state and the product more accurately.

New oxyfluorotellurates(IV): MTeO3F (M = FeIII, GaIII and CrIII).

PubMed

Laval, Jean Paul; Jennene Boukharrata, Nefla; Thomas, Philippe

2008-02-01

The crystal structures of the new isomorphous compounds iron(III) oxyfluorotellurate(IV), FeTeO(3)F, gallium(III) oxyfluorotellurate(IV), GaTeO(3)F, and chromium(III) oxyfluorotellurate(IV), CrTeO(3)F, consist of zigzag chains of MO(4)F(2) distorted octahedra alternately sharing O-O and F-F edges and connected via TeO(3) trigonal pyramids. A full O/F anionic ordering is observed and the electronic lone pair of the Te(IV) cation is stereochemically active.

Structure-Activity Relationships of Constrained Phenylethylamine Ligands for the Serotonin 5-HT2 Receptors

PubMed Central

Isberg, Vignir; Paine, James; Leth-Petersen, Sebastian; Kristensen, Jesper L.; Gloriam, David E.

2013-01-01

Serotonergic ligands have proven effective drugs in the treatment of migraine, pain, obesity, and a wide range of psychiatric and neurological disorders. There is a clinical need for more highly 5-HT2 receptor subtype-selective ligands and the most attention has been given to the phenethylamine class. Conformationally constrained phenethylamine analogs have demonstrated that for optimal activity the free lone pair electrons of the 2-oxygen must be oriented syn and the 5-oxygen lone pairs anti relative to the ethylamine moiety. Also the ethyl linker has been constrained providing information about the bioactive conformation of the amine functionality. However, combined 1,2-constriction by cyclization has only been tested with one compound. Here, we present three new 1,2-cyclized phenylethylamines, 9–11, and describe their synthetic routes. Ligand docking in the 5-HT2B crystal structure showed that the 1,2-heterocyclized compounds can be accommodated in the binding site. Conformational analysis showed that 11 can only bind in a higher-energy conformation, which would explain its absent or low affinity. The amine and 2-oxygen interactions with D3.32 and S3.36, respectively, can form but shift the placement of the core scaffold. The constraints in 9–11 resulted in docking poses with the 4-bromine in closer vicinity to 5.46, which is polar only in the human 5-HT2A subtype, for which 9–11 have the lowest affinity. The new ligands, conformational analysis and docking expand the structure-activity relationships of constrained phenethylamines and contributes towards the development of 5-HT2 receptor subtype-selective ligands. PMID:24244317

Structure-activity relationships of constrained phenylethylamine ligands for the serotonin 5-HT2 receptors.

PubMed

Isberg, Vignir; Paine, James; Leth-Petersen, Sebastian; Kristensen, Jesper L; Gloriam, David E

2013-01-01

Serotonergic ligands have proven effective drugs in the treatment of migraine, pain, obesity, and a wide range of psychiatric and neurological disorders. There is a clinical need for more highly 5-HT2 receptor subtype-selective ligands and the most attention has been given to the phenethylamine class. Conformationally constrained phenethylamine analogs have demonstrated that for optimal activity the free lone pair electrons of the 2-oxygen must be oriented syn and the 5-oxygen lone pairs anti relative to the ethylamine moiety. Also the ethyl linker has been constrained providing information about the bioactive conformation of the amine functionality. However, combined 1,2-constriction by cyclization has only been tested with one compound. Here, we present three new 1,2-cyclized phenylethylamines, 9-11, and describe their synthetic routes. Ligand docking in the 5-HT2B crystal structure showed that the 1,2-heterocyclized compounds can be accommodated in the binding site. Conformational analysis showed that 11 can only bind in a higher-energy conformation, which would explain its absent or low affinity. The amine and 2-oxygen interactions with D3.32 and S3.36, respectively, can form but shift the placement of the core scaffold. The constraints in 9-11 resulted in docking poses with the 4-bromine in closer vicinity to 5.46, which is polar only in the human 5-HT2A subtype, for which 9-11 have the lowest affinity. The new ligands, conformational analysis and docking expand the structure-activity relationships of constrained phenethylamines and contributes towards the development of 5-HT2 receptor subtype-selective ligands.

Effect of lone-electron-pair cations on the orientation of crystallographic shear planes in anion-deficient perovskites.

PubMed

Batuk, Dmitry; Batuk, Maria; Abakumov, Artem M; Tsirlin, Alexander A; McCammon, Catherine; Dubrovinsky, Leonid; Hadermann, Joke

2013-09-03

Factors affecting the structure and orientation of the crystallographic shear (CS) planes in anion-deficient perovskites were investigated using the (Pb(1-z)Sr(z))(1-x)Fe(1+x)O(3-y) perovskites as a model system. The isovalent substitution of Sr(2+) for Pb(2+) highlights the influence of the A cation electronic structure because these cations exhibit very close ionic radii. Two compositional ranges have been identified in the system: 0.05 ≤ z ≤ 0.2, where the CS plane orientation gradually varies but stays close to (203)p, and 0.3 ≤ z ≤ 0.45 with (101)p CS planes. The incommensurately modulated structure of Pb0.792Sr0.168Fe1.040O2.529 was refined from neutron powder diffraction data using the (3 + 1)D approach (space group X2/m(α0γ), X = (1/2, 1/2, 1/2, 1/2), a = 3.9512(1) Å, b = 3.9483(1) Å, c = 3.9165(1) Å, β = 93.268(2)°, q = 0.0879(1)a* + 0.1276(1)c*, RF = 0.023, RP = 0.029, and T = 900 K). A comparison of the compounds with different CS planes indicates that the orientation of the CS planes is governed mainly by the stereochemical activity of the lone-electron-pair cations inside the perovskite blocks.

Synthesis and antibacterial activity of sulfonamides. SAR and DFT studies

NASA Astrophysics Data System (ADS)

Boufas, Wahida; Dupont, Nathalie; Berredjem, Malika; Berrezag, Kamel; Becheker, Imène; Berredjem, Hajira; Aouf, Nour-Eddine

2014-09-01

A series of substituted sulfonamide derivatives were synthesized from chlorosulfonyl isocyanate (CSI) in tree steps (carbamoylation, sulfamoylation and deprotection). Antibacterial activity in vitro of some newly formed compounds investigated against clinical strains Gram-positive and Gram-negative: Escherichia coli and Staphylococcus aureus applying the method of dilution and minimal inhibition concentration (MIC) methods. These compounds have significant bacteriostatic activity with totalities of bacterial strains used. DFT calculations with B3LYP/6-31G(d) level have been used to analyze the electronic and geometric characteristics deduced for the stable structure of three compounds presenting conjugation between a nitrogen atom N through its lone pair and an aromatic ring next to it. The principal quantum chemical descriptors have been correlated with the antibacterial activity.

Electron (charge) density studies of cellulose models

USDA-ARS?s Scientific Manuscript database

Introductory material first describes electron density approaches and demonstrates visualization of electron lone pairs and bonding as concentrations of electron density. Then it focuses on the application of Bader’s Quantum Theory of Atoms-in-Molecules (AIM) to cellulose models. The purpose of the ...

Photoinduced intramolecular charge transfer (ICT) reaction in trans-methyl p-(dimethylamino) cinnamate: A combined fluorescence measurement and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Chakraborty, Amrita; Kar, Samiran; Guchhait, Nikhil

2006-01-01

The photophysical behaviour of trans-methyl p-(dimethylamino) cinnamate ( t-MDMAC) donor-acceptor system has been investigated by steady-state absorption and emission spectroscopy and quantum chemical calculations. The molecule t-MDMAC shows an emission from the locally excited state in non-polar solvents. In addition to weak local emission, a strong solvent dependent red shifted fluorescence in polar aprotic solvents is attributed to highly polar intramolecular charge transfer state. However, the formation of hydrogen-bonded clusters with polar protic solvents has been suggested from a linear correlation between the observed red shifted fluorescence band maxima with hydrogen bonding parameters ( α). Calculations by ab initio and density functional theory show that the lone pair electron at nitrogen center is out of plane of the benzene ring in the global minimum ground state structure. In the gas phase, a potential energy surface along the twist coordinate at the donor (-NMe 2) and acceptor (-CH = CHCOOMe) sites shows stabilization of S 1 state and destabilization S 2 and S 0 states. A similar potential energy calculation along the twist coordinate in acetonitrile solvent using non-equilibrium polarized continuum model also shows more stabilization of S 1 state relative to other states and supports solvent dependent red shifted emission properties. In all types of calculations it is found that the nitrogen lone pair is delocalized over the benzene ring in the global minimum ground state and is localized on the nitrogen centre at the 90° twisted configuration. The S 1 energy state stabilization along the twist coordinate at the donor site and localized nitrogen lone pair at the perpendicular configuration support well the observed dual fluorescence in terms of proposed twisted intramolecular charge transfer (TICT) model.

On the structure and dynamics of the hydrated sulfite ion in aqueous solution--an ab initio QMCF MD simulation and large angle X-ray scattering study.

PubMed

Eklund, Lars; Hofer, Thomas S; Pribil, Andreas B; Rode, Bernd M; Persson, Ingmar

2012-05-07

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) formalism has been applied in conjunction to experimental large angle X-ray scattering to study the structure and dynamics of the hydrated sulfite ion in aqueous solution. The results show that there is a considerable effect of the lone electron-pair on sulfur concerning structure and dynamics in comparison with the sulfate ion with higher oxidation number and symmetry of the hydration shell. The S-O bond distance in the hydrated sulfite ion has been determined to 1.53(1) Å by both methods. The hydrogen bonds between the three water molecules bound to each sulfite oxygen are only slightly stronger than those in bulk water. The sulfite ion can therefore be regarded as a weak structure maker. The water exchange rate is somewhat slower for the sulfite ion than for the sulfate ion, τ(0.5) = 3.2 and 2.6 ps, respectively. An even more striking observation in the angular radial distribution (ARD) functions is that the for sulfite ion the water exchange takes place in close vicinity of the lone electron-pair directed at its sides, while in principle no water exchange did take place of the water molecules hydrogen bound to sulfite oxygens during the simulation time. This is also confirmed when detailed pathway analysis is conducted. The simulation showed that the water molecules hydrogen bound to the sulfite oxygens can move inside the hydration shell to the area outside the lone electron-pair and there be exchanged. On the other hand, for the hydrated sulfate ion in aqueous solution one can clearly see from the ARD that the distribution of exchange events is symmetrical around the entire hydration sphere.

Manganese(II), iron(II), cobalt(II), and copper(II) complexes of an extended inherently chiral tris-bipyridyl cage.

PubMed

Perkins, David F; Lindoy, Leonard F; McAuley, Alexander; Meehan, George V; Turner, Peter

2006-01-17

Manganese(II), iron(II), cobalt(II), and copper(II) derivatives of two inherently chiral, Tris(bipyridyl) cages (L and L') of type [ML]-(PF(6))(2)(solvent)(n) and [FeL'](ClO(4))(2) are reported, where L is the hexa-tertiary butyl-substituted derivative of L'. These products were obtained by using the free cage and metal template procedures; the latter involved the reductive amination of the respective Tris-dialdehyde precursor complexes of iron(II), cobalt(II), or nickel(II). Electrochemical, EPR, and NMR studies have been used to probe the nature of the individual complexes. X-ray structures of the manganese(II), iron(II), and copper(II) complexes of L and the iron(II) complex of L' are presented; these are compared with the previously reported structures of the corresponding nickel(II) complex and metal-free cage (L). In each complex the metal cation occupies the cage's central cavity and is coordinated to six nitrogens from the three bipyridyl groups. The cations [MnL](2+) and [FeL](2+) are isostructural but both exhibit a different arrangement of the bound cage to that observed in the corresponding nickel(II) and copper(II) complexes. The latter have an exo-exo arrangement of the bridgehead nitrogen lone pairs, with the metal inducing a triple helical twist that extends approximately 22 A along the axial length of each complex. In contrast, [MnL](2+) and [FeL](2+) have their terminal nitrogen lone pairs directed endo, causing a significant change in the configuration of the bound ligand. In [FeL'](2+), the cage has both bridgehead nitrogen lone pairs orientated exo. Semiempirical calculations indicate that the observed endo-endo and exo-exo arrangements are of comparable energy.

Quantifying intermolecular interactions in solid state indapamide and other popular diuretic drugs: Insights from Hirshfeld surface study

NASA Astrophysics Data System (ADS)

Bojarska, Joanna; Fruziński, Andrzej; Maniukiewicz, Waldemar

2016-07-01

Hirshfeld surfaces (HS) and two-dimensional fingerprint plots are used to analyze the intermolecular interactions in indapamide and other popular thiazide diuretic derivatives. The crystal structure of indapamide (INDP) at 100 K determined by single-crystal X-ray analysis, is also reported. The title compound crystallizes in the centrosymmetric I2/a space group with one indapamide and half water molecule (lying on the glide plane) in the asymmetric unit. An interplay of N-H⋯O hydrogen bonds connects the indapamide molecules generating chains with the graph-set motifs: C (8) and C23 (16), and together with C-H⋯O and π⋯π stacking interactions create a 3D net. The Hirshfeld surface study facilitates comparison of diverse and numerous intercontacts, such as H⋯H, O⋯H, Cl⋯H, C⋯C (π⋯π), C⋯O (π⋯lone pair), O⋯O (lone pair⋯lone pair), Cl⋯O, Cl⋯Cl, N⋯N, C⋯H (C-H⋯π) with regard to building self-assembled framework of indapamide and related thiazide derivatives retrieved from the Cambridge Structural Database. The HS analysis highlights that H⋯H, O⋯H/H⋯O and C⋯H/H⋯C contacts play an influential role contributing to about 80% of the HS areas in this class of compounds. Nevertheless, in the case of INDP the H⋯H interactions, while in hydrochlorothiazide (HCTZ) O⋯H/H⋯O are dominant amongst all intercontacts towards the HS. Notably, indapamide has the highest proportion of C⋯C contacts.

Evaluation of the thiazole Schiff bases as β-glucuronidase inhibitors and their in silico studies.

PubMed

Khan, Khalid Mohammed; Karim, Aneela; Saied, Sumayya; Ambreen, Nida; Rustamova, Xayale; Naureen, Shagufta; Mansoor, Sajid; Ali, Muhammad; Perveen, Shahnaz; Choudhary, M Iqbal; Morales, Guillermo Antonio

2014-05-01

Twenty eight (28) derivatives 2-29 were synthesized and four analogs were found to exhibit single-digit IC(50) values as β-glucuronidase inhibitors. Molecular modeling indicates that three factors: substituent R, lone pair on the nitrogen of azomethine part, and the interactions made by the main skeleton of the molecule, determined the enzyme inhibitory potential of these compounds. The planar conformation of the molecules allows them to fit deep inside the pocket while blocking the entry of other physiological substrates seems to play an important role in their activity.

Synthesis, characterization and SERS activity of biosynthesized silver nanoparticles

NASA Astrophysics Data System (ADS)

Bindhu, M. R.; Sathe, V.; Umadevi, M.

2013-11-01

Silver nanoparticles were rapidly synthesized using Moringa oleifera flower extract as the reducing agent shows surface plasmon resonance peak at 439 nm. The size and shape of the nanoparticles controlled by varying the concentration of M. oleifera flower extract in the reaction medium. The synthesized silver nanoparticles were well-dispersed spherical nanoparticles with the average size of 14 nm. The retinoic acid present in M. oleifera flower extract used as reducing agent and proteins was responsible for capping of the bioreduced silver nanoparticles. The obtained nanoparticle shows size-dependent SERS activity. The SERS spectrum indicates that the pyridine adsorbed on the silver surface in a stand-on orientation via its nitrogen lone pair electrons.

On the correlations between the polyhedron eccentricity parameters and the bond-valence sums for the cations with one lone electron pair. Addendum.

PubMed

Sidey, Vasyl

2009-06-01

Systematic variations of the bond-valence sums calculated from the poorly determined bond-valence parameters [Sidey (2008), Acta Cryst. B64, 515-518] have been illustrated using a simple graphical scheme.

Lone pair effect, structural distortions, and potential for superconductivity in Tl perovskites.

PubMed

Schoop, Leslie M; Müchler, Lukas; Felser, Claudia; Cava, R J

2013-05-06

Drawing the analogy to BaBiO3, we investigate via ab initio electronic structure calculations potential new superconductors of the type ATlX3 with A = Rb and Cs and X = F, Cl, and Br, with a particular emphasis on RbTlCl3. On the basis of chemical reasoning, supported by the calculations, we show that Tl-based perovskites have structural and charge instabilities driven by the lone pair effect, similar to the case of BaBiO3, effectively becoming A2Tl(+)Tl(3+)X6. We find that upon hole doping of RbTlCl3, structures without Tl(+) and Tl(3+) charge disproportionation become more stable, although the ideal cubic perovskite, often viewed as the best host for superconductivity, should not be the most stable phase in the system. The known superconductor (Sr,K)BiO3 and hole doped RbTlCl3, predicted to be most stable in the same tetragonal structure, display highly analogous calculated electronic band structures.

CH stretching overtone spectra of trimethyl amine and dimethyl sulfide

NASA Astrophysics Data System (ADS)

Billinghurst, Brant E.; Gough, Kathleen M.; Low, Geoffrey R.; Kjaergaard, Henrik G.

2004-01-01

Trimethyl amine (TMA) exhibits the largest known difference in CH bond lengths within a methyl group, due to what is known as the lone pair trans effect. Dimethyl sulfide also exhibits this effect, but to a far lesser extent, making it ideal for comparison to TMA. In this paper, the first through fourth overtone spectra of N(CH3)3, N(CD3)3, N(CD2H)(CD3)2, N(CH3)(CD3)2, N(CD3)(CH3)2 and S(CH3)2 are reported and all major bands are assigned. The intensities of the observed bands are compared to intensities predicted by the harmonically coupled anharmonic oscillator local mode model. Good correlation is found between the experimental intensities and those predicted with the local mode model and HF/6-311++G(2d,2p) calculated dipole moment functions. An increase in the ability to resolve peaks as methyl groups are deuterated suggests that the lone pair mediates increased coupling between methyl groups.

NEXAFS spectroscopy of ionic liquids: experiments versus calculations.

PubMed

Fogarty, Richard M; Matthews, Richard P; Clough, Matthew T; Ashworth, Claire R; Brandt-Talbot, Agnieszka; Corbett, Paul J; Palgrave, Robert G; Bourne, Richard A; Chamberlain, Thomas W; Vander Hoogerstraete, Tom; Thompson, Paul B J; Hunt, Patricia A; Besley, Nicholas A; Lovelock, Kevin R J

2017-11-29

Experimental near edge X-ray absorption fine structure (NEXAFS) spectra are reported for 12 ionic liquids (ILs) encompassing a range of chemical structures for both the sulfur 1s and nitrogen 1s edges and compared with time-dependent density functional theory (TD-DFT) calculations. The energy scales for the experimental data were carefully calibrated against literature data. Gas phase calculations were performed on lone ions, ion pairs and ion pair dimers, with a wide range of ion pair conformers considered. For the first time, it is demonstrated that TD-DFT is a suitable method for simulating NEXAFS spectra of ILs, although the number of ions included in the calculations and their conformations are important considerations. For most of the ILs studied, calculations on lone ions in the gas phase were sufficient to successfully reproduce the experimental NEXAFS spectra. However, for certain ILs - for example, those containing a protic ammonium cation - calculations on ion pairs were required to obtain a good agreement with experimental spectra. Furthermore, significant conformational dependence was observed for the protic ammonium ILs, providing insight into the predominant liquid phase cation-anion interactions. Among the 12 investigated ILs, we find that four have an excited state that is delocalised across both the cation and the anion, which has implications for any process that depends on the excited state, for example, radiolysis. Considering the collective experimental and theoretical data, we recommend that ion pairs should be the minimum number of ions used for the calculation of NEXAFS spectra of ILs.

DNA interactions of non-chelating tinidazole-based coordination compounds and their structural, redox and cytotoxic properties.

PubMed

Castro-Ramírez, Rodrigo; Ortiz-Pastrana, Naytzé; Caballero, Ana B; Zimmerman, Matthew T; Stadelman, Bradley S; Gaertner, Andrea A E; Brumaghim, Julia L; Korrodi-Gregório, Luís; Pérez-Tomás, Ricardo; Gamez, Patrick; Barba-Behrens, Norah

2018-05-23

Novel tinidazole (tnz) coordination compounds of different geometries were synthesised, whose respective solid-state packing appears to be driven by inter- and intramolecular lone pairπ interactions. The copper(ii) compounds exhibit interesting redox properties originating from both the tnz and the metal ions. These complexes interact with DNA through two distinct ways, namely via electrostatic interactions or/and groove binding, and they can mediate the generation of ROS that damage the biomolecule. Cytotoxic studies revealed an interesting activity of the dinuclear compound [Cu(tnz)2(μ-Cl)Cl]2 7, which is further more efficient towards cancer cells, compared with normal cells.

Roles of the Lewis acid and base in the chemical reduction of CO2 catalyzed by frustrated Lewis pairs.

PubMed

Lim, Chern-Hooi; Holder, Aaron M; Hynes, James T; Musgrave, Charles B

2013-09-03

We employ quantum chemical calculations to discover how frustrated Lewis pairs (FLP) catalyze the reduction of CO2 by ammonia borane (AB); specifically, we examine how the Lewis acid (LA) and Lewis base (LB) of an FLP activate CO2 for reduction. We find that the LA (trichloroaluminum, AlCl3) alone catalyzes hydride transfer (HT) to CO2 while the LB (trimesitylenephosphine, PMes3) actually hinders HT; inclusion of the LB increases the HT barrier by ∼8 kcal/mol relative to the reaction catalyzed by LAs only. The LB hinders HT by donating its lone pair to the LUMO of CO2, increasing the electron density on the C atom and thus lowering its hydride affinity. Although the LB hinders HT, it nonetheless plays a crucial role by stabilizing the active FLP·CO2 complex relative to the LA dimer, free CO2, and free LB. This greatly increases the concentration of the reactive complex in the form FLP·CO2 and thus increases the rate of reaction. We expect that the principles we describe will aid in understanding other catalytic CO2 reductions.

Average and local structure of the Pb-free ferroelectric perovskites ( Sr , Sn ) TiO 3 and ( Ba , Ca , Sn ) TiO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laurita, Geneva; Page, Katharine; Suzuki, Shoichiro

2015-12-16

The characteristic structural off -centering of Pb 2+ in oxides, associated with its 6s 2 lone pair, allows it to play a dominant role in polar materials, and makes it a somewhat ubiquitous component of ferroelectrics. In this work, we examine the compounds Sr 0.9Sn 0.1TiO 3 and Ba 0.79Ca 0.16Sn 0.05TiO 3 using neutron total scattering techniques with data acquired at di erent temperatures. In these compounds, previously reported as ferroelectrics, Sn 2+ appears to display some of the characteristics of Pb 2+. We compare the local and long-range structures of the Sn2+-substituted compositions to the unsubstituted parent compoundsmore » SrTiO 3 and BaTiO 3. Lastly, we find that even at these small substitution levels, the Sn 2+ lone pairs drive the local ordering behavior, with the local structure of both compounds more similar to the structure of PbTiO 3 rather than the parent compounds.« less

Pnicogen bonds between X═PH3 (X = O, S, NH, CH2) and phosphorus and nitrogen bases.

PubMed

Alkorta, Ibon; Sánchez-Sanz, Goar; Elguero, José; Del Bene, Janet E

2014-02-27

Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the pnicogen bonded complexes formed between the acids O═PH3, S═PH3, HN═PH3, and H2C═PH3 and the bases NH3, NCH, N2, PH3, and PCH. All nitrogen and phosphorus bases form complexes in which the bases are lone pair electron donors. The binding energies of complexes involving the stronger bases NH3, NCH, and PH3 differentiate among the acids, but the binding energies of complexes with the weaker bases do not. These complexes are stabilized by charge transfer from the lone pair orbital of N or P to the σ*P═A orbital of X═PH3, where A is the atom of X directly bonded to P. PCH also forms complexes with the X═PH3 acids as a π electron donor to the σ*P═A orbital. The binding energies and the charge-transfer energies of the π complexes are greater than those of the complexes in which PCH is a lone pair donor. Whether the positive charge on P increases, decreases, or remains the same upon complex formation, the chemical shieldings of (31)P decrease in the complexes relative to the corresponding monomers. (1p)J(P-N) and (1p)J(P-P) values correlate best with the corresponding P-N and P-P distances as a function of the nature of the base. (1)J(P-A) values do not correlate with P-A distances. Rather, the absolute values of (1)J(P-O), (1)J(P-S), and (1)J(P-N) decrease upon complexation. Decreasing (1)J(P-A) values correlate linearly with increasing complex binding energies. In contrast, (1)J(P-C) values increase upon complexation and correlate linearly with increasing binding energies.

A study of N-methylacetamide in water clusters: based on atom-bond electronegativity equalization method fused into molecular mechanics.

PubMed

Yang, Zhong-Zhi; Qian, Ping

2006-08-14

N-methylacetamide (NMA) is a very interesting compound and often serves as a model of the peptide bond. The interaction between NMA and water provides a convenient prototype for the solvation of the peptides in aqueous solutions. Here we present NMA-water potential model based on atom-bond electronegativity equalization method fused into molecular mechanics (ABEEM/MM) that is to take ABEEM charges of all atoms, bonds, and lone-pair electrons of NMA and water molecules into the electrostatic interaction term in molecular mechanics. The model has the following characters: (1)it allows the charges in system to fluctuate responding to the ambient environment; (2) for two major types of intermolecular hydrogen bonds, which are the hydrogen bond forming between the lone-pair electron on amide oxygen and the water hydrogen, and the one forming between the lone-pair electron on water oxygen and the amide hydrogen, we take special treatments in describing the electrostatic interaction by the use of the parameters k(lpO=, H) and k(lpO(-), HN(-)), respectively. The newly constructed potential model based on ABEEM/MM is first applied to amide-water clusters and reproduces gas-phase state properties of NMA(H(2)O)(n) (n=1-3) including optimal structures, dipole moments, ABEEM charge distributions, energy difference of the isolated trans- and cis-NMA, interaction energies, hydrogen bonding cooperative effects, and so on, whose results show the good agreement with those measured by available experiments and calculated by ab initio methods. In order to further test the reasonableness of this model and the correctness and transferability of the parameters, many static properties of the larger NMA-water complexes NMA(H(2)O)(n) (n=4-6) are also studied including optimal structures and interaction energies. The results also show fair consistency with those of our quantum chemistry calculations.

Distorted Carbon Nitride Structure with Substituted Benzene Moieties for Enhanced Visible Light Photocatalytic Activities.

PubMed

Kim, Hyejin; Gim, Suji; Jeon, Tae Hwa; Kim, Hyungjun; Choi, Wonyong

2017-11-22

Carbon nitride (CN) is being intensively investigated as a low-cost visible light active photocatalyst, but its practical applications are limited because of the fast charge pair recombination and low visible light absorption. Here, we introduce a new strategy for enhancing its visible light photocatalytic activity by designing the CN structure in which the nitrogen of tertiary amine is substituted with a benzene molecule connected by three heptazine rings. The intramolecular benzene doping induced the structural changes from planar symmetric structure to distorted geometry, which could be predicted by density functional theory calculation. This structural distortion facilitated the spatial separation of photogenerated charge pairs and retarded charge recombination via exciton dissociation. Such unique properties of the benzene-incorporated CN were confirmed by the photoluminescence (PL) and photoelectrochemical analyses. The optimal loading of benzene doping reduced the PL of the conjugated ring system (π → π* transition) but enhanced the PL of the forbidden n → π* transition at the nitrogen atoms with lone pair electrons due to the distortion from the planar geometry. The photoelectrode of benzene-doped CN exhibited higher photocurrent and lower charge transfer resistance than bare CN electrode, indicating that the photogenerated charge pairs are more efficiently separated. As a result, the benzene-doped CN markedly increased the photocatalytic activity for the degradation of various organic pollutants and that for H 2 O 2 production (via O 2 reduction). This study proposes a simple strategy for chemical structural modification of carbon nitride to boost the visible light photocatalytic activity.

Maxima of |Ψ|2: a connection between quantum mechanics and Lewis structures.

PubMed

Lüchow, Arne

2014-04-30

The maxima of squared electronic wave functions |Ψ|2 are analyzed for a number of small molecules. They are in principle observables and show considerable chemical insight from first principles. The maxima contain substantial information about the relative electron positions in a molecule, such as the pairing of opposite spin electrons and the Pauli repulsion which are lost in the electron density. Single bond and double bond as well as polar bond pairs and lone pairs are obtained from the maximum analysis. In many cases, we find a correspondence to the electron arrangements in molecules as assumed by Lewis in 1916. Copyright © 2014 Wiley Periodicals, Inc.

Structural variations and dielectric properties of (Bi1-xL ax ) 2Si O5 (0 ≤x ≤0.1 ): Polycrystallines synthesized by crystallization of Bi-Si-O and Bi-La-Si-O glasses

NASA Astrophysics Data System (ADS)

Taniguchi, Hiroki; Tatewaki, Shingo; Yasui, Shintaro; Fujii, Yasuhiro; Yamaura, Jun-ichi; Terasaki, Ichiro

2018-04-01

This paper focuses on effects of isovalent La substitution on the crystal structure and dielectric properties of ferroelectric B i2Si O5 . Polycrystalline samples of (Bi1-xL ax ) 2Si O5 are synthesized by crystallization of Bi-Si-O and Bi-La-Si-O glasses with a composition range of 0 ≤x ≤0.1 . The crystal structure changes from monoclinic to tetragonal with increasing La-substitution rate x at room temperature. This structural variation stems from the change in orientation of Si O4 tetrahedra that form one-dimensional chains when they are in the ordered configuration, thus suggesting that lone-pair electrons play an important role in sustaining one-dimensional chains of Si O4 tetrahedra. Synchronizing with the disordering of Si O4 chains, ferroelectric phase transition temperature of (Bi1-xL ax ) 2Si O5 sharply decreases as x increases, and ferroelectricity finally vanishes at around x =0.03 . The present results demonstrate that lone-pair electrons of Bi play an important role in the ferroelectricity of B i2Si O5 through propping the ordered structure of one-dimensional Si O4 chains with stereochemical activity. Furthermore, an additional phase transition has been first discovered in the low-temperature region of (Bi1-xL ax ) 2Si O5 with x ≤0.01 , where the ordered one-dimensional Si O4 chains remain.

Investigation of structural and multiferroic properties of three phases of BiFeO3 using modified Becke Johnson potential technique

NASA Astrophysics Data System (ADS)

Sagar, Elle; Mahesh, R.; Pavan Kumar, N.; Venugopal Reddy, P.

2017-11-01

Electronic band structure, ferroelectric and ferromagnetic properties of Cubic, Tetragonal and Rhombohedral (hexagonal axis) phases of multiferroic BiFeO3 compound has been investigated using first-principles calculations under the generalized gradient (GGA) and TB-mBJ semi local (Tran-Blaha modified Becke-Johnson) potential approximations using WIEN2k code. For this purpose, the total energies were calculated as a function of reduced volumes and the data were fitted to Brich Murnaghan equation. The estimated ground state parameters are found to be comparable with those of experimental ones. The semiconducting behavior of the material was obtained using TB-mBJ method in the spin polarized mode. Analysis of the density of states indicates that the valence band consists of Fe-d and O-p states, while the conduction band is composed of Fe-d and Bi-p states. The analysis of electron localization function shows that stereochemically active lone-pair electrons are present at Bi sites of Rhombohedral and Tetragonal phases and are responsible for the displacements of Bi atoms from the centro-symmetric to the non-centrosymmetric structure leading to the exhibition of ferroelectricity. Further, it has been concluded that the "lone pair" may have been formed due to the hybridization of 6s and 6p atomic orbitals with 6s2 electrons filling one of the resulting orbitals in Bi. The Polarization and the magnetic properties including susceptibility were obtained. The calculated magnetic moments at the iron sites are not integer values, since Fe electrons have a hybridization interaction with the neighboring O ions.

First-principles study lone-pair effects of Sb (III)-S chromophore influence on SHG response in quaternary potassium containing silver antimony sulfides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Junben; School of Physics Science and Technology, Xinjiang University, Urumqi 830046; Su, Xin

2017-05-15

First-principles studies of the geometric structures, electronic structures and optical properties of non-centrosymmetrical (NCS) KAg{sub 2}SbS{sub 4}, K{sub 2}AgSbS{sub 4} and K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} and centrosymmetrical (CS) KAg{sub 2}SbS{sub 3} and K{sub 3}Ag{sub 9}Sb{sub 4}S{sub 12} have been performed by means of density functional theory. It is indicated that although they have similarity in their anionic groups and, the electronic structures, prominent features of the optical anisotropy or second-order nonlinear optical (NLO) susceptibilities are apparently different. The calculated birefringences are 0.0537, 0.0343, 0.1324, 0.2217 and 0.0604 which are attributed to the different anionic groups [SbS{sub 3}] and trianglesmore » [AgS{sub 3}]. Also, the calculated NLO responses are about 0.5×, 1.0× and 2.0× times than that commercial AgGaS{sub 2} (AGS, d{sub 36}=11 pm/V) for K{sub 2}AgSbS{sub 4}, KAg{sub 2}SbS{sub 4} and K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7}, respectively. In comparison with the absolute magnitude of second harmonic generation (SHG) coefficients, the order K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7}>KAg{sub 2}SbS{sub 4}>K{sub 2}AgSbS{sub 4} is clearly established in the SHG response. Further analysis based on the real-space atom-cutting method reveals that the main sources of the SHG properties of these compounds are from the Sb-S group, especially K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} is mainly attributed to the lone pair stereochemical activity of Sb (III)-S group. - Graphical abstract: Compounds K{sub 2}AgSbS{sub 4}, KAg{sub 2}SbS{sub 4} and K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} exhibit second-order NLO response: 15×, 30× and 62× times than that KDP (KH{sub 2}PO{sub 4}, d{sub 36}=0.39 pm/V), respectively. First-principles methods reveal that the large SHG response of K{sub 2}Ag{sub 3}Sb{sub 3}S{sub 7} is dominated by the Sb-S chromophore with lone pairs.« less

A -cation control of magnetoelectric quadrupole order in A (TiO)Cu 4(PO4)4(A =Ba ,Sr, and Pb)

NASA Astrophysics Data System (ADS)

Kimura, K.; Toyoda, M.; Babkevich, P.; Yamauchi, K.; Sera, M.; Nassif, V.; Rønnow, H. M.; Kimura, T.

2018-04-01

Ferroic magnetic quadrupole order exhibiting macroscopic magnetoelectric activity is discovered in the novel compound A (TiO ) Cu4(PO4)4 with A = Pb, which is in contrast with antiferroic quadrupole order observed in the isostructural compounds with A = Ba and Sr. Unlike the famous lone-pair stereochemical activity which often triggers ferroelectricity as in PbTiO3, the Pb2 + cation in Pb (TiO ) Cu4(PO4)4 is stereochemically inactive but dramatically alters specific magnetic interactions and consequently switches the quadrupole order from antiferroic to ferroic. Our first-principles calculations uncover a positive correlation between the degree of A -O bond covalency and a stability of the ferroic quadrupole order.

Rabbit Ears Concepts of Water Lone Pairs: A Reply to Comments of Hiberty, Danovich, and Shaik

ERIC Educational Resources Information Center

Clauss, A. D.; Ayoub, M.; Moore, J. W.; Landis, C. R.; Weinhold, F.

2015-01-01

This article is a response to a commentary entitled "Comment on 'Rabbit-Ears Hybrids, VSEPR Sterics, and Other Orbital Anachronisms': A Reply to a Criticism," which focuses on the fundamental question of whether there exists a unique set of supposedly "real," or "best," orbitals for a given molecule. The authors of…

Pseudopotential SCF-MO studies of hypervalent compounds. II. XeF+5 and XeF6

NASA Astrophysics Data System (ADS)

Rothman, Michael J.; Bartell, Lawrence S.; Ewig, Carl S.; Van Wazer, John R.

1980-07-01

New evidence bearing upon the anomalous properties of xenon hexafluoride has been obtained via the ab initio molecular orbital approach applied successfully to the di- and tetrafluorides in paper I. Structures of both XeF+5 and XeF6 are governed by a stereochemically active lone pair. In the case of the square-pyramidal cation the Fax-Xe-Feq angle calculated for the bare ion is within 2° of the value observed in the crystalline complex. For the hexafluoride, however, the calculated deformation from Oh symmetry is appreciably greater than that deduced from electron diffraction intensities. Nevertheless, the results of calculations are in sufficient conformity with the Bartell-Gavin, Pitzer-Bernstein interpretation and at variance with the ''electronic-isomers'' interpretation to leave little doubt about the answer. With increasing fluorination in the XeFn series the HOMO-LUMO energy difference decreases and the second-order Jahn-Teller effect is enhanced. Increasing fluorination (and increased positive charge on Xe) also shortens bond lengths; calculated shortenings parallel observed shortenings. The deformation of XeF6 from Oh is along t1u bend and stretch coordinates to a C3v structure with long bonds adjacent to the lone pair, as expected according to the valence-shell-electron-pair-repulsion model. Pure t2g deformations are destabilizing but anharmonic t1u-t2g coupling significantly stabilizes the deformation. Steric aspects of the structure and force field are diagnosed and found to be minor. Values for the force constants f44, f55, f¯4444, f¯444'4', and f¯445 are derived and found to be of the magnitude forecast in the Bartell-Gavin and Pitzer-Bernstein treatments except that the calculations do not reproduce the delicate balances believed to lead to almost free pseudorotation in XeF6.

Investigation of the mineral potential of the Clipper Gap, Lone Mountain-Weepah, and Pipe Spring plutons, Nevada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tingley, J.V.; Maldonado, F.

1983-09-15

The Clipper Gap pluton, composed mostly of quartz monzonite with minor granite, granodiorite, and crosscutting alaskite dikes, intrudes Paleozoic western facies strata. A narrow zone of contact metamorphism is present at the intrusive-sediment contact. No mineral production has been recorded from Clipper Gap, but quartz veins containing gold-silver-copper mineral occurrences have been prospected there from the late 1800's to the present. Areas of the Lone Mountain-Weepah plutons that were studied are located in Esmeralda County about 14 km west of Tonopah, Nevada. At Lone Mountain, a Cretaceous intrusive cuts folded Precambrian and Cambrian sediments. Lead-zinc ores have been mined frommore » small replacement ore bodies in the Alpine district, west of Lone Mountain. Copper and molybdenum occurrences have been found along the east flank of Lone Mountain, and altered areas were noted in intrusive outcrops around the south end of Lone Mountain. Mineral occurrences are widespread and varied with mining activity dating back to the 1860's. The Pipe Spring pluton study area is flanked by two important mining districts, Manhattan to the north and Belmont to the northeast. Mining activity at Belmont dates from 1865. Activity at Manhattan was mainly between 1907 and 1947, but the district is active at the present time (1979). Four smaller mining areas, Monarch, Spanish Springs, Baxter Spring, and Willow Springs, are within the general boundary of the area. The Pipe Spring pluton study area contains numerous prospects along the northern contact zone of the pluton. Tungsten-bearing veins occur within the pluton near Spanish Springs, with potential for gold-tungsten placer in the Ralston Valley. Nickel and associated metals occur at Willow Spring and Monarch Ranch, where prospects may be associated with the margin of the Big Ten Peak Caldera.« less

Structural behavior of Tl-exchanged natrolite at high pressure depending on the composition of pressure-transmitting medium

NASA Astrophysics Data System (ADS)

Seryotkin, Yu. V.; Bakakin, V. V.; Likhacheva, A. Yu.; Dementiev, S. N.; Rashchenko, S. V.

2017-10-01

The structural evolution of Tl-exchanged natrolite with idealized formula Tl2[Al2Si3O10]·2H2O, compressed in penetrating (water:ethanol 1:1) and non-penetrating (paraffin) media, was studied up to 4 GPa. The presence of Tl+ with non-bonded electron lone pairs, which can be either stereo-chemically active or passive, determines distinctive features of the high-pressure behavior of the Tl-form. The effective volume of assemblages Tl+(O,H2O) n depends on the E-pairs activity: single-sided coordination correlates with smaller volumes. At ambient conditions, there are two types of Tl positions, only one of them having a nearly single-sided coordination as a characteristic of stereo-activity of the Tl+ E pair. Upon the compression in paraffin, a phase transition occurs: a 5% volume contraction of flexible natrolite framework is accompanied by the conversion of all the Tl+ cations into stereo-chemically active state with a single-sided coordination. This effect requires the reconstruction of all the extra-framework subsystems with the inversion of the cation and H2O positions. The compression in water-containing medium leads to the increase of H2O content up to three molecules pfu through the filling of partly vacant positions. This hinders a single-sided coordination of Tl ions and preserves the configuration of their ion-molecular subsystem. It is likely that the extra-framework subsystem is responsible for the super-structure modulation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Devadoss, C.; Fessenden, R.W.

The transient that is produced in the quenching of triplet benzophenone by 1,4-diazabicyclo(2.2.2)octane (DABCO) has been examined by use of nano- and picosecond laser photolysis. The initial step in all solvents, both polar and nonpolar, is electron transfer to form a triplet contact ion pair. In nonpolar solvents, the ion pair remains in this form until it decays. For polar solvents, the spectra change somewhat over the first 100 ps showing that the solvation changes and the ion pair becomes solvent separated. The lifetime of the ion pair varies greatly with the solvent. In saturated hydrocarbons it is about 80more » ps. Nonpolar solvents with either {pi} electrons or a lone pair of electrons stabilize the ion pair on the nanosecond to microsecond time scale. A small amount of alcohol in benzene also stabilizes the ion pair by hydrogen bonding. A shift in the peak position with time toward the blue accompanies the formation of hydrogen bonds in this case.« less

Electronic structure of monodentate-coordinated diphosphine complexes. Photoelectron spectra of Mo(CO)[sub 5](P(CH[sub 3])[sub 2]CH[sub 2]P(CH[sub 3])[sub 2]) and Mo(CO)[sub 5](P(CH[sub 3])[sub 2]CH[sub 2]CH[sub 2]P(CH[sub 3])[sub 2])

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lichtenberger, D.L.; Jatcko, M.E.

1992-02-05

Photoelectron spectroscopy is used to study the electronic structure of molybdenum carbonyl complexes that contain diphosphine ligands bound to the metal through only one of the two phosphorus atoms. Photoelectron spectra are reported for Mo(CO)[sub 5]DMPE and Mo(CO)[sub 5]DMPM and compared to the spectra of Mo(CO)[sub 5]PMe[sub 3] and the corresponding free phosphine and diphosphine ligands (PMe[sub 3] is trimethylphosphine, DMPE is 1,2-bis(dimethylphosphino)ethane, and DMPM is bis(dimethylphosphino)methane). The energy splittings between the d[sup 6] metal-based ionizations of these complexes indicate that the [pi]-back-bonding ability is the same for each of these phosphine ligands and is relatively small, about 25% thatmore » of carbon monoxide. The metal-based ionizations shift only slightly to lower binding energy from the PMe[sub 3] to the DMPE to the DMPM complex due to a slightly increasing negative charge potential at the metal along this series. This would normally be interpreted as slightly increasing [sigma]-donor strength in the order PMe[sub 3] < DMPE < DMPM. However, the difference between the ionization energy of the coordinated lone pair (CLP) of the phosphine and the ionization energy of the lone pair of the free ligand indicates an opposite trend in [sigma]-donor strength with PMe[sub 3] (1.28 eV) > DMPE (1.27 eV) > DMPM (1.23 eV). The shift of the uncoordinated phosphine lone-pair ionization (ULP) of the monocoordinated diphosphine complexes, which is affected primarily by charge potential effects, reveals that the important factor is a transfer of negative charge from the uncoordinated end of the phosphine through the alkyl linkage to the coordinated phosphine. Aside from these subtle details of charge distribution, the primary conclusion is that the diphosphine ligands, DMPE and DMPM, have [sigma]-donor and [pi]-acceptor strengths extremely similar to those of PMe[sub 3].« less

Remedial investigation and feasibility study Point Lonely Radar Installation, Alaska. Volume 1. Appendices a - c. Final report, January 1995-April 1996

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-04-01

This report presents the findings of Remedial Investigations and Feasibility Studies at sites located at the Point Lonely radar installation in northern Alaska. The sites were characterized based on sampling and analyses conducted during Remedial Investigation activities performed during August and September 1993.

Relating Bond Angles of Dihalo- and Tetrahydro--Methanes, -Silanes, and -Germanes to Electronegativities

ERIC Educational Resources Information Center

Kirschenbaum, Louis J.; Ruekberg, Ben

2012-01-01

Our previous work correlated bond angles of group V and group VI hydrides (AH[subscript 3]E and AH[subscript 2]E[subscript 2], respectively, where E represents a lone electron pair) to the electronegativities of the atoms using the fraction of s character to relate the two. Here we have extended the correlation to the AH[subscript 2]X[subscript 2]…

On the origin of red and blue shifts of X-H and C-H stretching vibrations in formic acid (formate ion) and proton donor complexes.

PubMed

Tâme Parreira, Renato Luis; Galembeck, Sérgio Emanuel; Hobza, Pavel

2007-01-08

Complexes between formic acid or formate anion and various proton donors (HF, H(2)O, NH(3), and CH(4)) are studied by the MP2 and B3LYP methods with the 6-311++G(3df,3pd) basis set. Formation of a complex is characterized by electron-density transfer from electron donor to ligands. This transfer is much larger with the formate anion, for which it exceeds 0.1 e. Electron-density transfer from electron lone pairs of the electron donor is directed into sigma* antibonding orbitals of X--H bonds of the electron acceptor and leads to elongation of the bond and a red shift of the X--H stretching frequency (standard H-bonding). However, pronounced electron-density transfer from electron lone pairs of the electron donor also leads to reorganization of the electron density in the electron donor, which results in changes in geometry and vibrational frequency. These changes are largest for the C--H bonds of formic acid and formate anion, which do not participate in H-bonding. The resulting blue shift of this stretching frequency is substantial and amounts to almost 35 and 170 cm(-1), respectively.

Synthesis, structure, and electronic structure calculation of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Feng; Wang, Li, E-mail: wangliresearch@163.com; Stoumpos, Constantinos C.

2016-08-15

The synthesis, structure, and characterization of a new centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] based on anion-centered OPb{sub 4} tetrahedra are reported. Pb{sub 2}O[BO{sub 2}(OH)] crystallizes in monoclinic space group C2/m with a=12.725(7) Å, b=5.698(3) Å, c=7.344(4) Å, β=116.277(6)°. The electronic band structure and density of states of Pb{sub 2}O[BO{sub 2}(OH)] have been calculated via the density functional theory (DFT). Electron density difference calculation indicates that lone-pair electrons of Pb{sup 2+} cation should be stereoactive. - Graphical abstract: An indirect gap compound of Pb{sub 2}O[BO{sub 2}(OH)] with 2D inorganic layers motif based on OPb{sub 4} tetrahedra has been synthesized and fullmore » characterized by crystallographic, IR, TG, UV–vis-NIR Diffuse Reflectance, and theoretical calculations. Display Omitted - Highlights: • A centrosymmetric borate Pb{sub 2}O[BO{sub 2}(OH)] was synthesized and characterized. • The crystalstructure, electronic band and density states was analyzed. • The lone-pair electrons of Pb{sup 2+} were proved to be stereoactive.« less

Tick-borne diseases in North Carolina: is "Rickettsia amblyommii" a possible cause of rickettsiosis reported as Rocky Mountain spotted fever?

PubMed

Apperson, Charles S; Engber, Barry; Nicholson, William L; Mead, Daniel G; Engel, Jeffrey; Yabsley, Michael J; Dail, Kathy; Johnson, Joey; Watson, D Wesley

2008-10-01

Cases of Rocky Mountain spotted fever (RMSF) in North Carolina have escalated markedly since 2000. In 2005, we identified a county in the Piedmont region with high case numbers of RMSF. We collected ticks and examined them for bacterial pathogens using molecular methods to determine if a novel tick vector or spotted fever group rickettsiae (SFGR) might be emerging. Amblyomma americanum, the lone star tick, comprised 99.6% of 6,502 specimens collected in suburban landscapes. In contrast, Dermacentor variabilis, the American dog tick, a principal vector of Rickettsia rickettsii, comprised < 1% of the ticks collected. Eleven of 25 lone star tick pools tested were infected with "Rickettsia amblyommii," an informally named SFGR. Sera from patients from the same county who were presumptively diagnosed by local physicians with a tick-borne illness were tested by an indirect immunofluorescence antibody (IFA) assay to confirm clinical diagnoses. Three of six patients classified as probable RMSF cases demonstrated a fourfold or greater rise in IgG class antibody titers between paired acute and convalescent sera to "R. amblyommii" antigens, but not to R. rickettsii antigens. White-tailed deer, Odocoileus virginianus, are preferred hosts of lone star ticks. Blood samples collected from hunter-killed deer from the same county were tested by IFA test for antibodies to Ehrlichia chaffeensis and "R. amblyommii." Twenty-eight (87%) of 32 deer were positive for antibodies to E. chaffeensis, but only 1 (3%) of the deer exhibited antibodies to "R. amblyommii," suggesting that deer are not the source of "R. amblyommii" infection for lone star ticks. We propose that some cases of rickettsiosis reported as RMSF may have been caused by "R. amblyommii" transmitted through the bite of A. americanum.

Polymorphism in Bi2(SO4)3

NASA Astrophysics Data System (ADS)

Subban, Chinmayee V.; Rousse, Gwenaëlle; Courty, Matthieu; Barboux, Philippe; Tarascon, Jean-Marie

2014-12-01

A new polymorph of Bi2(SO4)3 was prepared by reaction of LiBiO2 with H2SO4 and its crystal structure was solved from X-ray powder diffraction. This new polymorph crystallizes in C2/c space group with lattice parameters a = 17.3383(3) Å, b = 6.77803(12) Å, c = 8.30978(13) Å, β = 101.4300(12)°. Bi2(SO4)3 presents a layered structure made of SO4 sulfate groups and signs of stereochemically active Bi3+ lone pairs. The new Bi2(SO4)3 absorbs water to form Bi2(H2O)2(SO4)2(OH)2 through an intermediate Bi2O(OH)2SO4 phase, and the transition is reversible when heated under vacuum.

Locating the Place and Meaning of Physical Activity in the Lives of Young People from Low-Income, Lone-Parent Families

ERIC Educational Resources Information Center

Quarmby, Thomas; Dagkas, Symeon

2013-01-01

Background: In the United Kingdom (UK), it is predicted that economic cuts and a subsequent increase in child poverty will affect those already on the lowest incomes and, in particular, those living in lone-parent families. As a result, the informal pedagogic encounters within the family that contribute to the development of physical…

Source Hierarchy List. Volume 1. A through D

DTIC Science & Technology

1994-07-01

TECHNOLOGY DIV 04 LAKE CITY ARMY AMMUNITION PLANT INDEPENDENCE MO INDUSTRIAL ENGINEERING DIV 03 LONE STAR ARMY AMMUNITION PLANT TEXARKANA TX 03...INDEPENDENCE MO INDUSTRIAL ENGINEERING DIV 03 LONE STAR ARMY AMMUNITION PLANT TEXARKANA TX 03 LONGHORN ARMY AMMUNITION PLANT MARSHALL TX 03 LOUISIANA...STORAGE ACTIVITY SAN ANTONIO TX* 02 COATING AND CHEMICAL LAB ABERDEEN PROVING GROUND MD 02 DARCOM INTERN TRAINING CENTER TEXARKANA TX 03 ARMY MATERIEL

Connecting Dopant Bond Type with Electronic Structure in N-Doped Graphene

DTIC Science & Technology

2012-06-29

dopant forms one σ-bond with its C neighbor, forms σ-bonds to two H (or one N-lone-pair orbital in the unhydrogenated case). Two electrons go into the...pyridinic groups (Table 1), the additional charge from nitrogen is forced to go to the extended carbon π-network, essentially neutralizing the p-doping...T.; Bouchet-Fabre, B.; Granier, A.; Turban, G. XPS and NEXAFS characterisation of plasma deposited vertically aligned N-doped MWCNT . Diamond Relat

A combined theoretical and Cambridge Structural Database study of π-hole pnicogen bonding complexes between electron rich molecules and both nitro compounds and inorganic bromides (YO2Br, Y = N, P, and As).

PubMed

Bauzá, Antonio; Ramis, Rafael; Frontera, Antonio

2014-04-17

Quantum calculations at the DFT-D3/def2-TZVPD level of theory have been used to examine complexes between O2YBr (Y═N, P, and As) molecules and several Lewis bases, that is, NH3, H2O, and HF. The interactions of the lone pair of the ammonia, water, and hydrogen fluoride with the σ-hole and π-hole of O2YBr molecules have been considered. In general, the complexes where the Lewis base lone pair interacts with the π-hole are more favorable than those with σ-hole. The nature of the interactions has been characterized with the Bader theory of atoms in molecules (AIM). We have also studied the ability of trifluoronitromethane and nitromethane to interact with anions using their π-hole along with an analysis the Cambridge Structural Database. We have found a large number of hits that provide strong experimental support for ability of the nitryl (-NO2) group to interact with anions and Lewis bases. In some X-ray structures, the π-hole interaction is crucial in the crystal packing and has a strong influence in the solid state architecture of the complexes. Finally, due to the relevance in atmospheric chemistry, we have studied noncovalent σ/π-hole complexes of nitryl bromide with ozone.

Molecular electrostatic potential and "atoms-in-molecules" analyses of the interplay between π-hole and lone pair···π/X-H···π/metal···π interactions.

PubMed

Bauzá, Antonio; Seth, Saikat Kumar; Frontera, Antonio

2018-04-05

Using ab initio calculations, we analyze the interplay between π-hole interactions involving the nitro group of 1,4-dinitrobenzene and lone pair···π (lp···π), C-H···π or metal(M)···π noncovalent interactions. Moreover, we have also used 1,4-phenylenebis(phosphine dioxide) for comparison purposes. Interesting cooperativity effects are found when π-hole (F···N,P) and lp···π/C-H···π/M···π interactions coexist in the same supramolecular assembly. These effects are studied theoretically in terms of energetic and geometric features of the complexes, which are computed by ab initio methods (RI-MP2/def2-TZVP). A charge density analysis using the Bader's theory of "atoms in molecules" is carried out to characterize the interactions and to analyze their strengthening or weakening depending on the variation of charge density at critical points. The importance of electrostatic effects on the mutual influence of the interaction is studied by means of molecular electrostatic potential calculations. By taking advantage of these computational tools, the present study examines interplay of these interactions. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Stepping Stone Mechanism: Carrier-Free Long-Range Magnetism Mediated by Magnetized Cation States in Quintuple Layer

NASA Astrophysics Data System (ADS)

Chan, Chunkai; Zhang, Xiaodong; Zhang, Yiou; Tse, Kinfai; Deng, Bei; Zhang, Jingzhao; Zhu, Junyi

2018-01-01

The long-range magnetism observed in group-V tellurides quintuple layers is the only working example of carrier-free dilute magnetic semiconductors (DMS), whereas the physical mechanism is unclear, except the speculation on the band topology enhanced van Vleck paramagnetism. Based on DFT calculations, we find a stable long-range ferromagnetic order in a single quintuple layer of Cr-doped Bi2Te3 or Sb2Te3, with the dopant separation more than 9 Å. This configuration is the global energy minimum among all configurations. Different from the conventional super exchange theory, the magnetism is facilitated by the lone pair derived anti-bonding states near the cations. Such anti-bonding states work as stepping stones merged in the electron sea and conduct magnetism. Further, spin orbit coupling induced band inversion is found to be insignificant in the magnetism. Therefore, our findings directly dismiss the common misbelief that band topology is the only factor that enhances the magnetism. We further demonstrate that removal of the lone pair derived states destroys the long-range magnetism. This novel mechanism sheds light on the fundamental understanding of long-range magnetism and may lead to discoveries of new classes of DMS. Supported by Chinese University of Hong Kong (CUHK) under Grant No 4053084, University Grants Committee of Hong Kong under Grant No 24300814, and the Start-up Funding of CUHK.

Experimental charge density analysis of a gallium(I) N-heterocyclic carbene analogue.

PubMed

Overgaard, Jacob; Jones, Cameron; Dange, Deepak; Platts, James A

2011-09-05

The experimental electron density of the only known example of a four-membered Ga(I) N-heterocyclic carbene analogue has been determined by multipole modeling of 90 K X-ray diffraction data and compared to theoretical data. In order to obtain a satisfactory model, it is necessary to modify the radial dependency of the core electrons of Ga using two separate scaling parameters for s,p- and d-electrons. Evidence for significant lone-pair density on Ga is found in the electron density and derived properties despite the partial positive charge of this atom. Static deformation density and molecular electrostatic potential clearly show a directional lone pair on Ga, whereas the Laplacian of the total electron density does not; this feature is, however, present in the Laplacian of the valence-only density. The Ga center also acts as an acceptor in four intramolecular C-H···Ga contacts, whose nature is probed by density properties. Substantial covalent character is apparent in the Ga-N bonds, but no sign of donation from filled N p-orbitals to empty Ga p-orbitals is found, whereas π-delocalization over the organic ligand is evident. This study highlights the utility of experimental charge density analysis as a technique to investigate the unusual bonding and electronic characteristics of low oxidation state/low coordinate p-block complexes.

Hydrogen bonded C-H···Y (Y = O, S, Hal) molecular complexes: A natural bond orbital analysis

NASA Astrophysics Data System (ADS)

Isaev, A. N.

2016-03-01

Hydrogen bonded C-H···Y complexes formed by H2O, H2S molecules, hydrogen halides, and halogen-ions with methane, halogen substituted methane as well as with the C2H2 and NCH molecules were studied at the MP2/aug-cc-pVDZ level. The structure of NBOs corresponding to lone pair of acceptor Y, n Y, and vacant anti-σ-bond C-H of proton donor was analyzed and estimates of second order perturbation energy E(2) characterizing donor-acceptor n Y → σ C-H * charge-transfer interaction were obtained. Computational results for complexes of methane and its halogen substituted derivatives show that for each set of analogous structures, the EnY→σ*C-H (2) energy tends to grow with an increase in the s-component percentage in the lone pair NBO of acceptor Y. Calculations for different C···Y distances show that the equilibrium geometries of complexes lie in the region where the E(2) energy is highest and it changes symbatically with the length of the covalent E-H bond when the R(C···Y) distance is varied. The performed analysis allows us to divide the hydrogen bonded complexes into two groups, depending on the pattern of overlapping for NBOs of the hydrogen bridge.

49 CFR 214.347 - Training and qualification for lone workers.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 49 Transportation 4 2011-10-01 2011-10-01 false Training and qualification for lone workers. 214... § 214.347 Training and qualification for lone workers. Each lone worker shall be trained and qualified... training and qualification for lone workers shall include, as a minimum, consideration of the following...

49 CFR 214.347 - Training and qualification for lone workers.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Training and qualification for lone workers. 214... § 214.347 Training and qualification for lone workers. Each lone worker shall be trained and qualified... training and qualification for lone workers shall include, as a minimum, consideration of the following...

Phenylazopyridine as Switch in Photochemical Reactions. A Detailed Computational Description of the Mechanism of Its Photoisomerization

PubMed Central

Casellas, Josep; Alcover-Fortuny, Gerard; de Graaf, Coen

2017-01-01

Azo compounds are organic photochromic systems that have the possibility of switching between cis and trans isomers under irradiation. The different photochemical properties of these isomers make azo compounds into good light-triggered switches, and their significantly different geometries make them very interesting as components in molecular engines or mechanical switches. For instance, azo ligands are used in coordination complexes to trigger photoresponsive properties. The light-induced trans-to-cis isomerization of phenylazopyridine (PAPy) plays a fundamental role in the room-temperature switchable spin crossover of Ni-porphyrin derivatives. In this work, we present a computational study developed at the SA-CASSCF/CASPT2 level (State Averaged Complete Active Space Self Consistent Field/CAS second order Perturbation Theory) to elucidate the mechanism, up to now unknown, of the cis–trans photoisomerization of 3-PAPy. We have analyzed the possible reaction pathways along its lowest excited states, generated by excitation of one or two electrons from the lone pairs of the N atoms of the azo group (nazoπ*2 and nazo2π*2 states), from a π delocalized molecular orbital (ππ* state), or from the lone pair of the N atom of the pyridine moiety (npyπ* state). Our results show that the mechanism proceeds mainly along the rotation coordinate in both the nazoπ* and ππ* excited states, although the nazo2π*2 state can also be populated temporarily, while the npyπ* does not intervene in the reaction. For rotationally constrained systems, accessible paths to reach the cis minimum along planar geometries have also been located, again on the nazoπ* and ππ* potential energy surfaces, while the nazo2π*2 and npyπ* states are not involved in the reaction. The relative energies of the different paths differ from those found for azobenzene in a previous work, so our results predict some differences between the reactivities of both compounds. PMID:29168765

Physical origins of weak H 2 binding on carbon nanostructures: Insight from ab initio studies of chemically functionalized graphene nanoribbons

DOE PAGES

Ulman, Kanchan; Bhaumik, Debarati; Wood, Brandon C.; ...

2014-05-05

Here, we have performed ab initio density functional theory calculations, incorporating London dispersion corrections, to study the absorption of molecular hydrogen on zigzag graphene nanoribbons whose edges have been functionalized by OH, NH 2, COOH, NO 2, or H 2PO 3. We find that hydrogen molecules always preferentially bind at or near the functionalized edge, and display induced dipole moments. Binding is generally enhanced by the presence of polar functional groups. Furthermore, the largest gains are observed for groups with oxygen lone pairs that can facilitate local charge reorganization, with the biggest single enhancement in adsorption energy found for “strongmore » functionalization” by H 2PO 3 (115 meV/H 2 versus 52 meV/H 2 on bare graphene). We show that for binding on the “outer edge” near the functional group, the presence of the group can introduce appreciable contributions from Debye interactions and higher-order multipole electrostatic terms, in addition to the dominant London dispersion interactions. For those functional groups that contain the OH moiety, the adsorption energy is linearly proportional to the number of lone pairs on oxygen atoms. Mixed functionalization with two different functional groups on a graphene edge can also have a synergistic effect, particularly when electron-donating and electron-withdrawing groups are combined. For binding on the “inner edge” somewhat farther from the functional group, most of the binding again arises from London interactions; however, there is also significant charge redistribution in the π manifold, which directly reflects the electron donating or withdrawing capacity of the functional group. These results offer insight into the specific origins of weak binding of gas molecules on graphene, and suggest that edge functionalization could perhaps be used in combination with other strategies to increase the uptake of hydrogen in graphene. They also have relevance for the storage of hydrogen in porous carbon materials, such as activated carbons.« less

Inhomogeneity of PAGs in resist film studied by molecular-dynamics simulations for EUV lithography

NASA Astrophysics Data System (ADS)

Toriumi, Minoru; Itani, Toshiro

2014-03-01

EUV resist materials are requested simultaneously to improve the resolution, line-edge roughness (LER), and sensitivity (RLS). In a resist film inhomogeneous structures in nanometer region may have large effects on directly the resolution and LER and indirectly on sensitivity. Inhomogeneity of PAGs in a hybrid resist for EUV lithography was investigated using molecular dynamics simulations. The hybrid resist film showed the inhomogeneous positions and motions of PAG cations and anions. Free volumes in resist matrix influence the motions of PAGs. Molecular structure such as bulky phenyl groups of a PAG cation localize the positions and reduce the motion of a cation. Chemical properties such as ionic interactions and lone-pair interaction also play an important role to determine the inhomogeneity of PAGs. Fluorine interaction enables active motions of PAG anions.

Self-rated health and mental health of lone fathers compared with lone mothers and partnered fathers: a population-based cross-sectional study.

PubMed

Chiu, Maria; Rahman, Farah; Kurdyak, Paul; Cairney, John; Jembere, Nathaniel; Vigod, Simone

2017-05-01

Lone parenthood is associated with poorer health; however, the vast majority of previous studies have examined lone mothers and only a few have focused on lone fathers. We aimed to examine the self-rated health and mental health status among a large population-based cross-sectional sample of Canadian lone fathers compared with both partnered fathers and lone mothers. We investigated differences in self-rated health and mental health among 1058 lone fathers compared with 20 692 partnered fathers and 5725 lone mothers using the Ontario component of the Canadian Community Health Survey (2001-2013). Multivariable logistic regression was used to compare the odds of poor/fair self-rated health and mental health between the study groups while adjusting for a comprehensive list of sociodemographic factors, stressors and lifestyle factors. Lone fathers and lone mothers showed similar prevalence of poor/fair self-rated health (11.6% and 12.5%, respectively) and mental health (6.2% and 8.4%, respectively); the odds were similar even after multivariable adjustment. Lone fathers showed higher odds of poor/fair self-rated health (OR 1.53, 95% CI 1.07 to 2.17) and mental health (OR 2.09, 95% CI 1.26 to 3.46) than partnered fathers after adjustment for sociodemographic factors; however, these differences were no longer significant after accounting for stressors, including low income and unemployment. In this large population-based study, lone fathers had worse self-rated health and mental health than partnered fathers and similarly poor self-rated health and mental health as lone mothers. Interventions, supports and social policies designed for single parents should also recognise the needs of lone fathers. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

Atomic charges of sulfur in ionic liquids: experiments and calculations.

PubMed

Fogarty, Richard M; Rowe, Rebecca; Matthews, Richard P; Clough, Matthew T; Ashworth, Claire R; Brandt, Agnieszka; Corbett, Paul J; Palgrave, Robert G; Smith, Emily F; Bourne, Richard A; Chamberlain, Thomas W; Thompson, Paul B J; Hunt, Patricia A; Lovelock, Kevin R J

2017-12-14

Experimental near edge X-ray absorption fine structure (NEXAFS) spectra, X-ray photoelectron (XP) spectra and Auger electron spectra are reported for sulfur in ionic liquids (ILs) with a range of chemical structures. These values provide experimental measures of the atomic charge in each IL and enable the evaluation of the suitability of NEXAFS spectroscopy and XPS for probing the relative atomic charge of sulfur. In addition, we use Auger electron spectroscopy to show that when XPS binding energies differ by less than 0.5 eV, conclusions on atomic charge should be treated with caution. Our experimental data provides a benchmark for calculations of the atomic charge of sulfur obtained using different methods. Atomic charges were computed for lone ions and ion pairs, both in the gas phase (GP) and in a solvation model (SMD), with a wide range of ion pair conformers considered. Three methods were used to compute the atomic charges: charges from the electrostatic potential using a grid based method (ChelpG), natural bond orbital (NBO) population analysis and Bader's atoms in molecules (AIM) approach. By comparing the experimental and calculated measures of the atomic charge of sulfur, we provide an order for the sulfur atoms, ranging from the most negative to the most positive atomic charge. Furthermore, we show that both ChelpG and NBO are reasonable methods for calculating the atomic charge of sulfur in ILs, based on the agreement with both the XPS and NEXAFS spectroscopy results. However, the atomic charges of sulfur derived from ChelpG are found to display significant, non-physical conformational dependence. Only small differences in individual atomic charge of sulfur were observed between lone ion (GP) and ion pair IL(SMD) model systems, indicating that ion-ion interactions do not strongly influence individual atomic charges.

A probabilistic analysis of the implications of instrument failures on ESA's Swarm mission for its individual satellite orbit deployments

NASA Astrophysics Data System (ADS)

Jackson, Andrew

2015-07-01

On launch, one of Swarm's absolute scalar magnetometers (ASMs) failed to function, leaving an asymmetrical arrangement of redundant spares on different spacecrafts. A decision was required concerning the deployment of individual satellites into the low-orbit pair or the higher "lonely" orbit. I analyse the probabilities for successful operation of two of the science components of the Swarm mission in terms of a classical probabilistic failure analysis, with a view to concluding a favourable assignment for the satellite with the single working ASM. I concentrate on the following two science aspects: the east-west gradiometer aspect of the lower pair of satellites and the constellation aspect, which requires a working ASM in each of the two orbital planes. I use the so-called "expert solicitation" probabilities for instrument failure solicited from Mission Advisory Group (MAG) members. My conclusion from the analysis is that it is better to have redundancy of ASMs in the lonely satellite orbit. Although the opposite scenario, having redundancy (and thus four ASMs) in the lower orbit, increases the chance of a working gradiometer late in the mission; it does so at the expense of a likely constellation. Although the results are presented based on actual MAG members' probabilities, the results are rather generic, excepting the case when the probability of individual ASM failure is very small; in this case, any arrangement will ensure a successful mission since there is essentially no failure expected at all. Since the very design of the lower pair is to enable common mode rejection of external signals, it is likely that its work can be successfully achieved during the first 5 years of the mission.

75 FR 64972 - Proposed Revocation of Class E Airspace; Lone Star, TX

Federal Register 2010, 2011, 2012, 2013, 2014

2010-10-21

...-0772; Airspace Docket No. 10-ASW-10] Proposed Revocation of Class E Airspace; Lone Star, TX AGENCY... action proposes to remove Class E airspace at Lone Star, TX. Abandonment of the former Lone Star Steel... need for controlled airspace in the Lone Star, TX, area. The FAA is taking this action to ensure the...

The Impact of Modernization on the Military Capabilities of the People’s Republic of China.

DTIC Science & Technology

1982-04-19

pair of allies on the Standing Committee were Ye Jianying and Li Xiannian, who represented both the veteran cadres who had survived the Cultural...in October with the arrest of the four leading radical figures ("Gang of Four") in a coup lead by the Defense Minister, Marshall Ye Jianying who...Dengkui, and Wu De, from the Politburo. A new Standing Committee was constituted on which Hua Guofeng now sat in lonely isolation; Marshal Ye Jianying and

Rotational Spectra and Nuclear Quadrupole Coupling Constants of Iodoimidazoles

NASA Astrophysics Data System (ADS)

Cooper, Graham A.; Anderson, Cara J.; Medcraft, Chris; Legon, Anthony; Walker, Nick

2017-06-01

The microwave spectra of two isomers of iodoimidazole have been recorded and assigned with resolution of their nuclear quadrupole coupling constants. These constants have been analysed in terms of the conjugation between the lone pairs on the iodine atom and the aromatic π-bonding system, and the effect of this conjugation on the distribution of π-electron density in the ring. A comparison of these properties has been made between iodoimidazole and other 5- and 6-membered aromatic rings bonded to halogen atoms.

Halogen bonds in clathrate cages: A real space perspective.

PubMed

Guevara-Vela, José Manuel; Ochoa-Resendiz, David; Costales, Aurora; Hernández-Lamoneda, Ramón; Martin Pendas, Angel

2018-06-22

In this paper we present real space analyses of the nature of the dihalogen-water cage interactions in the 5^{12} and 5^{12}6^2 clathrate cages containing chlorine and bromine, respectively. Our Quantum Theory of Atoms in Molecules and Interacting Quantum Atoms results provide strong indications that halogen bonding is present even though the lone pairs of water molecules are already engaged in hydrogen bonding interactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure and bonding of [Pd2Sn18]4-: an interesting example of the mutual delocalisation phenomenon.

PubMed

Sheong, Fu Kit; Chen, Wen-Jie; Zhang, Jing-Xuan; Li, Yang; Lin, Zhenyang

2017-02-14

In this article, we have presented a computational analysis on the structure and bonding of [Pd 2 Sn 18 ] 4- and illustrated that it serves as an interesting example of OMO-UMO mutual delocalisation with two identical [PdE 9 ] 2- fragments. We have also illustrated the alternative roles that could be played by an [ME 9 ] 2- /[E 9 ] 2- fragment, a simple L-type donor and a lone-pair acceptor.

Density functional theory study on the ionic liquid pyridinium hydrogen sulfate

NASA Astrophysics Data System (ADS)

Tankov, Ivaylo; Yankova, Rumyana; Genieva, Svetlana; Mitkova, Magdalena; Stratiev, Dicho

2017-07-01

The geometry, electronic structure and chemical reactivity of a pyridinium-based ionic liquid, pyridinium hydrogen sulfate ([H-Pyr]+[HSO4]-), have been discussed on the basis of quantum chemical density functional theory calculations using B3LYP/6-311+G(d,p) and B3LYP/6-311++G(2d,2p) approaches. The calculations indicated that [H-Pyr]+[HSO4]- exists in the form of an ion pair. A large electropositive potential was found on the pyridinium ring, while the regions of a negative electrostatic potential is linked with the lone pair of electronegative oxygen atoms in hydrogen sulfate anion ([HSO4]-). Electron transfer both within the anion, and between the anion and cation of an ion pair were described using natural bond orbital theory. The energy values of -7.1375 and -2.8801 eV were related to HOMO and LUMO orbitals, respectively.

The Effect of Loneliness on Social Networking Sites Use and Its Related Behaviors.

PubMed

Ranaeiy, Samira; Taghavi, Mohammad Reza; Goodarzi, Mohammad Ali

2016-08-01

The current research was conducted to examine the effect of "Loneliness", on time spent in Social Networking Sites (S.N.S), main reasons for S.N.S use, and its related behaviors. 156 students of Shiraz University voluntarily participated in this research. Loneliness was assessed usingthe UCLA Loneliness scale. 25% of highest scoring students reported that they were lonely whereas 25% of the lowest scoring students were considered to be non-lonely. The positive and negative reasons of using S.N.S were assessed based on Reasons for Internet Use Scale, and internet behaviors were assessed based on Scale of Internet Behaviors. There was no difference in time spent in S.N.S as well as the positive and negative reasons of using S.N.S (contrary to literature), but internet behaviors showed a significant difference between "lonely" and "non-lonely" individuals. "Lonely" and "non-lonely" individuals showed a significant difference in "social aspect" of S.N.S behaviors. There was also a significant difference between "Lonely" and "non-Lonely" individuals in "Negative impact" of S.N.S behaviors. Yet, there seemed to be no difference in "competency and convenience aspect" of S.N.S behaviors. This study suggested that there is no difference between lonely and non-lonely individuals in reasons for using S.N.S and time spent in S.N.S. This finding stands contrary to previous research findings and general literature on the subject In other words, what drives people to S.N.S at the first place shows no significant difference between lonely and non-lonely individuals while after attending S.N.S, social behavior of lonely individuals shows a significant difference which is consistently enhanced online. Lonely people also significantly develop internet-related problems in their daily functioning, including interference with real life socializing.

Two-thumb technique is superior to two-finger technique during lone rescuer infant manikin CPR.

PubMed

Udassi, Sharda; Udassi, Jai P; Lamb, Melissa A; Theriaque, Douglas W; Shuster, Jonathan J; Zaritsky, Arno L; Haque, Ikram U

2010-06-01

Infant CPR guidelines recommend two-finger chest compression with a lone rescuer and two-thumb with two rescuers. Two-thumb provides better chest compression but is perceived to be associated with increased ventilation hands-off time. We hypothesized that lone rescuer two-thumb CPR is associated with increased ventilation cycle time, decreased ventilation quality and fewer chest compressions compared to two-finger CPR in an infant manikin model. Crossover observational study randomizing 34 healthcare providers to perform 2 min CPR at a compression rate of 100 min(-1) using a 30:2 compression:ventilation ratio comparing two-thumb vs. two-finger techniques. A Laerdal Baby ALS Trainer manikin was modified to digitally record compression rate, compression depth and compression pressure and ventilation cycle time (two mouth-to-mouth breaths). Manikin chest rise with breaths was video recorded and later reviewed by two blinded CPR instructors for percent effective breaths. Data (mean+/-SD) were analyzed using a two-tailed paired t-test. Significance was defined qualitatively as p< or =0.05. Mean % effective breaths were 90+/-18.6% in two-thumb and 88.9+/-21.1% in two-finger, p=0.65. Mean time (s) to deliver two mouth-to-mouth breaths was 7.6+/-1.6 in two-thumb and 7.0+/-1.5 in two-finger, p<0.0001. Mean delivered compressions per minute were 87+/-11 in two-thumb and 92+/-12 in two-finger, p=0.0005. Two-thumb resulted in significantly higher compression depth and compression pressure compared to the two-finger technique. Healthcare providers required 0.6s longer time to deliver two breaths during two-thumb lone rescuer infant CPR, but there was no significant difference in percent effective breaths delivered between the two techniques. Two-thumb CPR had 4 fewer delivered compressions per minute, which may be offset by far more effective compression depth and compression pressure compared to two-finger technique. Copyright 2010 Elsevier Ireland Ltd. All rights reserved.

Long-term endurance sport is a risk factor for development of lone atrial flutter.

PubMed

Claessen, Guido; Colyn, Erwin; La Gerche, André; Koopman, Pieter; Alzand, Becker; Garweg, Christophe; Willems, Rik; Nuyens, Dieter; Heidbuchel, Hein

2011-06-01

To evaluate whether in a population of patients with 'lone atrial flutter', the proportion of those engaged in long-term endurance sports is higher than that observed in the general population. An age and sex-matched retrospective case-control study. A database with 638 consecutive patients who underwent ablation for atrial flutter at the University of Leuven. Sixty-one patients (55 men, 90%) fitted the inclusion criteria of 'lone atrial flutter', ie, aged 65 years or less, without documented atrial fibrillation and without identifiable underlying disease (including hypertension). Sex, age and inclusion criteria-matched controls, two for each flutter patient, were selected in a general practice in the same geographical region. Sports activity was evaluated by detailed questionnaires, which were available in 58 flutter patients (95%). A transthoracic echocardiogram was performed in all lone flutter patients. Types of sports, number of years of participation and average number of hours per week. The proportion of regular sportsmen (≥3 h of sports practice per week) among patients with lone atrial flutter was significantly higher than that observed in the general population (50% vs 17%; p<0.0001). The proportion of sportsmen engaged in long-term endurance sports (participation in cycling, running or swimming for ≥3 h/week) was also significantly higher in lone flutter patients than in controls (31% vs 8%; p=0.0003). Those flutter patients performing endurance sports had a larger left atrium than non-sportsmen (p=0.04, by one-way analysis of variance). A history of endurance sports and subsequent left atrial remodelling may be a risk factor for the development of atrial flutter.

Effect of the Pb(2+) lone electron pair in the structure and properties of the double perovskites Pb2Sc(Ti0.5Te0.5)O6 and Pb2Sc(Sc0.33Te0.66)O6: relaxor state due to intrinsic partial disorder.

PubMed

Larrégola, S A; Alonso, J A; Algueró, M; Jiménez, R; Suard, E; Porcher, F; Pedregosa, J C

2010-06-07

We describe the preparation, the crystal structure refined from neutron powder diffraction (NPD) data, and study of the permittivity of two related double perovskites, Pb2Sc(Ti0.5Te0.5)O6 and Pb2Sc(Sc0.33Te0.66)O6. These compounds were synthesized by standard ceramic procedures; Rietveld refinements from room temperature NPD data show that the crystal structures are well defined in a cubic unit cell (space group Fm3m) with double parameter, a = 2a0 ≈ 8 Å. They contain a completely ordered array of ScO6 and (B,Te)O6 (B = Sc, Ti) octahedra sharing corners; the PbO12 polyhedra present an off-center displacement of the lead atoms along the [1 1 1] directions, due to the electrostatic repulsion between the Pb(2+) 6 s electron lone-pair and the Pb-O bonds of the cuboctahedron. Both compounds present a low temperature, highly dispersive maximum in permittivity, the position of which follows the Vogel-Fulcher relation with freezing temperatures of 156 and 99 K for Pb2Sc(Ti0.5Te0.5)O6 and Pb2Sc(Sc0.33Te0.66)O6, respectively, exhibiting a typical phenomenology of relaxors.

Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide.

PubMed

Fabini, Douglas H; Stoumpos, Constantinos C; Laurita, Geneva; Kaltzoglou, Andreas; Kontos, Athanassios G; Falaras, Polycarpos; Kanatzidis, Mercouri G; Seshadri, Ram

2016-12-05

The structure of the hybrid perovskite HC(NH 2 ) 2 PbI 3 (formamidinium lead iodide) reflects competing interactions associated with molecular motion, hydrogen bonding tendencies, thermally activated soft octahedral rotations, and the propensity for the Pb 2+ lone pair to express its stereochemistry. High-resolution synchrotron X-ray powder diffraction reveals a continuous transition from the cubic α-phase (Pm3‾ m, #221) to a tetragonal β-phase (P4/mbm, #127) at around 285 K, followed by a first-order transition to a tetragonal γ-phase (retaining P4/mbm, #127) at 140 K. An unusual reentrant pseudosymmetry in the β-to-γ phase transition is seen that is also reflected in the photoluminescence. Around room temperature, the coefficient of volumetric thermal expansion is among the largest for any extended crystalline solid. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab initio study of the barrier to internal rotation in simple amides. 1. N, N-dimethylformamide and N, N-dimethylcarbamic halogenides

NASA Astrophysics Data System (ADS)

Vassilev, Nikolay G.; Dimitrov, Valentin S.

1999-06-01

Free energies of activation for rotation about the amide C-N bond in X-C(O)N(CH 3) 2 (X=H, F, Cl and Br) were calculated at the MP2(fc)/6-31+G*//6-31G* and MP2(fc)/6-311++G**//6-311++G** levels and compared with NMR gas-phase data. The results of calculations indicate that the repulsion between X and methyl group in ground state and the repulsion between X or oxygen and nitrogen lone pair in transition states (TS) are largely responsible for the difference in the free energies of the studied amides. For X=H (DMF), the anti TS is more stable; for the cases X=Cl, Br, the syn TS is more stable, while for the case X=F the two transition states are energetically almost equivalent.

Influence of 6s{sup 2} lone pair electrons of Bi{sup 3+} on its preferential site occupancy in fluorapatite, NaCa{sub 3}Bi(PO{sub 4}){sub 3}F – An insight from Eu{sup 3+} luminescent probe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lakshminarasimhan, N., E-mail: nlnsimha@gmail.com; Varadaraju, U.V.

2014-12-15

Graphical abstract: Eu{sup 3+} structural probe – difference in Eu{sup 3+} PL emission in (a) NaCa{sub 3}Bi{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F and (b) NaCa{sub 3}La{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F suggests Bi{sup 3+} with preferential site occupancy at M(II) site directing Eu{sup 3+} to M(I) site. - Highlights: • Eu{sup 3+} luminescent probe used for establishing the role of 6s{sup 2} lone pair electrons of Bi{sup 3+} in fluorapatite. • Difference in Eu{sup 3+} PL emission spectral features in NaCa{sub 3}Bi{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F and NaCa{sub 3}La{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F. • Preferential site occupancy of Bi{sup 3+} in M(II)more » site directs Eu{sup 3+} to M(I) site in NaCa{sub 3}Bi{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F. - Abstract: Eu{sup 3+} luminescence was used as a structural probe in understanding the preferential site occupancy of lone pair cation, Bi{sup 3+}, in fluorapatite by comparing the photoluminescence (PL) emission spectral features with that of in analogous La{sup 3+} based fluorapatite. The fluorapatites, NaCa{sub 3}Bi{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F and NaCa{sub 3}La{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F, were synthesized by conventional high temperature solid state reaction method and characterized by powder X-ray diffraction (XRD) and FT-IR spectroscopy. The Eu{sup 3+} PL results revealed a difference in the emission spectral features in NaCa{sub 3}Bi{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F and NaCa{sub 3}La{sub 0.95}Eu{sub 0.05}(PO{sub 4}){sub 3}F. This difference in Eu{sup 3+} PL emission can be attributed to the difference in its site occupancy in the studied fluorapatites.« less

Loneliness and Mortality Among Older Adults in China

PubMed Central

Waite, Linda J.

2014-01-01

Objectives. To examine the relationships between loneliness, social and health behaviors, health, and mortality among older adults in China. Method. Data came from a nationally representative sample of 14,072 adults aged 65 and older from the 2002, 2005, and 2008 waves of the Chinese Longitudinal Healthy Longevity Survey. A cross-lagged model combined with survival analysis was used to assess the relationships between loneliness, behavioral and health outcomes, and risk of mortality. Results. About 28% of older Chinese adults reported feeling lonely, and lonely adults faced increased risks of dying over the subsequent years. Some of the effect was explained by social and health behaviors, but most of the effect was explained by health outcomes. Loneliness both affects and is affected by social activities, solitary leisure activities, physical exercise, emotional health, self-rated health, and functional limitations over a 3-year period. Discussion. Loneliness is part of a constellation of poor social, emotional, and health outcomes for Chinese older adults. Interventions to increase the social involvement of lonely individuals may improve well-being and lengthen life. PMID:24550354

The free jet microwave spectrum of 2-phenylethylamine-water.

PubMed

Melandri, Sonia; Maris, Assimo; Giuliano, Barbara M; Favero, Laura B; Caminati, Walther

2010-09-21

We observed the rotational spectrum of the 1:1 molecular adduct between 2-phenylethylamine and water (normal and H(2)(18)O species) by free jet absorption microwave spectroscopy in the frequency region 60-78 GHz. The dominant spectrum belongs to the structure where the PEA moiety is in the most stable gauche conformation and the water molecule is hydrogen bound to the nitrogen lone pair. The orientation of the water molecule is such that the oxygen atom is almost equidistant (ca. 2.5 A) from the closest methylenic and aromatic hydrogen atoms.

Rearrangement of 3-Membered 1,1,2-Trifluorobromonium and Iodonium Ions and Comparison of Trifluorochloronium to Fluorocarbeniuim Ions (Postprint)

DTIC Science & Technology

2008-01-01

The steric effect and repulsive forces from the lone-pair electrons on the fluorine atoms of 5 shield the carbon nucleus, rendering it resistant to... Electrophilic addition of Cl2 to alkene 2 gives 2% of rearranged product (Table 3, run 5). Intermediate 5 (Scheme 1, X ) Y ) Cl; Z ) Br) is 22.1 kcal...71 and 190. Chambers, R. D. Fluorine in Organic Chemistry; Wiley: New York, 1973; p 98. (4) (a) Heine, H. W.; Siegfried, W. J. Am. Chem. Soc. 1954

New acceptor-bridge-donor strategy for enhancing NLO response with long-range excess electron transfer from the NH2...M/M3O donor (M = Li, Na, K) to inside the electron hole cage C20F19 acceptor through the unusual σ chain bridge (CH2)4.

PubMed

Bai, Yang; Zhou, Zhong-Jun; Wang, Jia-Jun; Li, Ying; Wu, Di; Chen, Wei; Li, Zhi-Ru; Sun, Chia-Chung

2013-04-04

Using the strong electron hole cage C20F19 acceptor, the NH2...M/M3O (M = Li, Na, and K) complicated donors with excess electron, and the unusual σ chain (CH2)4 bridge, we construct a new kind of electride molecular salt e(-)@C20F19-(CH2)4-NH2...M(+)/M3O(+) (M = Li, Na, and K) with excess electron anion inside the hole cage (to be encapsulated excess electron-hole pair) serving as a new A-B-D strategy for enhancing nonlinear optical (NLO) response. An interesting push-pull mechanism of excess electron generation and its long-range transfer is exhibited. The excess electron is pushed out from the (super)alkali atom M/M3O by the lone pair of NH2 in the donor and further pulled inside the hole cage C20F19 acceptor through the efficient long σ chain (CH2)4 bridge. Owing to the long-range electron transfer, the new designed electride molecular salts with the excess electron-hole pair exhibit large NLO response. For the e(-)@C20F19-(CH2)4-NH2...Na(+), its large first hyperpolarizability (β0) reaches up to 9.5 × 10(6) au, which is about 2.4 × 10(4) times the 400 au for the relative e(-)@C20F20...Na(+) without the extended chain (CH2)4-NH2. It is shown that the new strategy is considerably efficient in enhancing the NLO response for the salts. In addition, the effects of different bridges and alkali atomic number on β0 are also exhibited. Further, three modulating factors are found for enhancing NLO response. They are the σ chain bridge, bridge-end group with lone pair, and (super)alkali atom. The new knowledge may be significant for designing new NLO materials and electronic devices with electrons inside the cages. They may also be the basis of establishing potential organic chemistry with electron-hole pair.

Physical origins of weak H{sub 2} binding on carbon nanostructures: Insight from ab initio studies of chemically functionalized graphene nanoribbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ulman, Kanchan; Bhaumik, Debarati; Wood, Brandon C.

2014-05-07

We have performed ab initio density functional theory calculations, incorporating London dispersion corrections, to study the absorption of molecular hydrogen on zigzag graphene nanoribbons whose edges have been functionalized by OH, NH{sub 2}, COOH, NO{sub 2}, or H{sub 2}PO{sub 3}. We find that hydrogen molecules always preferentially bind at or near the functionalized edge, and display induced dipole moments. Binding is generally enhanced by the presence of polar functional groups. The largest gains are observed for groups with oxygen lone pairs that can facilitate local charge reorganization, with the biggest single enhancement in adsorption energy found for “strong functionalization” bymore » H{sub 2}PO{sub 3} (115 meV/H{sub 2} versus 52 meV/H{sub 2} on bare graphene). We show that for binding on the “outer edge” near the functional group, the presence of the group can introduce appreciable contributions from Debye interactions and higher-order multipole electrostatic terms, in addition to the dominant London dispersion interactions. For those functional groups that contain the OH moiety, the adsorption energy is linearly proportional to the number of lone pairs on oxygen atoms. Mixed functionalization with two different functional groups on a graphene edge can also have a synergistic effect, particularly when electron-donating and electron-withdrawing groups are combined. For binding on the “inner edge” somewhat farther from the functional group, most of the binding again arises from London interactions; however, there is also significant charge redistribution in the π manifold, which directly reflects the electron donating or withdrawing capacity of the functional group. Our results offer insight into the specific origins of weak binding of gas molecules on graphene, and suggest that edge functionalization could perhaps be used in combination with other strategies to increase the uptake of hydrogen in graphene. They also have relevance for the storage of hydrogen in porous carbon materials, such as activated carbons.« less

An ab initio MO study of heavy atom effects on the zero-field splitting tensors of high-spin nitrenes: how the spin-orbit contributions are affected.

PubMed

Sugisaki, Kenji; Toyota, Kazuo; Sato, Kazunobu; Shiomi, Daisuke; Kitagawa, Masahiro; Takui, Takeji

2014-05-21

The CASSCF and the hybrid CASSCF-MRMP2 methods are applied to the calculations of spin-spin and spin-orbit contributions to the zero-field splitting tensors (D tensors) of the halogen-substituted spin-septet 2,4,6-trinitrenopyridines, focusing on the heavy atom effects on the spin-orbit term of the D tensors (D(SO) tensors). The calculations reproduced experimentally determined |D| values within an error of 15%. Halogen substitutions at the 3,5-positions are less influential in the spin-spin dipolar (D(SS)) term of 2,4,6-trinitrenopyridines, although the D(SO) terms are strongly affected by the introduction of heavier halogens. The absolute sign of the D(SO) value (D = D(ZZ) - (D(XX) + D(YY))/2) of 3,5-dibromo derivative 3 is predicted to be negative, which contradicts the Pederson-Khanna (PK) DFT result previously reported. The large negative contributions to the D(SO) value of 3 arise from the excited spin-septet states ascribed mainly to the excitations of in-plane lone pair of bromine atoms → SOMO of π nature. The importance of the excited states involving electron transitions from the lone pair orbital of the halogen atom is also confirmed in the D(SO) tensors of halogen-substituted para-phenylnitrenes. A new scheme based on the orbital region partitioning is proposed for the analysis of the D(SO) tensors as calculated by means of the PK-DFT approach.

Castaways: addressing hostility and helplessness in severely lonely adults.

PubMed

Loboprabhu, Sheila; Molinari, Victor; Asghar-Ali, Ali Abbas

2015-03-01

Hostility and helplessness are recurrent themes in severely lonely adults, and they can be both causes and effects of subjective feelings of loneliness. Since many lonely patients report a history of abuse, hostile and helpless states of mind may reflect identification with hostile (aggressor) or helpless (passive) attachment figures. Hostile intrusiveness and helpless withdrawal by the parent are 2 distinct patterns of parent-child misattunement that can lead to infant disorganization via disrupted emotional communication and to loneliness later in life. Anxious-ambivalent lonely older adults tend to exhibit hyperactivating hostile behaviors (to deal with a core sense of powerlessness), whereas those with fearful-avoidant attachment styles exhibit deactivating helpless behaviors (to deflect intense underlying feelings of rage). Based on this model, we outline different treatment approaches for lonely persons with different attachment styles by describing the successful treatment of two severely lonely, suicidal veterans. We describe an approach to treating hostile and helpless behaviors in lonely patients, using validation, mentalization, reality orientation, and socialization. Validation provides a sense of safety and rapport. Mentalization allows the lonely individual to better appreciate his or her own mental processes and those of others. Reality orientation provides feedback to lonely individuals on whether their perceptions are accurate and reality-based and helps them appreciate the consequences their behavior may have for self and others. Finally, socialization reduces disenfranchisement by teaching/re-teaching individuals social skills that may have become impaired by prolonged isolation.

A false dichotomy? Mental illness and lone-actor terrorism.

PubMed

Corner, Emily; Gill, Paul

2015-02-01

We test whether significant differences in mental illness exist in a matched sample of lone- and group-based terrorists. We then test whether there are distinct behavioral differences between lone-actor terrorists with and without mental illness. We then stratify our sample across a range of diagnoses and again test whether significant differences exist. We conduct a series of bivariate, multivariate, and multinomial statistical tests using a unique dataset of 119 lone-actor terrorists and a matched sample of group-based terrorists. The odds of a lone-actor terrorist having a mental illness is 13.49 times higher than the odds of a group actor having a mental illness. Lone actors who were mentally ill were 18.07 times more likely to have a spouse or partner who was involved in a wider movement than those without a history of mental illness. Those with a mental illness were more likely to have a proximate upcoming life change, more likely to have been a recent victim of prejudice, and experienced proximate and chronic stress. The results identify behaviors and traits that security agencies can utilize to monitor and prevent lone-actor terrorism events. The correlated behaviors provide an image of how risk can crystalize within the individual offender and that our understanding of lone-actor terrorism should be multivariate in nature.

The three-dimensional structure of "Lonely Guy" from Claviceps purpurea provides insights into the phosphoribohydrolase function of Rossmann fold-containing lysine decarboxylase-like proteins.

PubMed

Dzurová, Lenka; Forneris, Federico; Savino, Simone; Galuszka, Petr; Vrabka, Josef; Frébort, Ivo

2015-08-01

The recently discovered cytokinin (CK)-specific phosphoribohydrolase "Lonely Guy" (LOG) is a key enzyme of CK biosynthesis, converting inactive CK nucleotides into biologically active free bases. We have determined the crystal structures of LOG from Claviceps purpurea (cpLOG) and its complex with the enzymatic product phosphoribose. The structures reveal a dimeric arrangement of Rossmann folds, with the ligands bound to large pockets at the interface between cpLOG monomers. Structural comparisons highlight the homology of cpLOG to putative lysine decarboxylases. Extended sequence analysis enabled identification of a distinguishing LOG sequence signature. Taken together, our data suggest phosphoribohydrolase activity for several proteins of unknown function. © 2015 Wiley Periodicals, Inc.

Lone Actor Terrorist Attack Planning and Preparation: A Data-Driven Analysis.

PubMed

Schuurman, Bart; Bakker, Edwin; Gill, Paul; Bouhana, Noémie

2017-10-23

This article provides an in-depth assessment of lone actor terrorists' attack planning and preparation. A codebook of 198 variables related to different aspects of pre-attack behavior is applied to a sample of 55 lone actor terrorists. Data were drawn from open-source materials and complemented where possible with primary sources. Most lone actors are not highly lethal or surreptitious attackers. They are generally poor at maintaining operational security, leak their motivations and capabilities in numerous ways, and generally do so months and even years before an attack. Moreover, the "loneness" thought to define this type of terrorism is generally absent; most lone actors uphold social ties that are crucial to their adoption and maintenance of the motivation and capability to commit terrorist violence. The results offer concrete input for those working to detect and prevent this form of terrorism and argue for a re-evaluation of the "lone actor" concept. © 2017 The Authors. Journal of Forensic Sciences published by Wiley Periodicals, Inc. on behalf of American Academy of Forensic Sciences.

Copper(I)-catalyzed substitution reactions of propargylic amines: importance of C(sp)-C(sp3) bond cleavage in generation of iminium intermediates.

PubMed

Sugiishi, Tsuyuka; Kimura, Akifumi; Nakamura, Hiroyuki

2010-04-21

Substitution reactions of propargylic amines proceed in the presence of copper(I) catalysts. Mechanistic studies showed that C(sp)-C(sp(3)) bond cleavage assisted by nitrogen lone-pair electrons is essential for the reaction, and the resulting iminium intermediates undergo amine exchange, aldehyde exchange, and alkyne addition reactions. Because iminium intermediates are key to aldehyde-alkyne-amine (A(3)) coupling reactions, this transformation is effective not only for reconstruction of propargylic amines but also for chiral induction of racemic compounds in the presence of chiral catalysts.

External validity of a generic safety climate scale for lone workers across different industries and companies.

PubMed

Lee, Jin; Huang, Yueng-hsiang; Robertson, Michelle M; Murphy, Lauren A; Garabet, Angela; Chang, Wen-Ruey

2014-02-01

The goal of this study was to examine the external validity of a 12-item generic safety climate scale for lone workers in order to evaluate the appropriateness of generalized use of the scale in the measurement of safety climate across various lone work settings. External validity evidence was established by investigating the measurement equivalence (ME) across different industries and companies. Confirmatory factor analysis (CFA)-based and item response theory (IRT)-based perspectives were adopted to examine the ME of the generic safety climate scale for lone workers across 11 companies from the trucking, electrical utility, and cable television industries. Fairly strong evidence of ME was observed for both organization- and group-level generic safety climate sub-scales. Although significant invariance was observed in the item intercepts across the different lone work settings, absolute model fit indices remained satisfactory in the most robust step of CFA-based ME testing. IRT-based ME testing identified only one differentially functioning item from the organization-level generic safety climate sub-scale, but its impact was minimal and strong ME was supported. The generic safety climate scale for lone workers reported good external validity and supported the presence of a common feature of safety climate among lone workers. The scale can be used as an effective safety evaluation tool in various lone work situations. Copyright © 2013 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mitkova, Maria; Butt, Darryl; Kozicki, Michael

For many decades, various radiation detecting material have been extensively researched, to find a better material or mechanism for radiation sensing. Recently, there is a growing need for a smaller and effective material or device that can perform similar functions of bulkier Geiger counters and other measurement options, which fail the requirement for easy, cheap and accurate radiation dose measurement. Here arises the use of thin film chalcogenide glass, which has unique properties of high thermal stability along with high sensitivity towards short wavelength radiation. The unique properties of chalcogenide glasses are attributed to the lone pair p-shell electrons, whichmore » provide some distinctive optical properties when compared to crystalline material. These qualities are derived from the energy band diagram and the presence of localized states in the band gap. Chalcogenide glasses have band tail states and localized states, along with the two band states. These extra states are primarily due to the lone pair electrons as well as the amorphous structure of the glasses. The localized states between the conductance band (CB) and valence band (VB) are primarily due to the presence of the lone pair electrons, while the band tail states are attributed to the Van der Waal's forces between layers of atoms [1]. Localized states are trap locations within the band gap where electrons from the valence band can hop into, in their path towards the conduction band. Tail states on the other hand are locations near the band gap edges and are known as Urbach tail states (Eu). These states are occupied with many electrons that can participate in the various transformations due to interaction with photons. According to Y. Utsugi et. al.[2], the electron-phonon interactions are responsible for the generation of the Urbach tails. These states are responsible for setting the absorption edge for these glasses and photons with energy near the band gap affect these states. We have studied the effect of x-rays and γ-rays, on thin film chalcogenide glasses and applied them in conjunction with film incorporating a silver source in a new type of radiation sensor for which we have an US patent application [3]. In this report, we give data about our studies regarding our designed radiation sensor along with the testing and performance at various radiation doses. These studies have been preceded by materials characterization research related to the compositional and structural characteristics of the active materials used in the radiation sensor design. During the work on the project, we collected a large volume of material since every experiment was repeated many times to verify the results. We conducted a comprehensive material research, analysis and discussion with the aim to understand the nature of the occurring effects, design different structures to harness these effects, generated models to aid in the understanding the effects, built different device structures and collected data to quantify device performance. These various aspects of our investigation have been detailed in previous quarterly reports. In this report, we present our main results and emphasize on the results pertaining to the core project goals materials development, sensor design and testing and with an emphasis on classifying the appropriate material and design for the optimal application. The report has three main parts: (i) Presentation of the main data; (ii) Bulleted summary of the most important results; (iii) List of the patent, journal publications, conference proceedings and conferences participation, occurring as a result of working on the project.« less

High-pressure modulation of the structure of the bacterial photochemical reaction center at physiological and cryogenic temperatures

NASA Astrophysics Data System (ADS)

Timpmann, Kõu; Kangur, Liina; Lõhmus, Ants; Freiberg, Arvi

2017-07-01

The optical absorption and fluorescence response to external high pressure of the reaction center membrane chromoprotein complex from the wild-type non-sulfur photosynthetic bacterium Rhodobacter sphaeroides was investigated using the native pigment cofactors as local molecular probes of the reaction center structure at physiological (ambient) and cryogenic (79 K) temperatures. In detergent-purified complexes at ambient temperature, abrupt blue shift and accompanied broadening of the special pair band was observed at about 265 MPa. These reversible in pressure features were assigned to a pressure-induced rupture of a lone hydrogen bond that binds the photo-chemically active L-branch primary electron donor bacteriochlorophyll cofactor to the surrounding protein scaffold. In native membrane-protected complexes the hydrogen bond rupture appeared significantly restricted and occurred close to about 500 MPa. The free energy change associated with the rupture of the special pair hydrogen bond in isolate complexes was estimated to be equal to about 12 kJ mol-1. In frozen samples at cryogenic temperatures the hydrogen bond remained apparently intact up to the maximum utilized pressure of 600 MPa. In this case, however, heterogeneous spectral response of the cofactors from the L-and M-branches was observed due to anisotropic build-up of the protein structure. While in solid phase, the special pair fluorescence as a function of pressure exactly followed the respective absorption spectrum at a constant Stokes shift, at ambient temperature, the two paths began to deviate strongly from one other at the hydrogen bond rupture pressure. This effect was tentatively interpreted by different emission properties of hydrogen-bound and hydrogen-unbound special pair exciton states.

Understanding Phase-Change Memory Alloys from a Chemical Perspective

NASA Astrophysics Data System (ADS)

Kolobov, A. V.; Fons, P.; Tominaga, J.

2015-09-01

Phase-change memories (PCM) are associated with reversible ultra-fast low-energy crystal-to-amorphous switching in GeTe-based alloys co-existing with the high stability of the two phases at ambient temperature, a unique property that has been recently explained by the high fragility of the glass-forming liquid phase, where the activation barrier for crystallisation drastically increases as the temperature decreases from the glass-transition to room temperature. At the same time the atomistic dynamics of the phase-change process and the associated changes in the nature of bonding have remained unknown. In this work we demonstrate that key to this behavior is the formation of transient three-center bonds in the excited state that is enabled due to the presence of lone-pair electrons. Our findings additionally reveal previously ignored fundamental similarities between the mechanisms of reversible photoinduced structural changes in chalcogenide glasses and phase-change alloys and offer new insights into the development of efficient PCM materials.

Understanding Phase-Change Memory Alloys from a Chemical Perspective.

PubMed

Kolobov, A V; Fons, P; Tominaga, J

2015-09-01

Phase-change memories (PCM) are associated with reversible ultra-fast low-energy crystal-to-amorphous switching in GeTe-based alloys co-existing with the high stability of the two phases at ambient temperature, a unique property that has been recently explained by the high fragility of the glass-forming liquid phase, where the activation barrier for crystallisation drastically increases as the temperature decreases from the glass-transition to room temperature. At the same time the atomistic dynamics of the phase-change process and the associated changes in the nature of bonding have remained unknown. In this work we demonstrate that key to this behavior is the formation of transient three-center bonds in the excited state that is enabled due to the presence of lone-pair electrons. Our findings additionally reveal previously ignored fundamental similarities between the mechanisms of reversible photoinduced structural changes in chalcogenide glasses and phase-change alloys and offer new insights into the development of efficient PCM materials.

Zn3Sb4O6F6: Hydrothermal synthesis, crystal structure and nonlinear optical properties

NASA Astrophysics Data System (ADS)

Ali, Sk Imran; Zhang, Weiguo; Halasyamani, P. Shiv; Johnsson, Mats

2017-12-01

Zn3Sb4O6F6 has been synthesized hydrothermally at 230 °C. The crystal structure was determined from single crystal X-ray diffraction data. It crystallizes in the cubic non-centrosymmetric space group I-43m with the unit cell parameter a = 8.1291(4) Å and is isostructural with M3Sb4O6F6 (M = Co, Ni). The new compound is the first oxofluoride containing Zn2+ and a p-element cation with a stereochemically active lone pair. The crystal structure is made up by [ZnO2F4] octahedra forming a network via corner sharing at F-atoms and [SbO3] trigonal pyramids that form [Sb4O6] cages that connect via the O-atoms to the Zn-atoms. Powder second-harmonic generation (SHG) measurements using 1064 nm radiation on Zn3Sb4O6F6 indicate an SHG intensity of approximately 40 × α-SiO2.

Active public Facebook use and adolescents' feelings of loneliness: Evidence for a curvilinear relationship.

PubMed

Wang, Kexin; Frison, Eline; Eggermont, Steven; Vandenbosch, Laura

2018-06-09

Inconsistent results have been reported concerning the relationships between SNS usage and loneliness. The current two-wave panel study with a one year interval examined the possibility of reciprocal and curvilinear relationships between active public Facebook use and adolescents' social/emotional loneliness. Belgian adolescents from fifteen high schools participated (N = 1188, 55% male). The results showed a U-shaped relationship between (1) active Facebook use and social/emotional loneliness and (2) emotional loneliness and active Facebook use. Specifically, active Facebook use predicted decreased social/emotional loneliness among low to moderate users, while among heavy users, increased levels of social/emotional loneliness were predicted by active Facebook use. Emotional loneliness predicted higher active Facebook use among lonely adolescents. At the same time, emotional loneliness predicted decreased active Facebook use among adolescents who did not feel lonely. These findings stress to consider different types of loneliness, and reciprocal and curvilinear relationships in future social media research. Copyright © 2018 The Foundation for Professionals in Services for Adolescents. Published by Elsevier Ltd. All rights reserved.

Does financial hardship account for elevated psychological distress in lone mothers?

PubMed

Hope, S; Power, C; Rodgers, B

1999-12-01

Lone mothers have been shown to have higher levels of psychological distress than married mothers, but it is not clear how this difference arises. Using data from the 1958 British birth cohort followed to age 33, we investigated alternative explanations for the excess distress of lone mothers. Logistic regression models were used to estimate odds ratios for distress (measured using the Malaise Inventory) in lone vs married mothers. Odds ratios were adjusted to assess the contribution of explanatory factors. At age 33, psychological distress was greater among lone than married mothers (OR 2.59, 95% CI 1.97, 3.41). The odds ratio decreased to 1.43 (95% CI 1.02, 2.01) after adjustment for all explanatory factors (prior psychological distress, age of youngest child and number of children in the household, and contemporary measures of financial hardship, employment, and social support). Attenuation of the odds ratio was most marked after taking account of financial hardship. Psychological distress was greater among divorced mothers than never married mothers, though not significantly (OR = 1.70, 95% CI 0.88, 3.28). This difference was not explained by the factors examined, and was not due to the immediate distress associated with a recent divorce. Elevated psychological distress of lone mothers appears to be related to financial hardship, while other explanations, including social support and selection, have a more modest impact. Not all of the elevated psychological distress among lone mothers was accounted for, particularly among divorced lone mothers.

Lone-pair interactions and photodissociation of compressed nitrogen trifluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurzydłowski, D., E-mail: dkurzydlowski@uw.edu.pl; Department of Biogeochemistry, Max Planck Institute for Chemistry, 55128 Mainz; Wang, H. B.

2014-08-14

High-pressure behavior of nitrogen trifluoride (NF{sub 3}) was investigated by Raman and IR spectroscopy at pressures up to 55 GPa and room temperature, as well as by periodic calculations up to 100 GPa. Experimentally, we find three solid-solid phase transitions at 9, 18, and 39.5 GPa. Vibrational spectroscopy indicates that in all observed phases NF{sub 3} remains in the molecular form, in contrast to the behavior of compressed ammonia. This finding is confirmed by density functional theory calculations, which also indicate that the phase transitions of compressed NF{sub 3} are governed by the interplay between lone‑pair interactions and efficient moleculemore » packing. Although nitrogen trifluoride is molecular in the whole pressure range studied, we show that it can be photodissociated by mid-IR laser radiation. This finding paves the way for the use of NF{sub 3} as an oxidizing and fluorinating agent in high-pressure reactions.« less

Stable Chloro- and Bromoxenate Cage Anions; [X3(XeO3)3]3- and [X4(XeO3)4]4- (X = Cl or Br).

PubMed

Goettel, James T; Haensch, Veit G; Schrobilgen, Gary J

2017-06-28

The number of isolable compounds which contain different noble-gas-element bonds is limited for xenon and even more so for krypton. Examples of Xe-Cl bonds are rare, and prior to this work, no Xe-Br bonded compound had been isolated in macroscopic quantities. The syntheses, isolation, and characterization of the first compounds to contain Xe-Br bonds and their chlorine analogues are described in the present work. The reactions of XeO 3 with [N(CH 3 ) 4 ]Br and [N(C 2 H 5 ) 4 ]Br have provided two bromoxenate salts, [N(C 2 H 5 ) 4 ] 3 [Br 3 (XeO 3 ) 3 ] and [N(CH 3 ) 4 ] 4 [Br 4 (XeO 3 ) 4 ], in which the cage anions have Xe-Br bond lengths that range from 3.0838(3) to 3.3181(8) Å. The isostructural chloroxenate anions (Xe-Cl bond lengths, 2.9316(2) to 3.101(4) Å) were synthesized by analogy with their bromine analogues. The bromo- and chloroxenate salts are stable in the atmosphere at room temperature and were characterized in the solid state by Raman spectroscopy and low-temperature single-crystal X-ray diffraction, and in the gas phase by quantum-chemical calculations. They are the only known examples of cage anions that contain a noble-gas element. The Xe-Br and Xe-Cl bonds are very weakly covalent and can be viewed as σ-hole interactions, similar to those encountered in halogen bonding. However, the halogen atoms in these cases are valence electron lone pair donors, and the σ* Xe-O orbitals are lone pair acceptors.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berastegui, P.; Hull, S., E-mail: stephen.hull@stfc.ac.u; Eriksson, S.G.

The compound CsSn{sub 2}F{sub 5} has been investigated over the temperature range from ambient to 545 K using differential scanning calorimetry, impedance spectroscopy and neutron powder diffraction methods. A first-order phase transition is observed from DSC measurements at 510(2) K, to a phase possessing a high ionic conductivity ({sigma}{approx}2.5x10{sup -2} {Omega}{sup -1} cm{sup -1} at 520 K). The crystal structure of the high temperature superionic phase (labelled {alpha}) has been determined to be tetragonal (space group I4/mmm, a=4.2606(10) A, c=19.739(5) A and Z=2) in which the cations form layers perpendicular to the [001] direction, with a stacking sequence CsSnSnCsSnSn... Allmore » the anions are located in two partially occupied sites in the gap between the Cs and Sn layers, whilst the space between the Sn cations is empty, due to the orientation of the lone-pair electrons associated with the Sn{sup 2+}. The structure of {alpha}-CsSn{sub 2}F{sub 5} is discussed in relation to two other layered F{sup -} conducting superionic phases containing Sn{sup 2+} cations, {alpha}-RbSn{sub 2}F{sub 5} and {alpha}-PbSnF{sub 4} and, to facilitate this comparison, an improved structural characterisation of the former is also presented. The wider issue of the role of lone-pair cations such as Sn{sup 2+} in promoting dynamic disorder within an anion substructure is also briefly addressed. - Graphical abstract: CsSn{sub 2}F{sub 5} is shown to undergo a first order phase transition at 510(2) K to a superionic phase in which the specific electronic configuration of the Sn{sup 2+} plays a key role in promoting extensive disorder of the anions.« less

A theoretical study on the electronic structure of Au-XO(0,-1,+1) (X=C, N, and O) complexes: effect of an external electric field.

PubMed

Tielens, Frederik; Gracia, Lourdes; Polo, Victor; Andrés, Juan

2007-12-20

A theoretical study on the nature of Au-XO(0,-1,+1) (X=C, N, O) interaction is carried out in order to provide a better understanding on the adsorption process of XO molecules on Au surfaces or Au-supported surfaces. The effect of the total charge as well as the presence of an external electric field on the formation processes of the Au-XO complex are analyzed and discussed using DFT (B3LYP) and high-level ab initio (CCSD(T)//MP2) methods employing a 6-311+G(3df) basis set for X and O atoms and Stuttgart pseudopotentials for Au atom. The presence of an electric field can increase the binding of O2 molecule to Au while weakening the formation of the Au-CO complex. These behaviors are discussed in the context of adsorption or deadsorption of these molecules on Au clusters. The formation of the Au-XO complex, the effect of addition/removal of one electron, and the role of the electric field are rationalized by studying the nature of the bonding interactions by means of the electron localization function (ELF) analysis. The net interaction between Au and XO fragments is governed by the interplay of three factors: (i) the amount of charge transfer from Au to XO, (ii) the sharing of the lone pair from X atom by the Au core (V(X, Au) basin), and (iii) the role of the lone pair of Au (V(Au) basin) mainly formed by 6s electrons. The total charge of the system and the applied electric field determine the population and orientation of the V(Au) basin and, subsequently, the degree of repulsion with the V(X, Au) basin.

Occurrence of Amblyomma americanum (Acari: Ixodidae) and Human Infection With Ehrlichia chaffeensis in Wisconsin, 2008-2015.

PubMed

Christenson, Megan; Lee, Xia; Larson, Scott; Johnson, Diep Hoang; Jensen, Julia; Meller, Megan; Paskewitz, Susan

2017-05-01

Because of the increasing incidence of human ehrlichiosis in Wisconsin, we assessed reports of human infections by Ehrlichia chaffeensis and the distribution of its vector, the lone star tick (Amblyomma americanum (L.)). From 2008 through 2015, 158 probable and confirmed human cases of E. chaffeensis infections were reported to the Wisconsin Department of Health Services. Five cases without travel history outside of Wisconsin were confirmed as E. chaffeensis by polymerase chain reaction. Surveillance for the vector occurred from 2008 through 2015 and was based on active and passive methods, including examination of white-tailed deer, collections from live-trapped small mammals, submissions of ticks removed from wild and domestic animals through the Wisconsin Surveillance of Animals for Ticks (SWAT) program, digital or physical submissions by the public to the University of Wisconsin Insect Diagnostic or Medical Entomology laboratories, and active tick dragging. More than 50 lone star ticks (46 adults, 6 nymphs, and 1 larva) were identified. Lone star ticks were more commonly found in south central Wisconsin, particularly in Dane County, where discovery of more than one life stage in a single year indicates possible establishment. © The Authors 2016. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Discrimination of Active and Weakly Active Human BACE1 Inhibitors Using Self-Organizing Map and Support Vector Machine.

PubMed

Li, Hang; Wang, Maolin; Gong, Ya-Nan; Yan, Aixia

2016-01-01

β-secretase (BACE1) is an aspartyl protease, which is considered as a novel vital target in Alzheimer`s disease therapy. We collected a data set of 294 BACE1 inhibitors, and built six classification models to discriminate active and weakly active inhibitors using Kohonen's Self-Organizing Map (SOM) method and Support Vector Machine (SVM) method. Each molecular descriptor was calculated using the program ADRIANA.Code. We adopted two different methods: random method and Self-Organizing Map method, for training/test set split. The descriptors were selected by F-score and stepwise linear regression analysis. The best SVM model Model2C has a good prediction performance on test set with prediction accuracy, sensitivity (SE), specificity (SP) and Matthews correlation coefficient (MCC) of 89.02%, 90%, 88%, 0.78, respectively. Model 1A is the best SOM model, whose accuracy and MCC of the test set were 94.57% and 0.98, respectively. The lone pair electronegativity and polarizability related descriptors importantly contributed to bioactivity of BACE1 inhibitor. The Extended-Connectivity Finger-Prints_4 (ECFP_4) analysis found some vitally key substructural features, which could be helpful for further drug design research. The SOM and SVM models built in this study can be obtained from the authors by email or other contacts.

Entry to lone parenthood: an analysis of marital dissolution in Great Britain.

PubMed

Ermisch, J F; Wright, R E

1994-01-01

"This paper examines some...socio-economic determinants of lone parenthood in Great Britain, in an attempt to understand further the reasons behind the rapid growth in lone parenthood. Since divorce and separation are the major 'causes' of lone parenthood, this paper focuses on the determinants of marital dissolution among women with dependent children. The empirical analysis is guided by hypotheses suggested by the 'economic theory of marriage'. Hazard regression equations are estimated with data collected in the 1980 Women and Employment Survey...." (SUMMARY IN FRE AND ITA) excerpt

Predicting stability and change in loneliness in later life

PubMed Central

Newall, Nancy E. G.; Chipperfield, Judith G.; Bailis, Daniel S.

2016-01-01

This study examined potential discriminators of groups of older adults showing different patterns of stability or change in loneliness over 5 years: those who became lonely, overcame loneliness, were persistently lonely, and were persistently not lonely. Discriminant function analysis results showed that the persistently lonely, compared with the persistently not lonely, were more often living alone, widowed, and experiencing poorer health and perceived control. Moreover, changes in living arrangements and perceived control predicted loneliness change. In conclusion, perceiving that one is able to meet social needs is a predictor of loneliness and loneliness change and appears to be more important than people’s friendships. Because the predictors were better able to predict entry into loneliness, results point to the promise of prevention approaches to loneliness interventions. PMID:27867246

Lone atrial fibrillation: where are we now?

PubMed

Potpara, Tatjana S; Lip, Gregory Y

2011-10-01

There is a growing pandemic of atrial fibrillation (AF), affecting nearly 2% of the general adult population. Atrial fibrillation is commonly associated with structural heart disease, and AF itself causes a sequence of complex processes of electrical, contractile, and structural remodeling of the atrial myocardium, which facilitate further AF progression. Nonetheless, AF may also affect individuals aged ≤ 65 years who have no evidence of associated cardiopulmonary or other disease, including hypertension; this is otherwise referred to as "lone" AF and is considered to have a generally favorable prognosis. The true prevalence of lone AF is unknown. Growing insights into the diversity of numerous mechanisms involved in the pathogenesis of AF, including acute atrial stretch, structural and electrophysiological alterations, systemic inflammation, oxidative stress, autonomic imbalance, genetic predisposition, and many others, and increasing recognition of novel risk factors for AF, including obesity, metabolic syndrome, subclinical atherosclerosis, sleep apnea, alcohol consumption, and endurance sports, suggest that apparently lone AF might not be so "lone" in many patients, which could have important prognostic and therapeutic implications. In this article, we summarize the current knowledge of epidemiology, etiopathogenesis, and pathophysiology of so-called lone AF and discuss the issues of long-term prognosis and management of patients who have an apparently lone AF.

Study of lone working magnetic resonance technologists in Western Australia.

PubMed

Dewland, Tracy Anne; Hancock, Lauren Nicole; Sargeant, Simone; Bailey, Rebecca Kim Min-Ae; Sarginson, Rodger Allan; Ng, Curtise Kin Cheung

2013-12-01

It is recommended that magnetic resonance (MR) technologists should not work alone due to potential occupational health risks although lone working is legally acceptable. The objective of this study was to investigate the current situation of lone working MR technologists in Western Australia (WA) and any issue against the regulations. A questionnaire regarding the issues of occupational health of lone working MR technologists was developed based on relevant literature and distributed to WA MR technologists. Descriptive (percentage of frequency, mean and standard deviation) and inferential statistics (Fisher's exact, Chi(2) and t tests, and analysis of variance) were used to analyze the responses of the yes/no, multiple choice and 5 pt scale questions from the returned questionnaires. The questionnaire response rate was 65.6% (59/90). It was found that about half of the MR technologists (45.8%, 27/59) experienced lone working. The private magnetic resonance imaging (MRI) centers were more likely to arrange technologists to work alone (p < 0.05). The respondents expressed positive views on issues of adequacy of training and arrangement, confidence and comfort towards lone working except immediate assistance for emergency (mean: 3). Factors of existence of MRI safety officer (p < 0.05) and nature of lone working (p < 0.001-0.05) affected MR technologists' concerns. Lone working of MR technologists is common in WA especially in private centers. The training and arrangement provided seem to be adequate for meeting the legal requirements. However, several areas should be improved by the workplaces including enhancement on immediate emergency assistance and concern relief.

Can HN[double bond, length as m-dash]NH, FN[double bond, length as m-dash]NH, or HN[double bond, length as m-dash]CHOH bridge the σ-hole and the lone pair at P in binary complexes with H2XP, for X = F, Cl, NC, OH, CN, CCH, CH3, and H?

PubMed

Del Bene, Janet E; Alkorta, Ibon; Elguero, José

2015-11-11

Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the properties of complexes formed between H2XP, for X = F, Cl, NC, OH, CN, CCH, CH3, and H, and the possible bridging molecules HN[double bond, length as m-dash]NH, FN[double bond, length as m-dash]NH, and HN[double bond, length as m-dash]CHOH. H2XP:HNNH and H2XP:FNNH complexes are stabilized by PN pnicogen bonds, except for H2(CH3)P:FNNH and H3P:FNNH which are stabilized by N-HP hydrogen bonds. H2XP:HNCHOH complexes are stabilized by PN pnicogen bonds and nonlinear O-HP hydrogen bonds. For a fixed H2XP molecule, binding energies decrease in the order HNCHOH > HNNH > FNNH, except for the binding energies of H2(CH3)P and H3P with HNNH and FNNH. Binding energies of complexes with HNCHOH and HNNH increase as the P-N1 distance decreases, but binding energies of complexes with FNNH show little dependence on this distance. The large binding energies of H2XP:HNCHOH complexes arise from a cooperative effect involving electron-pair acceptance by P to form a pnicogen bond, and electron-pair donation by P to form a hydrogen bond. The dominant charge-transfer interaction in these complexes involves electron-pair donation by N across the pnicogen bond, except for complexes in which X is one of the more electropositive substituents, CCH, CH3, and H. For these, lone-pair donation by P across the hydrogen bond dominates. AIM and NBO data for these complexes are consistent with their bonding characteristics, showing molecular graphs with bond critical points and charge-transfer interactions associated with hydrogen and pnicogen bonds. EOM-CCSD spin-spin coupling constants (1p)J(P-N) across the pnicogen bond for each series of complexes correlate with the P-N distance. In contrast, (2h)J(O-P) values for complexes H2XP:HNCHOH do not correlate with the O-P distance, a consequence of the nonlinearity of these hydrogen bonds.

PREFACE: Proceedings of the 7th Liquid Matter Conference (Lund, Sweden, 27 June 1 July 2008)

NASA Astrophysics Data System (ADS)

Kahl, Gerhard; Sciortino, Francesco; Ullner, Magnus

2008-12-01

The three-yearly Liquid Matter Conference is organized by the Liquids Section of the Condensed Matter Division of the European Physical Society. This series of meetings began in Lyon in 1990. The previous meeting was held in 2005 in Utrecht. The original aim of the Liquid Matter Conference was to bring together scientists working on the liquid state of matter. A closer analysis of the program booklets over the past 18 years reveals that new and highly active research fields that are closely related to liquid matter have been successfully integrated in the scope of the conference, notably the rapidly developing fields of soft matter and biophysics. Concomitantly, a broadening of the spectrum from the classical liquid state to a wide spectrum of phases and systems could be observed. Therefore, the rapidly growing field covered by this conference series at present includes physics, chemistry, biology, and chemical engineering as well as various applied research areas. Liquid state physics is at the interface of many research fields. As a consequence, many of the attendants come from adjacent fields and encounter at the Liquid Matter Conference a community where they can meet experts from other research areas. This aspect of the Liquid Matter Conference makes it an exciting meeting as it not only offers the participants an up-to-date picture of the status of research into the liquid state of matter, but it also allows them to establish new (and often unexpected) transdisciplinary contacts for joint scientific endeavours. This applies in particular to the area of soft condensed matter such as colloidal suspensions, polymeric systems and biological materials. The Lund meeting, organized in collaboration with Lund University, had 574 registered participants from five continents. During the conference, and following the tradition established at the Utrecht meeting, the second Liquid Matter Prize of the European Physical Society was awarded to Professor Henk Lekkerkerker (Utrecht) and to Professor Peter Pusey (Edinburgh) for their seminal studies of colloidal matter. In addition to plenary speeches by the two recipients of the Liquid Matter Prize, the scientific program consisted of ten plenary lectures, 108 symposia talks, 23 of which were keynote lectures, and 458 poster contributions. This special issue of Journal of Physics: Condensed Matter contains 47 of the oral communications. The conference was held in the buildings of Lund University and the Student Union facing the University Square in the heart of Lund. The organizers gratefully acknowledge the substantial financial support offered by the Nobel Foundation and by the Swedish Research Council. The success of the conference owes a great debt of gratitude to the members of the Local Organizing Committee and all the people who helped them tirelessly (and very efficiently) to make the conference run smoothly and to the members of the International Program Committee, who were deeply involved in the planning of the conference. During the conference dinner our colleague Lennart Piculell gave a singing performance, which included a song dedicated to the two winners of the Liquid Matter Prize, entitled Hard-Breaking Gel, whose lyrics are printed below. Finally, the Board of the Liquids Section of the European Physical Society decided that the 8th Liquid Matter Conference will be held in Vienna (Austria) 6-10 September 2011. Hard-Breaking Gel New lyrics by Lennart Piculell to the melody of Heartbreak Hotel, created in June 2008 for the 7th Liquid Matter Conference, dedicated to Henk Lekkerkerker and Peter Pusey. Well, since my baby left me, I found a new place to be! It's downtown Lund, in a narrow street, Where hundreds of cool people meet! There I don't feel lonely, No, I don't feel lonely - So, if you feel lonely, you should try! It's all about liquid matter: Liquids flow, and soft bodies swell! Your mind is blown, and your blood will boil To a hard-breaking gel. And you won't be lonely, No, you won't be lonely - So, if you feel lonely, you should try! A tough guy tells you: Freeze! This is something that you have to test, 'Cause when you freeze you'll be super-cool, Or else you'll be under arrest. But you won't be lonely, baby, No, you won't be lonely, baby - So, if you feel lonely, you should try! I learn that the slightest nano-rod, That wouldn't seem very large; It still can fill up a lot of space As soon as you give it some charge! So, if you feel lonely, baby, Yes, if you feel lonely, baby - If you feel lonely, you should try! Well, when the party's over, What memories will time erase? Well, the chemistry may be lost on me, But I never forget a phase! And I won't be lonely, No, I won't be lonely - I won't be lonely 'til I die!

Temporal variations in extension rate on the Lone Mountain fault and strain distribution in the eastern California shear zone-Walker Lane

NASA Astrophysics Data System (ADS)

Hoeft, J. S.; Frankel, K. L.

2010-12-01

The eastern California shear zone (ECSZ) and Walker Lane represent an evolving segment of the Pacific-North America plate boundary. Understanding temporal variations in strain accumulation and release along plate boundary structures is critical to assessing how deformation is accommodated throughout the lithosphere. Late Pleistocene displacement along the Lone Mountain fault suggests the Silver Peak-Lone Mountain (SPLM) extensional complex is an important structure in accommodating and transferring strain within the ECSZ and Walker Lane. Using geologic and geomorphic mapping, differential global positioning system surveys, and terrestrial cosmogenic nuclide (TCN) geochronology, we determined rates of extension across the Lone Mountain fault in western Nevada. The Lone Mountain fault displaces the northwestern Lone Mountain and Weepah Hills piedmonts and is the northeastern component of the SPLM extensional complex, a series of down-to-the-northwest normal faults. We mapped seven distinct alluvial fan deposits and dated three of the surfaces using 10Be TCN geochronology, yielding ages of 16.5 ± 1.2 ka, 92 ± 9 ka, and 137 ± 25 ka for the Q3b, Q2c, and Q2b deposits, respectively. The ages were combined with scarp profile measurements across the displaced fans to obtain minimum rates of extension; the Q2b and Q2c surfaces yield an extension rate between 0.1 ± 0.1 and 0.2 ± 01 mm/yr and the Q3b surface yields a rate of 0.2 ± 0.1 to 0.4 ± 0.1 mm/yr, depending on the dip of the fault. Active extension on the Lone Mountain fault suggests that it helps partition strain off of the major strike-slip faults in the northern ECSZ and transfers deformation to the east around the Mina Deflection and northward into the Walker Lane. Combining our results with estimates from other faults accommodating dextral shear in the northern ECSZ reveals an apparent discrepancy between short- and long-term rates of strain accumulation and release. If strain rates have remained constant since the late Pleistocene, this could reflect transient strain accumulation, similar to the Mojave segment of the ECSZ. However, our data also suggest a potential increase in strain rates between ~92 ka and ~17 ka, and possibly to present day, which may also help explain the mismatch between long- and short-term rates of deformation in the region.

Restricted amide rotation with steric hindrance induced multiple conformations

NASA Astrophysics Data System (ADS)

Krishnan, V. V.; Vazquez, Salvador; Maitra, Kalyani; Maitra, Santanu

2017-12-01

The Csbnd N bond character is dependent directly upon the resonance-contributor structure population driven by the delocalized nitrogen lone-pair of electrons. In the case of N, N-dibenzyl-ortho-toluamide (o-DBET), the molecule adopts subpopulations of conformers with distinct NMR spectral features, particularly at low temperatures. This conformational adaptation is unique to o-DBET, while the corresponding meta- and para- forms do not show such behavior. Variable-temperature (VT) NMR, two-dimensional exchange spectroscopy (EXSY), and qualitative molecular modeling studies are used to demonstrate how multiple competing interactions such as restricted amide rotation and steric hindrance effects can lead to versatile molecular adaptations in the solution state.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Hua; College of Physics and Optoelectronics, Taiyuan University of Technology, Taiyuan 030024; Kioussis, Nicholas, E-mail: nick.kioussis@csun.edu

Using ab initio based calculations, we have calculated the intrinsic lattice thermal conductivity of chiral tellurium. We show that the interplay between the strong covalent intrachain and weak van der Waals interchain interactions gives rise to the phonon band gap between the lower and higher optical phonon branches. The underlying mechanism of the large anisotropy of the thermal conductivity is the anisotropy of the phonon group velocities and of the anharmonic interatomic force constants (IFCs), where large interchain anharmonic IFCs are associated with the lone electron pairs. We predict that tellurium has a large three-phonon scattering phase space that resultsmore » in low thermal conductivity. The thermal conductivity anisotropy decreases under applied hydrostatic pressure.« less

σ-holes and π-holes: Similarities and differences.

PubMed

Politzer, Peter; Murray, Jane S

2018-04-05

σ-Holes and π-holes are regions of molecules with electronic densities lower than their surroundings. There are often positive electrostatic potentials associated with them. Through these potentials, the molecule can interact attractively with negative sites, such as lone pairs, π electrons, and anions. Such noncovalent interactions, "σ-hole bonding" and "π-hole bonding," are increasingly recognized as being important in a number of different areas. In this article, we discuss and compare the natures and characteristics of σ-holes and π-holes, and factors that influence the strengths and locations of the resulting electrostatic potentials. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

A diffuse reflectance infrared Fourier transform spectroscopic study of adsorbed hydrazines

NASA Technical Reports Server (NTRS)

Davis, Dennis D.; Kilduff, Jan E.; Koontz, Steven L.

1988-01-01

Diffuse reflectance spectroscopy of fuel hydrazines adsorbed on silica, silica-alumina and alimina surfaces indicates that the primary surface-hydrazine interaction is hydrogen bonding. Hydrazine, on adsorption to a deuterated silica surface, undergoes a rapid H/D exchange with deuterated surface silanol (Si-OD) groups. Adsorption equilibria are rapidly established at room temperature. Monomethylhydrazine and unsymmetrical dimethylhydrazine are similarly adsorbed. On adsorption, the C-H stretching and methyl deformation modes of the methylhydrazines are shifted to higher frequencies by 10 to 20 cm(-1). These shifts are postulated to be due to changes in the lone-pair electro-density on the adjacent nitrogen atom and an electronegativity effect.

Asymmetric intramolecular Pauson-Khand reaction mediated by a remote sulfenyl or sulfinyl group.

PubMed

García Ruano, José Luis; Torrente, Esther; Parra, Alejandro; Alemán, José; Martín-Castro, Ana M

2012-08-03

In this work, we report the use of the asymmetric intramolecular Pauson-Khand reactions of 4-aryl-4-cyano-1,6-enynes for obtaining enantiomerically enriched bicyclo[3.3.0]octenones, and the influence of both the quaternary stereocenter and the sulfur functions located at ortho-position of the aryl group, on their stereoselectivity and reactivity. The sulfenyl derivatives bearing substituted or unsubstituted triple bonds and mono- and disubstituted alkene moieties afford bicyclo[3.3.0]octenones in high yields with complete diastereocontrol. These results are explained by assuming the association of the lone electron pair at sulfur to the Co-alkyne complexes.

Why do the lonely stay lonely? Chronically lonely adolescents' attributions and emotions in situations of social inclusion and exclusion.

PubMed

Vanhalst, Janne; Soenens, Bart; Luyckx, Koen; Van Petegem, Stijn; Weeks, Molly S; Asher, Steven R

2015-11-01

The goal of this study was to identify mechanisms associated with chronic loneliness by examining the effect of adolescents' accumulated history of loneliness on responses to new social situations. Specifically, this study investigated whether attributions and emotions in situations of social inclusion and exclusion differ between chronically lonely adolescents and adolescents with a different loneliness history. A total of 730 adolescents (Mage at Wave 1 = 15.43 years) participated in a 4-wave longitudinal study with annual loneliness assessments. A chronic loneliness trajectory was identified, in addition to low-stable, moderate-stable, moderate-increasing, and high-decreasing loneliness trajectories. At Wave 4, vignettes depicting social inclusion and exclusion were presented, and participants rated a set of attributions and emotions following each vignette. Compared with individuals following other trajectories, chronically lonely adolescents were characterized by hypersensitivity to social exclusion (i.e., higher levels of negative emotions) and hyposensitivity to social inclusion (i.e., lower levels of enthusiasm). Further, chronically lonely adolescents had a stronger tendency to attribute social inclusion to circumstantial factors and social exclusion to internal and stable characteristics. This maladaptive attribution style partially mediated their emotional experiences. Together, results indicate that chronically lonely individuals respond to social situations in ways that may perpetuate rather than reduce their loneliness. (c) 2015 APA, all rights reserved).

Effects of Team-Skills Guidance on Accounting Students with Lone Wolf Tendencies

ERIC Educational Resources Information Center

Seow, Jean Lin; Gowri Shankar, Premila

2018-01-01

We investigate whether short-term in-class team-skills guidance impacts the perceptions of accounting students with lone wolf tendencies on team work, and peer evaluation systems adopted in team work. We find that students with greater lone wolf tendencies see fewer benefits from engaging in team work and are also less comfortable with peer…

Morphologies of the atria and pulmonary veins in relation to lone atrial fibrillation progression: a dual-source computed tomography scan study.

PubMed

Liu, Xing-Peng; Xu, Xia; Tian, Ying; Tang, Ri-Bo; Yu, Rong-Hui; Long, De-Yong; Sang, Cai-Hua; Jiang, Chen-Xi; Ning, Man; Dong, Jian-Zeng; Ma, Chang-Sheng

2012-11-01

Atrial Remodeling and Lone Atrial Fibrillation. We sought to investigate the role of anatomic remodeling of the atria and pulmonary veins (PVs) in the progression of lone atrial fibrillation (AF) using dual-source computed tomography (DSCT). From 1,308 consecutive patients referred for an index ablation procedure for AF, we prospectively enrolled 29 consecutive patients with recently developed (<3 months) lone persistent AF (PsAF) and 23 consecutive patients with short-lasting (6-12 months) lone PsAF, all of whom had a history of paroxysmal AF (PAF). The control group consisted of 33 patients with lone PAF. On DSCT, the recently developed PsAF group showed more extensive atrial anatomic remodeling than the PAF group as shown by ∼40% higher spot biatrial volume, even though the mean duration of continuous AF was only 6 weeks. In contrast, the DSCT variables in the recently developed PsAF group and the short-lasting PsAF group were comparable, despite the fact that the mean duration of continuous AF in the latter group was 8 months. Series of cross-sectional areas of the ostial 1.5 cm of PV trunks were comparable in the PAF and PsAF groups in all but 3 ostial planes. A higher spot left atrial volume was the only independent factor associated with the progression of lone PAF to PsAF (OR: 1.06, 95% CI: 1.03-1.09, P<0.0001) on logistic regression. Prominent anatomic remodeling of the atria, rather than the PVs, underlies the mechanism of recent progression of lone paroxysmal AF to the persistent variety. © 2012 Wiley Periodicals, Inc.

What's eating you? lone star tick (Amblyomma americanum).

PubMed

Reynolds, H Harris; Elston, Dirk M

2017-02-01

Amblyomma americanum , also known as the lone star tick, is found in much of the eastern United States. Since the mid-20th century, the lone star tick has been implicated in human disease. Today, A americanum remains an important vector for tick-borne illness. In addition to others, species of Rickettsia , Ehrlichia , and Borrelia are all transmitted by the lone star tick. Recently described conditions such as Southern tick-associated rash illness and anaphylaxis to red meat following tick bites have been attributed to the lone star tick. Impressive local reactions also can result after bites from A americanum . Early treatment of tick-borne illness is crucial to ensure good patient outcomes. Tick-control measures also are an important part of disease management in endemic areas. We discuss the tick's biology, human illnesses associated with A americanum , and methods to control tick numbers and eliminate disease in local reservoirs.

Problem solving and maternal distress at the time of a child's diagnosis of cancer in two-parent versus lone-parent households.

PubMed

Iobst, Emily A; Alderfer, Melissa A; Sahler, Olle Jane Z; Askins, Martha A; Fairclough, Diane L; Katz, Ernest R; Butler, Robert W; Dolgin, Michael J; Noll, Robert B

2009-09-01

To examine negative affectivity and problem-solving abilities for lone mothers and those who are married/partnered subsequent to a child's diagnosis with cancer. Negative affectivity and problem-solving strategies were assessed for 464 mothers (87 lone and 377 married/partnered) within 2-16 weeks of their child's diagnosis with cancer. The two groups of mothers did not differ significantly on measures of perceived posttraumatic stress or problem-solving; lone mothers reported significantly more symptoms of depression. This difference was no longer significant when maternal education was taken into account. Negative affectivity and problem-solving abilities were similar for lone mothers and those that are married/partnered shortly after their child has been diagnosed with cancer. Findings are discussed within the context of contemporary strategies to assess marital status as proxy variable for various underlying constructs.

Differences between Homicides Committed by Lone and Multiple Offenders in Korea.

PubMed

Park, Jisun; Cho, Joon Tag

2018-05-16

The aim of this study was to differentiate between homicides committed by multiple offenders and homicides committed by lone offenders. Using data on homicide incidents that occurred in South Korea between 1985 and 2008, we compared 134 homicides committed by multiple offenders, with 369 homicides committed by lone offenders. A greater proportion of homicides committed by multiple offenders involved injuries to the victim's head compared to homicides by lone offenders. Homicides committed by multiple offenders were more likely to involve blunt instruments and ligatures, whereas homicides by lone offenders were more likely to involve sharp instruments. In addition, a majority of the homicides committed by multiple offenders were planned. The results of this study have practical implications for homicide investigations, as well as theoretical implications for homicide research on the difference in offense behaviors based on the number of offenders. © 2018 American Academy of Forensic Sciences.

Choking under social pressure: social monitoring among the lonely.

PubMed

Knowles, Megan L; Lucas, Gale M; Baumeister, Roy F; Gardner, Wendi L

2015-06-01

Lonely individuals may decode social cues well but have difficulty putting such skills to use precisely when they need them--in social situations. In four studies, we examined whether lonely people choke under social pressure by asking participants to complete social sensitivity tasks framed as diagnostic of social skills or nonsocial skills. Across studies, lonely participants performed worse than nonlonely participants on social sensitivity tasks framed as tests of social aptitude, but they performed just as well or better than the nonlonely when the same tasks were framed as tests of academic aptitude. Mediational analyses in Study 3 and misattribution effects in Study 4 indicate that anxiety plays an important role in this choking effect. This research suggests that lonely individuals may not need to acquire social skills to escape loneliness; instead, they must learn to cope with performance anxiety in interpersonal interactions. © 2015 by the Society for Personality and Social Psychology, Inc.

Evaluation of four commercial natural products for repellency and toxicity against the lone star tick, Amblyomma americanum (Acari: Ixodidae).

PubMed

Machtinger, Erika T; Li, Andrew Y

2017-12-01

Lone star ticks are aggressive ectoparasites of domestic and wild animals, as well as humans. These ticks can transmit many pathogens that cause disease including Erhlichia and tularemia. Common compounds used for personal protection and area sprays are N-diethyl-3-methyl benzamide (DEET) and permethrin, but public concern over personal and environmental safety require the development of new, safer products. In the current study, four commercially available products (Wondercide, Essentria IC 3 , Vet's Best, and Mosquito Barrier) were tested for both repellent and toxic effects against lone star tick nymphs and adults. Overall, all four products were more effective against nymphs than against adults. Wondercide and Essentria IC 3 were as toxic to nymphs as permethrin at concentrations of 3.13% and higher, and as repellent as DEET at all concentrations. Nymphs were also repelled by Mosquito Barrier and Vet's Best, but these products had about half or less of the repellent effects of Wondercide and Essentria IC 3 at most of the concentrations. Adult ticks were repelled similarly by all products at all tested concentrations, but at lower levels than nymphs. Toxicity of the four tested products on adults was similar at concentrations of 12.5% and below, less than half of what was observed with permethrin with declining effectiveness as concentrations decreased. Overall, these four products may offer a natural way to repel lone star ticks, but further field testing is needed to determine rates of application and residual activity.

Lone Blazar

NASA Image and Video Library

2012-04-12

This image from NASA WISE spacecraft shows a blazar, a voracious supermassive black hole inside a galaxy with a jet that happens to be pointed right toward Earth. Active black holes are often found at the hearts of elliptical galaxies.

Structural insight into the Ragulator complex which anchors mTORC1 to the lysosomal membrane

PubMed Central

Mu, Zongkai; Wang, Lei; Deng, Wei; Wang, Jiawei; Wu, Geng

2017-01-01

The mechanistic target of rapamycin (mTOR) signal-transduction pathway plays a key role in regulating many aspects of metabolic processes. The central player of the mTOR signaling pathway, mTOR complex 1 (mTORC1), is recruited by the pentameric Ragulator complex and the heterodimeric Rag GTPase complex to the lysosomal membrane and thereafter activated. Here, we determined the crystal structure of the human Ragulator complex, which shows that Lamtor1 possesses a belt-like shape and wraps the other four subunits around. Extensive hydrophobic interactions occur between Lamtor1 and the Lamtor2-Lamtor3, Lamtor4-Lamtor5 roadblock domain protein pairs, while there is no substantial contact between Lamtor2-Lamtor3 and Lamtor4-Lamtor5 subcomplexes. Interestingly, an α-helix from Lamtor1 occupies each of the positions on Lamtor4 and Lamtor5 equivalent to the α3-helices of Lamtor2 and Lamtor3, thus stabilizing Lamtor4 and Lamtor5. Structural comparison between Ragulator and the yeast Ego1-Ego2-Ego3 ternary complex (Ego-TC) reveals that Ego-TC only corresponds to half of the Ragulator complex. Coupling with the fact that in the Ego-TC structure, Ego2 and Ego3 are lone roadblock domain proteins without another roadblock domain protein pairing with them, we suggest that additional components of the yeast Ego complex might exist. PMID:29285400

Growth and Characterization of the p-type Semiconductors Tin Sulfide and Bismuth Copper Oxy Selenide

NASA Astrophysics Data System (ADS)

Francis, Jason

BiCuOSe and SnS are layered, moderate band gap (epsilon G ≈ 1 eV) semiconductors that exhibit intrinsic p type conductivity. Doping of BiCuOSe with Ca results in a slight expansion of the lattice and an increase of the hole concentration from 10 18 cm--3 to greater than 1020 cm --3. The large carrier density in undoped films is the result of copper vacancies. Mobility is unaffected by doping, remaining constant at 1.5 cm2V--1s--1 in both undoped and doped films, because the Bi-O layers serve as the source of carriers, while transport occurs within the Cu-Se layers. Bi possesses a 6s2 lone pair that was expected to hybridize with the oxygen p states at the top of the valence band, resulting in high hole mobility as compared to similar materials such as LaCuOSe, which lack this lone pair. However, both LaCuOSe and BiCuOSe have similar hole mobility. X-ray absorption and emission spectroscopy, combined with density functional theory calculations, reveal that the Bi 6 s states contribute deep within the valence band, forming bonding and anti-bonding states with O 2p at 11 eV and 3 eV below the valence band maximum, respectively. Hence, the Bi lone pair does not contribute at the top of the valence band and does not enhance the hole mobility. The Bi 6p states contribute at the bottom of the conduction band, resulting in a smaller band gap for BiCuOSe than LaCuOSe (1 eV vs. 3 eV). SnS is a potential photovoltaic absorber composed of weakly coupled layers stacked along the long axis. This weak coupling results in the formation of strongly oriented films on amorphous substrates. The optical band gap is 1.2 eV, in agreement with GW calculations. Absorption reaches 105 cm--1 within 0.5 eV of the band gap. The p type conduction arises from energetically favorable tin vacancies. Variation of growth conditions yields carrier densities of 1014 -- 1016 cm--3 and hole mobility of 7 -- 15 cm2V--1s--1. SnS was alloyed with rocksalt CaS, which was predicted to form a rocksalt structure when the calcium content is increased past 18%. Films of Sn1--x CaxS with x from 0.4 to 0.9 adopt the rocksalt structure with a band gap of 1.1-1.3 eV, with absorption greater than 105 cm--1 within about 0.7 eV of the band gap. The lattice contracts as the calcium content of the films is increased, reaching 5.7 A when x = 0.93. Films are highly insulating, but Seebeck measurements do indicate p type conduction.

Evans hole and non linear optical activity in Bis(melaminium) sulphate dihydrate: A vibrational spectral study.

PubMed

Suresh Kumar, V R; Binoy, J; Dawn Dharma Roy, S; Marchewka, M K; Jayakumar, V S

2015-01-01

Bis(melaminium) sulphate dihydrate (BMSD), an interesting melaminium derivative for nonlinear optical activity, has been subjected to vibrational spectral analysis using FT IR and FT Raman spectra. The analysis has been aided by the Potential Energy Distribution (PED) of vibrational spectral bands, derived using density functional theory (DFT) at B3LYP/6-31G(d) level. The geometry is found to correlate well with the XRD structure and the band profiles for certain vibrations in the finger print region have been theoretically explained using Evans hole. The detailed Natural Bond Orbital (NBO) analysis of the hydrogen bonding in BMSD has also been carried out to understand the correlation between the stabilization energy of hyperconjugation of the lone pair of donor with the σ(∗) orbital of hydrogen-acceptor bond and the strength of hydrogen bond. The theoretical calculation shows that BMSD has NLO efficiency, 2.66 times that of urea. The frontier molecular orbital analysis points to a charge transfer, which contributes to NLO activity, through N-H…O intermolecular hydrogen bonding between the melaminium ring and the sulphate. The molecular electrostatic potential (MEP) mapping has also been performed for the detailed analysis of the mutual interactions between melaminium ring and sulphate ion. Copyright © 2015 Elsevier B.V. All rights reserved.

The Potential (F)utility of a Passive Organ Donor Registration Opportunity: A Conceptual Replication.

PubMed

Siegel, Jason T; Alvaro, Eusebio M; Tan, Cara N; Navarro, Mario A; Garner, Lori R; Jones, Sara Pace

2016-06-01

Approximately 22 people die each day in the United States as a result of the shortage of transplantable organs. This is particularly problematic among Spanish-dominant Hispanics. Increasing the number of registered organ donors can reduce this deficit. The goal of the current set of studies was to conceptually replicate a prior study indicating the lack of utility of a lone, immediate and complete registration opportunity (ICRO). The study, a quasi-experimental design involving a total of 4 waves of data collection, was conducted in 2 different Mexican consulates in the United States. Guided by the IIFF Model (ie, an ICRO, information, focused engagement, and favorable activation), each wave compared a lone ICRO to a condition that likewise included an ICRO but also included the 3 additional intervention components recommended by the model (ie, information, focused engagement, and favorable activation). Visitors to the Mexican consulates in Tucson, Arizona, and Albuquerque, New Mexico, constituted the participant pool. New organ donor registrations represented the dependent variable. When all 4 components of the IIFF Model were present, approximately 4 registrations per day were recorded; the lone ICRO resulted in approximately 1 registration every 15 days. An ICRO, without the other components of the IIFF Model, is of minimal use in regard to garnering organ donor registrations. Future studies should use the IIFF Model to consider how the utility of ICROs can be maximized. © 2016, NATCO.

Impact of Caregiving for a Child With Cancer on Parental Health Behaviors, Relationship Quality, and Spiritual Faith: Do Lone Parents Fare Worse?

PubMed Central

Wiener, Lori; Viola, Adrienne; Kearney, Julia; Mullins, Larry L.; Sherman-Bien, Sandra; Zadeh, Sima; Farkas-Patenaude, Andrea; Pao, Maryland

2016-01-01

Caregiving stress has been associated with changes in the psychological and physical health of parents of children with cancer, including both partnered and single parents. While parents who indicate “single” on a demographic checklist are typically designated as single parents, a parent can be legally single and still have considerable support caring for an ill child. Correspondingly, an individual can be married/partnered and feel alone when caring for a child with serious illness. In the current study, we report the results from our exploratory analyses of parent self-reports of behavior changes during their child’s treatment. Parents (N = 263) of children diagnosed with cancer were enrolled at 10 cancer centers. Parents reported significant worsening of all their own health behaviors surveyed, including poorer diet and nutrition, decreased physical activity, and less time spent engaged in enjoyable activities 6 to 18 months following their child’s diagnosis. More partnered parents found support from friends increased or stayed the same since their child’s diagnosis, whereas a higher proportion of lone parents reported relationships with friends getting worse. More lone parents reported that the quality of their relationship with the ill child’s siblings had gotten worse since their child’s diagnosis. Spiritual faith increased for all parents. PMID:26668211

Impact of Caregiving for a Child With Cancer on Parental Health Behaviors, Relationship Quality, and Spiritual Faith: Do Lone Parents Fare Worse?

PubMed

Wiener, Lori; Viola, Adrienne; Kearney, Julia; Mullins, Larry L; Sherman-Bien, Sandra; Zadeh, Sima; Farkas-Patenaude, Andrea; Pao, Maryland

2016-09-01

Caregiving stress has been associated with changes in the psychological and physical health of parents of children with cancer, including both partnered and single parents. While parents who indicate "single" on a demographic checklist are typically designated as single parents, a parent can be legally single and still have considerable support caring for an ill child. Correspondingly, an individual can be married/partnered and feel alone when caring for a child with serious illness. In the current study, we report the results from our exploratory analyses of parent self-reports of behavior changes during their child's treatment. Parents (N = 263) of children diagnosed with cancer were enrolled at 10 cancer centers. Parents reported significant worsening of all their own health behaviors surveyed, including poorer diet and nutrition, decreased physical activity, and less time spent engaged in enjoyable activities 6 to 18 months following their child's diagnosis. More partnered parents found support from friends increased or stayed the same since their child's diagnosis, whereas a higher proportion of lone parents reported relationships with friends getting worse. More lone parents reported that the quality of their relationship with the ill child's siblings had gotten worse since their child's diagnosis. Spiritual faith increased for all parents. © 2015 by Association of Pediatric Hematology/Oncology Nurses.

Bimodal Distribution of Geyser Preplay Eruptions: Lone Star Geyser, Yellowstone National Park

NASA Astrophysics Data System (ADS)

Namiki, A.; Hurwitz, S.; Murphy, F.; Manga, M.

2014-12-01

Geyser eruption intervals are determined by rates of water and heat discharge into shallow subsurface reservoirs and the conduit. In some geysers, small amounts of water discharge prior to a main eruption ('Preplay') can affect eruption intervals. Water discharge during preplay reduces the hydrostatic pressure, which in turn, induces boiling of water that is at, or near the critical temperature. Ascending steam slugs from depth can also lead to shorter eruption intervals (Namiki et al., 2014). In April 2014, we carried a five day experiment at Lone Star Geyser, Yellowstone National Park. Eruptions and their preplays were recorded with an infrared sensor that measured temperature variations immediately above the geyser cone (3.4~m high), temperature loggers that measured water temperature at the base of the cone and in the outflow channels, and visual observations. At Lone Star Geyser, during the preplay phase of the eruption, mainly liquid water is erupted, whereas the main phase of the eruption begins with the liquid-water dominated eruption and turns into the steam discharge. The temperature rise in an outflow channel indicates the occurrence of preplays and initiation of the main eruption. The acquired data suggests that the preplay patterns of Lone Star Geyser are vigorous and complex, consistent with previous observations (Karlstrom et al., 2013). Our new observations reveal two typical styles: 1) vigorous preplays with few events (<5) and long intervals (>20~minutes) that last approximately 40~minutes, and 2) less vigorous preplays that include several events (>5) with short intervals (few minutes), and continue approximately for one hour. Probability distributions of preplay durations show two peaks indicating the bimodal activity. The bimodality of Lone Star preplays may be a result of subtle change of temperature distribution in a convecting reservoir which has been observed in laboratory experiments (Toramaru and Maeda, 2013).

Ovarian development in a primitively eusocial wasp: social interactions affect behaviorally dominant and subordinate wasps in opposite directions relative to solitary females.

PubMed

Shukla, Shantanu; Pareek, Vidhi; Gadagkar, Raghavendra

2014-07-01

In many primitively eusocial wasp species new nests are founded either by a single female or by a small group of females. In the single foundress nests, the lone female develops her ovaries, lays eggs as well as tends her brood. In multiple foundress nests social interactions, especially dominance-subordinate interactions, result in only one 'dominant' female developing her ovaries and laying eggs. Ovaries of the remaining 'subordinate' cofoundresses remain suppressed and these individuals function as workers and tend the dominant's brood. Using the tropical, primitively eusocial polistine wasp Ropalidia marginata and by comparing wasps held in isolation and those kept as pairs in the laboratory, we demonstrate that social interactions affect ovarian development of dominant and subordinate wasps among the pairs in opposite directions, suppressing the ovaries of the subordinate member of the pair below that of solitary wasps and boosting the ovaries of dominant member of the pair above that of solitary females. In addition to being of physiological interest, such mirror image effects of aggression on the ovaries of the aggressors and their victims, suggest yet another mechanism by which subordinates can enhance their indirect fitness and facilitate the evolution of worker behavior by kin selection. Copyright © 2014 Elsevier B.V. All rights reserved.

For Parents Particularly--"Only the Lonely": The Latchkey Child.

ERIC Educational Resources Information Center

O'Brien, Shirley J.

1989-01-01

Discusses ways in which call-in hotlines provide assistance to latchkey children. Describes ways in which parents can provide a feeling of safety for latchkey children and cure feelings of loneliness and boredom through structured activities.(RJC)

Lone atrial fibrillation: what is known and what is to come.

PubMed

Potpara, T S; Lip, G Y H

2011-04-01

Atrial fibrillation (AF) is the most prevalent sustained cardiac arrhythmia in adults, affecting >1% of general population. Atrial fibrillation is commonly associated with structural heart disease and is a major cause of significant cardiovascular morbidity and mortality. AF sometimes develops in a subset of young patients (e.g. aged ≤60 years), with no evidence of associated cardiopulmonary or other comorbid disease (including hypertension), and has been referred to as 'lone AF'. The latter generally has a favourable prognosis; the prognostic and therapeutic implications of an accurate identification of patients with truly lone AF (that is, truly at low risk of complications), if any, would be of the utmost importance. The true prevalence of lone AF is unknown, varying between 1.6% and 30%, depending on the particular study population. Nonetheless, novel risk factors for AF, including obesity, metabolic syndrome, sleep apnea, alcohol consumption, endurance sports, anger, hostility, subclinical atherosclerosis and others, have been increasingly recognised. Also, various underlying pathophysiological mechanisms predisposing to AF, including increased atrial stretch, structural and electrophysiological alterations, autonomic imbalance, systemic inflammation, oxidative stress and genetic predisposition, have been proposed. The growing evidence of these diverse (and numerous) pathogenic mechanisms and factors related to AF inevitably raises the question of whether 'lone AF' does exist at all. In this review article, we summarise the current knowledge of the epidemiology, pathophysiology, clinical course and treatment of patients with so-called 'lone AF' and outline emerging insights into its pathogenesis and the potential therapeutic implications of a diagnosis of lone AF. © 2011 Blackwell Publishing Ltd.

Electron Pair Repulsion Responsible for the Peculiar Edge Effects and Surface Chemistry of Black Phosphorus.

PubMed

Kong, Xiang-Peng; Shen, Xiaomei; Jang, Joonkyung; Gao, Xingfa

2018-03-01

The electronic and optical properties of black phosphorus (black-P) are significantly modulated by fabricating the edges of this two-dimensional material. Electron lone pairs (ELPs) are ubiquitous in black-P, but their role in creating the edge effects of black-P is poorly understood. Using first-principle calculations, we report ELPs of black-P experience severe Coulomb repulsion and play a central role in creating the edge effects of black-P. We discover the outermost P atoms of the zigzag edges of black-PQDs are free of the Coulomb repulsion, but the P atoms of the armchair edges do experience the Coulomb repulsion. The Coulomb repulsion serves as a new chemical driving force to make electron donor-acceptor bonds with chemical groups bearing vacant orbitals. Our results provide insights into the mechanism responsible for the peculiar edge effects of black-P and highlight the opportunity to use the ELPs of black-P for their damage-free surface functionalization.

Structure and bonding in beta-HMX-characterization of a trans-annular N...N interaction.

PubMed

Zhurova, Elizabeth A; Zhurov, Vladimir V; Pinkerton, A Alan

2007-11-14

Chemical bonding in the beta-phase of the 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) crystal based on the experimental electron density obtained from X-ray diffraction data at 20 K, and solid state theoretical calculations, has been analyzed in terms of the quantum theory of atoms in molecules. Features of the intra- and intermolecular bond critical points and the oxygen atom lone-pair locations are discussed. An unusual N...N bonding interaction across the 8-membered ring has been discovered and characterized. Hydrogen bonding, O...O and O...C intermolecular interactions are reported. Atomic charges and features of the electrostatic potential are discussed.

Air and moisture stable covalently-bonded tin(ii) coordination polymers.

PubMed

de Lima, G M; Walton, R I; Clarkson, G J; Bitzer, R S; Ardisson, J D

2018-06-05

Four covalently-bonded tin(ii) coordination polymers, (1)-(4), were hydrothermally prepared in aqueous alkaline media by the reactions of SnSO4 with 1,2,4,5-benzenetetracarboxylic acid (1), 1,3,5-benzenetricarboxylic acid (2), 4-hydroxypyridine-2,6-dicarboxylic acid (3), and 1,3,5-cyclohexanetricarboxylic acid (4). All products were structurally authenticated by single-crystal X-ray diffraction, and the number of different tin centres and their oxidation states were confirmed by 119Sn Mössbauer spectroscopy. In addition, the comparison between experimental and simulated X-ray powder diffraction patterns confirmed the authenticity of the samples. Our crystallographic results for (1)-(4) show that the Sn(ii) centres are tetracoordinated and exhibit distorted disphenoidal geometries, corroborating the presence of one stereochemically active lone electron pair at each metal site. Products (1) and (2) display bi-dimensional polymeric structures, (3) exhibits a one-dimensional architecture, whereas (4) shows a remarkable three-dimensional coordination network. Hirshfeld surface and supramolecular analyses for the repeating units of (1)-(4) were also performed in order to identify structurally important non-covalent interactions.

Hole conduction pathways in transparent amorphous tin oxides

NASA Astrophysics Data System (ADS)

Wahila, Matthew; Lebens-Higgins, Zachary; Quackenbush, Nicholas; Piper, Louis; Butler, Keith; Hendon, Christopher; Walsh, Aron; Watson, Graeme

P-type transparent amorphous oxide semiconductors (TAOS) have yet to be sufficiently demonstrated or commercialized, severely limiting the possible device architecture of transparent and flexible oxide electronics. The lack of p-type amorphous oxide candidates mainly originates from the directional oxygen 2 p character of their topmost valence states. Previous attempts to create p-type oxides have involved hybridization of the O 2 p with metal orbitals, such as with CuAlO2 and its Cu 3 d - O 2 p hybridization. However, the highly directional nature of the utilized orbitals means that structural disorder inhibits hybridization and severely disrupts hole-conduction pathways. Crystalline stannous oxide (SnO) and other lone-pair active post-transition metal oxides can have reduced localization at the valence band edge due to complex hybridization between the O 2 p, metal p, and spherical metal s-orbitals. I will discuss our investigation of structural disorder in SnO. Using a combination of synchrotron spectroscopy, and atomistic calculations, our investigation elucidates the important interplay between atomistic and electronic structure in establishing continuous hole conduction pathways at the valence band edge of transparent amorphous oxides.

Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle-Kirmse Reaction of α-Diazo Pyrazoleamides.

PubMed

Lin, Xiaobin; Tang, Yu; Yang, Wei; Tan, Fei; Lin, Lili; Liu, Xiaohua; Feng, Xiaoming

2018-03-07

Although high enantioselectivity of [2,3]-sigmatropic rearrangement of sulfonium ylides (Doyle-Kirmse reaction) has proven surprisingly elusive using classic chiral Rh(II) and Cu(I) catalysts, in principle it is due to the difficulty in fine discrimination of the heterotopic lone pairs of sulfur and chirality inversion at sulfur of sulfonium ylides. Here, we show that the synergistic merger of new α-diazo pyrazoleamides and a chiral N, N'-dioxide-nickel(II) complex catalyst enables a highly enantioselective Doyle-Kirmse reaction. The pyrazoleamide substituent serves as both an activating and a directing group for the ready formation of a metal-carbene- and Lewis-acid-bonded ylide intermediate in the assistance of a dual-tasking nickel(II) complex. An alternative chiral Lewis-acid-bonded ylide pathway greatly improves the product enantiopurity even for the reaction of a symmetric diallylsulfane. The majority of transformations over a series of aryl- or vinyl-substituted α-diazo pyrazoleamindes and sulfides proceed rapidly (within 5-20 min in most cases) with excellent results (up to 99% yield and 96% ee), providing a breakthrough in enantioselective Doyle-Kirmse reaction.

Orientation of N-benzoyl glycine on silver nanoparticles: SERS and DFT studies

NASA Astrophysics Data System (ADS)

Parameswari, A.; Asath, R. Mohamed; Premkumar, R.; Benial, A. Milton Franklin

2017-05-01

Surface enhanced Raman scattering (SERS) studies of N-benzoyl glycine (NBG) adsorbed on silver nanoparticles (AgNPs) was studied by experimental and density functional theory (DFT) approach. Single crystals of NBG were prepared using slow evaporation method. The AgNPs were prepared and characterized. The DFT/ B3PW91 method with LanL2DZ basis set was used to optimize the molecular structure of NBG and NBG adsorbed on silver cluster. The calculated and observed vibrational frequencies were assingned on the basis of potential energy distribution calculation. The reduced band gap value was obtained for NBG adsorbed on silver nanoparticles from the frontier molecular orbitals analysis. Natural bond orbital analysis was carried out to inspect the intra-molecular stabilization interactions, which are responsible for the bio activity and nonlinear optical property of the molecule. The spectral analysis was also evidenced that NBG would adsorb tilted orientation on the silver surface over the binding sites such as lone pair electron of N atom in amine group and through phenyl ring π system.

A small modified hammerhead ribozyme and its conformational characteristics determined by mutagenesis and lattice calculation.

PubMed Central

Lustig, B; Lin, N H; Smith, S M; Jernigan, R L; Jeang, K T

1995-01-01

A prototypic hammerhead ribozyme has three helices that surround an asymmetrical central core loop. We have mutagenized a hammerhead type ribozyme. In agreement with previous studies, progressive removal of stem-loop II from a three stemmed ribozyme showed that this region is not absolutely critical for catalysis. However, complete elimination of stem II and its loop did reduce, but did not eliminate, function. In a stem-loop II-deleted ribozyme, activity was best preserved when a purine, preferably a G, was present at position 10.1. This G contributed to catalysis irregardless of its role as either one part of a canonical pair with a C residue at 11.1 or a lone nucleotide with C (11.1) deleted. Computational methods using lattices generated 87 million three-dimensional chain forms for a stem-loop II-deleted RNA complex that preserved one potential G.C base pair at positions 10.1 and 11.1. This exhaustive set of chain forms included one major class of structures with G(10.1) being spatially proximal to the GUCX cleavage site of the substrate strand. Strong correlations were observed between colinear arrangement of stems I and III, constraints of base-pairing in the central core loop, and one particular placement of G(10.1) relative to the cleavage site. Our calculations of a stem-loop II-deleted ribozyme indicate that without needing to invoke any other constraints, the inherent asymmetry in the lengths of the two loop strands (3 nt in one and 7 nt in the other) that compose the core and flank G10.1-C11.1 stipulated strongly this particular G placement. This suggests that the hammerhead ribozyme maintains an asymmetry in its internal loop for a necessary structure/function reason. Images PMID:7567466

Loneliness, Self-Disclosure, and Interpersonal Effectiveness.

ERIC Educational Resources Information Center

Chelune, Gordon J.; And Others

1980-01-01

Examined the relationship between interpersonal intimacy and loneliness, social skills, and social activity. Dispositional level of self-disclosure was found to be inversely related to loneliness. Results suggest that lonely individuals have difficulty appropriately revealing personal information in new relationships and nonstructured social…

From macro to micro: the health of Swedish lone mothers during changing economic and social circumstances.

PubMed

Fritzell, Sara; Ringbäck Weitoft, Gunilla; Fritzell, Johan; Burström, Bo

2007-12-01

The deep recession in Sweden in the early 1990s led to high unemployment levels. In addition, policy changes and reductions in welfare benefits increased costs of living. These changes may have affected lone mothers to a greater extent than other groups. How have these changes in the social context and policy context impacted on the health of lone mothers in comparison with couple mothers in Sweden between 1983 and 2001? Survey data on 19,192 mothers over the period of 1983-2001 were used to study changes in individual economic and social circumstances and self-rated health (SRH) with multivariate logistic regression. In addition, all-cause mortality, cause-specific mortality and severe morbidity were studied using registers for the whole population. Three cohorts of mothers aged 20-54 years (starting 1985, 1990 and 1996) were formed. Age-adjusted risk ratios were calculated using Poisson regression. The employment rate among lone mothers declined from 1983 to 2001. At the same time, prevalence of self-reported financial problems and exposure to violence increased. Lone mothers reported worse SRH and had higher risks of hospitalisation and mortality than couple mothers in all time periods. Despite changes in social context and policy context causing an increase of health detrimental exposures, and deteriorated levels of SRH 1980-2001 for lone mothers, there was no evidence of increased differentials over time between lone and couple mothers in less than good SRH, hospitalisation or mortality. Three alternative explanations are discussed: the Swedish welfare state still acts as a buffer for ill health; latency makes the follow-up time too short; and finally, the lack of increased differentials is due to methodological reasons.

Health care utilization, somatic and mental health distress, and well-being among widowed and non-widowed female survivors of war.

PubMed

Morina, Nexhmedin; Emmelkamp, Paul M G

2012-05-11

The aim of the study was to assess levels of somatic and mental health distress, well-being, AS WELL AS utilization of primary and specialist health care services among war-related widowed and non-widowed female civilian survivors of war. 100 war-related widowed lone mothers and 106 non-widowed mothers who had experienced the Kosovo war ten years previously participated in the study. Measures of somatic, depressive, post-traumatic stress, anxiety, and grief complaints, subjective well-being, and utilization of health care services during the previous three months were used. Compared to non-widowed mothers, widowed lone mothers reported significantly higher levels of somatic, depressive, post-traumatic stress, and anxiety complaints. Further, they reported significantly lower levels of subjective well-being as composed of positive and negative affect and satisfaction with life. More than half of both widowed and non-widowed mothers reported utilization of health care services during the last three months, without significant differences between the groups. However, only three percent of widowed lone mothers and four percent of non-bereaved mothers reported utilization of mental health services during the last three months, despite high levels of mental health distress especially among widowed lone mothers. Among widowed lone mothers, severity of prolonged grief symptoms significantly predicted number of contacts of specialist health care use over and above sociodemographic variables, number of war-related events, and other psychopathology. War-related widowed lone mothers suffer from elevated somatic and mental distress even a decade after the war. The tiny proportion of widowed lone mothers in use of mental health services can be seen as a reflection of lack of previous and current mental health services to meet mental health needs of this population.

Health care utilization, somatic and mental health distress, and well-being among widowed and non-widowed female survivors of war

PubMed Central

2012-01-01

Background The aim of the study was to assess levels of somatic and mental health distress, well-being, AS WELL AS utilization of primary and specialist health care services among war-related widowed and non-widowed female civilian survivors of war. Methods 100 war-related widowed lone mothers and 106 non-widowed mothers who had experienced the Kosovo war ten years previously participated in the study. Measures of somatic, depressive, post-traumatic stress, anxiety, and grief complaints, subjective well-being, and utilization of health care services during the previous three months were used. Results Compared to non-widowed mothers, widowed lone mothers reported significantly higher levels of somatic, depressive, post-traumatic stress, and anxiety complaints. Further, they reported significantly lower levels of subjective well-being as composed of positive and negative affect and satisfaction with life. More than half of both widowed and non-widowed mothers reported utilization of health care services during the last three months, without significant differences between the groups. However, only three percent of widowed lone mothers and four percent of non-bereaved mothers reported utilization of mental health services during the last three months, despite high levels of mental health distress especially among widowed lone mothers. Among widowed lone mothers, severity of prolonged grief symptoms significantly predicted number of contacts of specialist health care use over and above sociodemographic variables, number of war-related events, and other psychopathology. Conclusion War-related widowed lone mothers suffer from elevated somatic and mental distress even a decade after the war. The tiny proportion of widowed lone mothers in use of mental health services can be seen as a reflection of lack of previous and current mental health services to meet mental health needs of this population. PMID:22578096

A global study on lone mothers: exploring the associations of self-assessed general health with motherhood types and gender inequality in 32 countries.

PubMed

Witvliet, Margot I; Arah, Onyebuchi A; Stronks, Karien; Kunst, Anton E

2014-01-01

In a study of 32 mostly non-affluent countries, we aimed to i) compare lone mother's general health to the health of other women and ii) assess whether the association of health with gender inequality was stronger among lone mothers than among other women. World Health Survey data were analyzed on 57,182 women aged 18 to 50 in 32 countries. The main outcome was self-assessed general poor health. The Global Gender Gap Index (GGGI) was used to measure the magnitude of gender inequality within countries. Logistic multilevel regression was used to compare the health of different groups of women, and to study the possible influence of gender inequality. Compared with all other women, lone mothers had the highest odds of poor health odds ratio (OR, 1.15; 95% confidence interval [CI], 1.09-1.22), also at 35 years or older with an OR of 1.18 (95% CI, 1.10-1.27). Lone mothers in Ethiopia and Tunisia had the highest odds of reporting poor health (OR, 1.65 [95% CI, 1.21-2.26] and OR, 1.57 [95% CI, 0.92-2.68], respectively). The degree of gender inequality was weakly related to cross-national variations in health of women. These associations were about similar for all women. For example, the OR for the GGGI was 1.03 for all women except coupled mothers. As within North America, lone mothers in non-affluent countries tend to have higher rates of poor health. The degree of gender inequality is not related to the relative health of lone mothers, suggesting that other characteristics of nations might be more influential. Copyright © 2014 Jacobs Institute of Women's Health. Published by Elsevier Inc. All rights reserved.

Keeping it in the family: the self-rated health of lone mothers in different European welfare regimes.

PubMed

Van de Velde, Sarah; Bambra, Clare; Van der Bracht, Koen; Eikemo, Terje Andreas; Bracke, Piet

2014-11-01

This study examines whether health inequalities exist between lone and cohabiting mothers across Europe, and how these may differ by welfare regime. Data from the European Social Survey were used to compare self-rated general health, limiting long-standing illness and depressive feelings by means of a multi-level logistic regression. The 27 countries included in the analyses are classified into six welfare regimes (Anglo-Saxon, Bismarckian, Southern, Nordic, Central East Europe (CEE) (new EU) and CEE (non-EU). Lone motherhood is defined as mothers not cohabiting with a partner, regardless of their legal marital status. The results indicate that lone mothers are more at risk of poor health than cohabiting mothers. This is most pronounced in the Anglo-Saxon regime for self-rated general health and limiting long-standing illness, while for depressive feelings it is most pronounced in the Bismarckian welfare regime. While the risk difference is smallest in the CEE regimes, both lone and cohabiting mothers also reported the highest levels of poor health compared with the other regimes. The results also show that a vulnerable socioeconomic position is associated with ill-health in lone mothers and that welfare regimes differ in the degree to which they moderate this association. © 2014 The Authors. Sociology of Health & Illness © 2014 Foundation for the Sociology of Health & Illness/John Wiley & Sons Ltd.

It is all in their mind: A review on information processing bias in lonely individuals.

PubMed

Spithoven, Annette W M; Bijttebier, Patricia; Goossens, Luc

2017-12-01

Loneliness is a distressing emotional state that motivates individuals to renew and maintain social contact. It has been suggested that lonely individuals suffer from a cognitive bias towards social threatening stimuli. However, current models of loneliness remain vague on how this cognitive bias is expressed in lonely individuals. The current review provides an up-to-date overview of studies examining loneliness in relation to various aspects of cognitive functioning. These studies are interpreted in light of the Social Information Processing (SIP) model. A wide range of studies indicate that lonely individuals have a negative cognitive bias in all stages of SIP. More specifically, lonely individuals have an increased attention for social threatening stimuli, hold negative and hostile intent attributions, expect rejection, evaluate themselves and others negatively, endorse less promotion- and more prevention-oriented goals, and have a low self-efficacy. This negative cognitive bias seems specific to the social context. Avenues for future research and implications for clinical practice are discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

State Regulation, Family Breakdown, and Lone Motherhood

PubMed Central

Meek, Jeff

2014-01-01

Using a range of parish records, records from the Registrar General of Scotland, charity organizations, and media reports, this article contributes to the historiography which evaluates the effects of World War I in Britain as well as the history of lone mothers and their children. It highlights how during the war, women, especially lone mothers, made significant gains through the welfare system, changing approaches to illegitimacy and the plentiful nature of women’s work but also how in doing so this brought them under greater surveillance by the state, local parishes, and charity organizations. Moreover, as this article will demonstrate, many of the gains made by women were short-lived and in fact the war contributed to high levels of family breakdown and gendered and intergenerational poverty endured by lone mothers and their children. PMID:26538794

A theoretical and experimental study on the molecular and electronic structures of artemisinin and related drug molecules

NASA Astrophysics Data System (ADS)

Galasso, V.; Kovač, B.; Modelli, A.

2007-06-01

The equilibrium structures of artemisinin and a selection of its derivatives (potent antimalarial drugs) have been studied with the density functional theory ansatz B3LYP. Of the five rings of the artemisinin framework, it is only the pyranose ring B that exhibits a marked conformational flexibility, especially on addition of a pendant side chain at C-10. For the derivatives, the β isomer with the axial substituent group is found to be energetically more stable than the α isomer with the equatorial group. The assignment of the vibrational fundamentals has been supported by calculations on related model molecules and a normal coordinate analysis. This allows for a reliable characterization of the normal modes, mainly involving the peroxide linkage, in the claimed fingerprint region of 1,2,4-trioxanes. The electronic structures have also been studied by measuring and calculating significant features of the NMR, photoelectron and electron transmission spectra. In particular, a representative set of NMR chemical shifts and nuclear spin-spin coupling constants, obtained with DFT formalisms, compares favourably with experiment and fits expectation in terms of stereoelectronic effects of the vicinal oxygen lone pairs. Based on ab initio outer valence Green's function calculations, a consistent interpretation of the uppermost bands in the photoelectron spectra of artemisinin and derivatives has been advanced. The top ionization energies reflect a complex interaction of the various oxygen lone pair orbitals. Electron transmission spectroscopy is applied for the first time to compounds containing the peroxide bond and elucidates the empty level electronic structure of artemisinin and derivatives in the 0-6 eV energy range, with the support of MO calculations and comparison with the spectra of reference molecules. Electron attachment to the lowest-lying empty σ∗ MO, mainly localized on the O-O bridge, occurs at an energy (1.7 eV) exceptionally low for compounds not containing third-row or heavier elements.

The molecular structure of 5-X-isatines where (X = F, Cl, and Br) determined by gas-phase electron diffraction with theoretical calculations

NASA Astrophysics Data System (ADS)

Belyakov, Alexander V.; Nikolaenko, Kirill O.; Davidovich, Pavel B.; Ivanov, Anatolii D.; Ponyaev, Alexander I.; Rykov, Anatolii N.; Shishkov, Igor F.

2018-01-01

The molecular structures of 5-X-isatines where X = F (1), Cl (2), and Br (3) were studied by gas-phase electron diffraction (GED) and theoretical calculations at M062X/aug-cc-pVTZ and MP2/aug-cc-pVTZ levels. The best fit of the experimental scattering intensities was obtained for a molecular model of Cs symmetry. The small differences between similar geometric parameters were constrained at the values calculated at the M062X level. The bond distances in the benzene ring are in agreement with their standard values. The (Odbnd)Csbnd C(dbnd O) carbon-carbon bonds of the pyrrole moiety in title compounds (1.581(11), 1.578(8), 1.574(12) Å, respectively) are remarkably lengthened in comparison with standard C(sp2)-C(sp2) value, 1.425(11) Å for N-methylpyrrole. According to NBO analysis this lengthening cannot be attributed to the electrostatic repulsion of oxygen lone pairs alone and is, mainly, due to the hyperconjugation, that is delocalization of oxygen lone pairs of π-type into the corresponding carbon-carbon antibonding orbital, nπ(O)→σ*(Csbnd C). Deletion of σ*(Csbnd C) orbital followed by subsequent geometry optimization led to shortening of the corresponding Csbnd C bond by 0.05-0.06 Å. Electronegative halogen atoms led to increase of Csbnd CXsbnd C endocyclic bond angles at ipso carbon atom as compared with the value of 120° in regular hexagon. According to different aromaticity descriptors, aromaticity of benzene moiety of title compounds is smaller in comparison with benzene molecule. External magnetic field induces diatropic ring current in benzene moiety. Local reactivity descriptors that indicate sites in a molecule that are susceptible to nucleophilic, electrophilic and radical attack are calculated.

Bottom-up synthesis of WS2 nanosheets with synchronous surface modification for imaging guided tumor regression.

PubMed

Wang, Shige; Zhao, Jiulong; Yang, Hailun; Wu, Chenyao; Hu, Fei; Chang, Haizhou; Li, Guixiang; Ma, Dan; Zou, Duowu; Huang, Mingxian

2017-08-01

Two-dimensional transition metal dichalcogenides (TMDs) have been receiving great attention as NIR photothermal transducing agent in tumor photothermal therapy. Keeping in mind the low efficiency of the conventional top-down exfoliated 2D TMDs and the complexity of their surface modifications, we herein proposed a bottom-up strategy for the one-pot hydrothermal and controlled synthesis of surface polyvinyl pyrrolidone (PVP) modified WS 2 nanosheets. The material design was based on the chelating-coordinating effect between the lone pair electrons of oxygen of PVP carbonyl group and the unoccupied orbital (5d orbitals) of tungsten. The WS 2 nanosheets with synchronous surface PVP grafting showed an excellent photothermal conversion performance, while the surface anchored PVP guaranteed its colloidal stability. Moreover, the strong X-ray attenuation ability and near-infrared (NIR) absorbance of WS 2 -PVP 360kDa enabled the sensitive in vitro and in vivo computed tomography and photoacoustic imaging. The WS 2 -PVP 360kDa nanosheets were biocompatible and exhibited promising in vitro and in vivo anti-cancer efficacy. Findings in this report may greatly promote the design of colloidal stable and biocompatible 2D TMDs and their future clinical translations. A bottom-up strategy for the one-pot and controlled synthesis of surface polyvinyl pyrrolidone (PVP) modified WS 2 nanosheets was proposed for the first time. By hydrothermally treating the mixture solution of tetrathiotungstate and PVP, Owing to the chelating-coordinating effect between the lone pair electrons of oxygen of PVP carbonyl group and the unoccupied orbital (5d orbitals) of tungsten, PVP was synchronously graphed on WS 2 -PVP nanosheets surface. The formed WS 2 -PVP nanosheets were colloidal stable, biocompatible, and exhibited promising computed tomography, photoacoustic imaging and tumor photothermal therapy efficacy both in vitro and in vivo. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Ferrocene Orientation Determined Intramolecular Interactions Using Energy Decomposition Analysis.

PubMed

Wang, Feng; Islam, Shawkat; Vasilyev, Vladislav

2015-11-16

Two very different quantum mechanically based energy decomposition analyses (EDA) schemes are employed to study the dominant energy differences between the eclipsed and staggered ferrocene conformers. One is the extended transition state (ETS) based on the Amsterdam Density Functional (ADF) package and the other is natural EDA (NEDA) based in the General Atomic and Molecular Electronic Structure System (GAMESS) package. It reveals that in addition to the model (theory and basis set), the fragmentation channels more significantly affect the interaction energy terms (Δ E ) between the conformers. It is discovered that such an interaction energy can be absorbed into the pre-partitioned fragment channels so that to affect the interaction energies in a particular conformer of Fc. To avoid this, the present study employs a complete fragment channel-the fragments of ferrocene are individual neutral atoms. It therefore discovers that the major difference between the ferrocene conformers is due to the quantum mechanical Pauli repulsive energy and orbital attractive energy, leading to the eclipsed ferrocene the energy preferred structure. The NEDA scheme further indicates that the sum of attractive (negative) polarization (POL) and charge transfer (CL) energies prefers the eclipsed ferrocene. The repulsive (positive) deformation (DEF) energy, which is dominated by the cyclopentadienyle (Cp) rings, prefers the staggered ferrocene. Again, the cancellation results in a small energy residue in favour of the eclipsed ferrocene, in agreement with the ETS scheme. Further Natural Bond Orbital (NBO) analysis indicates that all NBO energies, total Lewis (no Fe) and lone pair (LP) deletion all prefer the eclipsed Fc conformer. The most significant energy preferring the eclipsed ferrocene without cancellation is the interactions between the donor lone pairs (LP) of the Fe atom and the acceptor antibond (BD*) NBOs of all C-C and C-H bonds in the ligand, LP(Fe)-BD*(C-C & C-H), which strongly stabilizes the eclipsed (D 5h ) conformation by -457.6 kcal·mol -1 .

Conformational preferences of γ-aminobutyric acid in the gas phase and in water

NASA Astrophysics Data System (ADS)

Song, Il Keun; Kang, Young Kee

2012-09-01

The conformational study of γ-aminobutyric acid (GABA) has been carried out at the M06-2X/cc-pVTZ level of theory in the gas phase and the SMD M06-2X/cc-pVTZ level of theory in water. In the gas phase, the folded conformation gG1 with gauche- and gauche+ conformations for the Cβsbnd Cα and Cγsbnd Cβ bonds, respectively, is found to be lowest in energy and enthalpy, which can be ascribed to the favored hyperconjugative n → π* interaction between the lone electron pair of the amine nitrogen atom and the Cdbnd O bond of the carboxylic group and the favored antiparallel dipole-dipole interaction between the Nsbnd H bond and the Cdbnd O bond. In addition, the intramolecular hydrogen bonds between the carboxylic group and the amine Nsbnd H group have contributed to stabilize some low-energy conformers. However, the most preferred conformation is found to be tG1 and more stable by 0.4 kcal/mol in ΔG than the conformer gG1, in which the favored entropic term due to the conformational flexibility and the other favored n → σ*, σ → σ*, and π → σ* interactions seem to play a role. The conformational preferences of the neutral GABA calculated by ΔG's are reasonably consistent with the populations deduced from FT microwave spectroscopy in supersonic jets combined with laser ablation. In water, the two folded conformers Gg and gG of the zwitterionic GABA are dominantly populated, each of which has the population of 47%, and the hydrogen bond between the ammonium Nsbnd H group and the lone electron pair of the Csbnd O- group seems to be crucial in stabilizing these conformers. Our calculated result that the folded conformers preferentially exist in water is consistent with the 1H NMR experiments in D2O.

Changing notions of lone motherhood in twentieth-century Finland.

PubMed

May, Vanessa

2011-01-01

Through written life stories of lone mothers, this article examines changes in lone motherhood in twentieth-century Finland. While the older life-story writers' narratives are clearly influenced by an 'ethos of survival' and the regulation of female sexuality, the younger writers relate their experiences with the help of scripts on gender equality and the psychological importance of 'good' parenting. These narrative shifts point to important changes in cultural scripts on women's positions in families, on the labour market, and in society.

Finding the Wolves in Sheeps Clothing: Ways to Distinguish and Deter Lone-Wolf Terrorists

DTIC Science & Technology

2015-03-01

Mark Hamm, “Lone-wolf Terrorism in America: Forging a New Way of Looking at an Old Problem,” YouTube video, 7:32, posted by the National Institute...that factors that influence most lone-wolf terrorists include, “to varying degrees and in variable combinations: personal aversion or depression ...Russia.”97 Also discovered after the bombings, “Tamerlan had a YouTube account that he used to post and watch violent Islamic extremist videos starting

The Nation That Cried Lone Wolf: A Data-Driven Analysis of Individual Terrorists in the United States Since 9/11

DTIC Science & Technology

2012-03-01

the “ Underwear Bomber.” He is not classified as a lone-wolf terrorist, although he did operationalize his attack as a lone individual. Abdulmutallab...commencing the attacks. 4. July 2002—Hesham Mohamed Hadayet Hesham Mohamed Hadayet opened fire in Los Angeles International Airport on July 4, 2002...killed Hadayet at the scene. 76 5. October 2002—Steve Kim Postal worker Steve Kim fired seven shots at the United Nations to physically protest

InSAR detection of aquifer recovery: Case studies of Koehn Lake (central California) and Lone Tree Gold Mine (Basin and Range)

NASA Astrophysics Data System (ADS)

Wdowinski, S.; Greene, F.; Amelung, F.

2013-12-01

Anthropogenic intervention in groundwater flow and aquifer storage often results in vertical movements of Earth's surface, which are well detected by InSAR observations. Most anthropogenic intervention occurs due to groundwater extraction for both agriculture and human consumption and results in land subsidence. However in some cases, ending anthropogenic intervention can lead to aquifer recovery and, consequently, surface uplift. In this study we present two such cases of aquifer recovery. The first case is the aquifer beneath Koehn Lake in Central California, which was overused to meet agricultural demands until the 1990's. The second case is the Lone Tree Gold Mine in Nevada that during active mining in the 1991-2006 groundwater pumping disrupted the aquifer and cause subsidence. But after mining ceased, groundwater flow was recovered and resulted in uplift. In both cases we studied the surface uplift using InSAR time series observations. We conduct an ERS and Envisat InSAR survey over Koehn Lake in California and Lone Tree Gold Mine in Nevada between 1992 and 2010. We followed the SBAS algorithm to generate a time-series of ground displacements and average velocities of pixels, which remain coherent through time in the SAR dataset. A total of 100 and 80 combined ERS and Envisat SAR dates are inverted for Koehn Lake and Lone Tree Gold Mine respectively. Results for the Koehn Lake area indicate a rapid uplift of about 3.5 mm/yr between 1992-2000 and a slower uplift rate of 1.6 mm/yr between 2000-2004, suggesting a decrease in the recovery process. The observed uplift correlates well with groundwater level increase in the Koehn Lake area. Results for the Lone Tree Gold Mine show a constant subsidence (~ 1 cm/yr) due to groundwater extraction between 1992-2006, but uplift of ~1 cm/yr since the beginning of 2007. In both case studies, InSAR observations reveal that the aquifer recovery is accompanied by surface uplift. We plan to use the InSAR observations and the groundwater level records to model and better understand aquifer recovery processes.

Higher Educational Consortia Organization: Functional Structures of Administration and Management.

ERIC Educational Resources Information Center

Lepchenske, George L.

The administrative and functional organization of higher education consortia are discussed. The need for cooperation between individual institutions has been established; one lone institution cannot encompass all knowledge generated. The rapid growth of consortia has generated extensive services, funding sources, developmental activities,…

2. Historic American Buildings Survey, Arthur W. Stewart, Photographer April ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

2. Historic American Buildings Survey, Arthur W. Stewart, Photographer April 24, 1936 EAST ELEVATION (FRONT). - O'Henry House, Lone Star Brewery, 600 Lone Star Boulevard, San Antonio, Bexar County, TX

Challenges of CPD for physiotherapists working as lone practitioners in amputee rehabilitation.

PubMed

Cole, Mary Jane; Morris, Jane; Scammell, Amy

2008-09-01

The aim of this study was to explore the issues around continuing professional development (CPD) for physiotherapists working as lone practitioners in amputee rehabilitation in the United Kingdom (UK). Qualitative method using a phenomenological approach via one to one semi-structured interviews and thematic data analysis. Ten physiotherapists with responsibility for amputee rehabilitation working as lone practitioners in hospitals or specialist centres in the UK. CPD is valued and there is commitment towards the process. Current solutions are identified but there are frustrations around more structured CPD and organizational issues. These include inadequate access to learning opportunities, lack of professional feedback, insufficient time and limited learning skills. There are opportunities for improving CPD through organizational structures but specialist input is recommended to support lone practitioners and managers with the process, e.g., consultant or peripatetic therapists.

The Myth of the Lone Physician: Toward a Collaborative Alternative

PubMed Central

Saba, George W.; Villela, Teresa J.; Chen, Ellen; Hammer, Hali; Bodenheimer, Thomas

2012-01-01

Cultural values and beliefs about the primary care physician bolster the myth of the lone physician: a competent professional who is esteemed by colleagues and patients for his or her willingness to sacrifice self, accept complete responsibility for care, maintain continuity and accessibility, and assume the role of lone decision maker in clinical care. Yet the reality of current primary care models is often fragmented, impersonal care for patients and isolation and burnout for many primary care physicians. An alternative to the mythological lone physician would require a paradigm shift that places the primary care physician within the context of a highly functioning health care team. This new mythology better fulfills the collaborative, interprofessional, patient-centered needs of new models of care, and might help to ensure that the work of primary care physicians remains compassionate, gratifying, and meaningful. PMID:22412010

A brief history of 'lone' atrial fibrillation: from 'a peculiar pulse irregularity' to a modern public health concern.

PubMed

Potpara, Tatjana S; Lip, Gregory Y H

2015-01-01

Ever since the original description of a 'peculiar pulse irregularity', atrial fibrillation (AF) has been studied extensively and has come a long journey from the recognition of its cardiac origins, to the modern concept of AF as a serious public health challenge with profound social and economic implications. This arrhythmia affects around 2% of adult population, and the most common underlying heart diseases accompanying AF in the modern era are hypertension, heart failure and coronary artery disease, as well as valvular heart diseases and numerous other cardiac as well as non-cardiac disorders which have been shown to predispose to AF. On occasions, AF occurs in young otherwise apparently healthy individuals (so called 'lone AF'). For a long time, 'lone' AF has been believed to bear a favourable prognosis as compared to AF with underlying structural heart disease, but increasing evidence suggests that 'lone' AF patients represent a rather heterogeneous cohort, with highly variable individual risk profiles due to the presence of various subclinical cardiovascular risk factors or genetically determined subtle alterations at the cellular or molecular level. For these reasons, the existence of truly 'lone' AF has recently been questioned. In this review article, we present a brief history of the recognition of the public health burden of AF. We discuss some of the misconceptions and breakthroughs on modern knowledge on AF, including the rise (and fall) of the 'lone' AF concept.

Density-Difference-Driven Optimized Embedding Potential Method To Study the Spectroscopy of Br₂ in Water Clusters.

PubMed

Roncero, Octavio; Aguado, Alfredo; Batista-Romero, Fidel A; Bernal-Uruchurtu, Margarita I; Hernández-Lamoneda, Ramón

2015-03-10

A variant of the density difference driven optimized embedding potential (DDD-OEP) method, proposed by Roncero et al. (J. Chem. Phys. 2009, 131, 234110), has been applied to the calculation of excited states of Br2 within small water clusters. It is found that the strong interaction of Br2 with the lone electronic pair of the water molecules makes necessary to optimize specific embedding potentials for ground and excited electronic states, separately and using the corresponding densities. Diagnosis and convergence studies are presented with the aim of providing methods to be applied for the study of chromophores in solution. Also, some preliminary results obtained for the study of electronic states of Br2 in clathrate cages are presented.

Natural chemical shielding analysis of nuclear magnetic resonance shielding tensors from gauge-including atomic orbital calculations

NASA Astrophysics Data System (ADS)

Bohmann, Jonathan A.; Weinhold, Frank; Farrar, Thomas C.

1997-07-01

Nuclear magnetic shielding tensors computed by the gauge including atomic orbital (GIAO) method in the Hartree-Fock self-consistent-field (HF-SCF) framework are partitioned into magnetic contributions from chemical bonds and lone pairs by means of natural chemical shielding (NCS) analysis, an extension of natural bond orbital (NBO) analysis. NCS analysis complements the description provided by alternative localized orbital methods by directly calculating chemical shieldings due to delocalized features in the electronic structure, such as bond conjugation and hyperconjugation. Examples of NCS tensor decomposition are reported for CH4, CO, and H2CO, for which a graphical mnemonic due to Cornwell is used to illustrate the effect of hyperconjugative delocalization on the carbon shielding.

Time-resolved XAFS spectroscopic studies of B-H and N-H oxidative addition to transition metal catalysts relevant to hydrogen storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bitterwolf, Thomas E.

2014-12-09

Successful catalytic dehydrogenation of aminoborane, H 3NBH 3, prompted questions as to the potential role of N-H oxidative addition in the mechanisms of these processes. N-H oxidative addition reactions are rare, and in all cases appear to involve initial dative bonding to the metal by the amine lone pairs followed by transfer of a proton to the basic metal. Aminoborane and its trimethylborane derivative block this mechanism and, in principle, should permit authentic N-H oxidative attrition to occur. Extensive experimental work failed to confirm this hypothesis. In all cases either B-H complexation or oxidative addition of solvent C-H bonds dominatemore » the chemistry.« less

Ab initio molecular orbital and infrared spectroscopic study of the conformation of secondary amides: derivatives of formanilide, acetanilide and benzylamides

NASA Astrophysics Data System (ADS)

Ilieva, S.; Hadjieva, B.; Galabov, B.

1999-09-01

Ab initio molecular orbital calculations at HF/4-31G level and infrared spectroscopic data for the frequencies are applied to analyse the grouping in a series model aromatic secondary amides: formanilide; acetanilide; o-methylacetanilide; 2,6-dimethylformanilide, 2,6-dimethylacetanilide; N-benzylacetamide and N-benzylformamide. The theoretical and experimental data obtained show that the conformational state of the molecules studied is determined by the fine balance of several intramolecular factors: resonance effect between the amide group and the aromatic ring, steric interaction between various substituents around the -NH-CO- grouping in the aromatic ring, conjugation between the carbonyl bond and the nitrogen lone pair as well as direct field influences inside the amide group.

Nitriles as directionally tolerant hydrogen bond acceptors: IR-UV ion depletion spectroscopy of benzenepropanenitrile and its hydrate clusters

NASA Astrophysics Data System (ADS)

Robertson, Patrick A.; Lobo, Isabella A.; Wilson, David J. D.; Robertson, Evan G.

2016-09-01

Benzenepropanenitrile (BPN) and its hydrate clusters are studied by R2PI and IR-UV ion-depletion spectroscopy in the CH/OH stretch regions, aided by theoretical calculations. A single water molecule binds to the terminal nitrile 'lone-pair' of the anti-BPN host, but there is also evidence for a side-type structure with OH donating to the nitrile π-electrons. In the gauche-BPN cluster, water is located at an intermediate angle that facilitates O⋯HC(ortho) interaction. A wide range of attachment angles is possible, as the intrinsic preference for linear hydrogen bonding is mediated by additional CH⋯O interactions that depend on molecular geometry near the nitrile group.

Public health assessment for Lone Star Army Ammunition Plant, Texarkana, Bowie County, Texas, Region 6, CERCLIS number TX7213821831. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

Lone Star Army Ammunition Plant (Lone Star) is a 15,546-acre government-owned contractor-operated industrial facility 12 miles west of Texarkana, Texas in Bowie County. Lone Star is near the communities of Hooks and Leary to the north, and Redwater and Maud to the south. The Old Demolition Area (ODA), a 19-acre section of land on the Lone Star facility used for the disposal of explosives by detonation, was placed on the National Priorities List (NPL) on July 22, 1987. The Texas Department of Health (TDH) and the Agency for Toxic Substances and Disease Registry (ATSDR) evaluated the environmental information available formore » the site and identified several exposure situations for evaluation. These exposure situations include possible contact with site contaminants in sediment, soil, ordnance debris, surface water, and groundwater. Based on available data the authors have concluded that overall there are no public health hazards related to environmental contamination at the ODA. In the future, the conclusion category for the whole site could change if additional information indicates that a public health hazard exists.« less

Young Children's Attitudes and Perceptions of Older Adults.

ERIC Educational Resources Information Center

Burke, Judith Lee

1981-01-01

Studied the responses of children aged four to seven to photographs of older adults. Results indicated age discrimination was highly accurate by age six. Most expressed positive views of activities shared with grandparents but identified older adults in general as sad, lonely, and not busy. (Author/JAC)

Unexplained Cases of Allergic Reactions Linked to Red Meat

MedlinePlus

... that starts after being bitten by a lone star tick may cause unexplained cases of recurrent anaphylaxis. ... after eating meat. Previous studies have linked lone star tick bites to this unusual food allergy. The ...

Loneliness and Hypervigilance to Social Cues in Females: An Eye-Tracking Study

PubMed Central

Lodder, Gerine M. A.; Scholte, Ron H. J.; Clemens, Ivar A. H.; Engels, Rutger C. M. E.; Goossens, Luc; Verhagen, Maaike

2015-01-01

The goal of the present study was to examine whether lonely individuals differ from nonlonely individuals in their overt visual attention to social cues. Previous studies showed that loneliness was related to biased post-attentive processing of social cues (e.g., negative interpretation bias), but research on whether lonely and nonlonely individuals also show differences in an earlier information processing stage (gazing behavior) is very limited. A sample of 25 lonely and 25 nonlonely students took part in an eye-tracking study consisting of four tasks. We measured gazing (duration, number of fixations and first fixation) at the eyes, nose and mouth region of faces expressing emotions (Task 1), at emotion quadrants (anger, fear, happiness and neutral expression) (Task 2), at quadrants with positive and negative social and nonsocial images (Task 3), and at the facial area of actors in video clips with positive and negative content (Task 4). In general, participants tended to gaze most often and longest at areas that conveyed most social information, such as the eye region of the face (T1), and social images (T3). Participants gazed most often and longest at happy faces (T2) in still images, and more often and longer at the facial area in negative than in positive video clips (T4). No differences occurred between lonely and nonlonely participants in their gazing times and frequencies, nor at first fixations at social cues in the four different tasks. Based on this study, we found no evidence that overt visual attention to social cues differs between lonely and nonlonely individuals. This implies that biases in social information processing of lonely individuals may be limited to other phases of social information processing. Alternatively, biased overt attention to social cues may only occur under specific conditions, for specific stimuli or for specific lonely individuals. PMID:25915656

The role of poverty in explaining health variations in 7-year-old children from different family structures: findings from the UK Millennium Cohort Study.

PubMed

Pearce, Anna; Lewis, Hannah; Law, Catherine

2013-02-01

Despite rises in reconstituted and lone-parent families, relatively little is known about how the health of children in different family types varies, and the extent to which any differences might be explained by poverty. The authors examined this using cross-sectional data on 13 681 seven-year-olds from the Millennium Cohort Study. The authors estimated RRs and 95% CIs for having poor physical (general health, long-standing illness, injury, overweight, asthma, fits) and mental health (using strengths and difficulties scores) according to family structure using Poisson regression. The authors adjusted for confounders (aRR) and then investigated the role of poverty as a mediator by entering a poverty score (based on income, receipt of benefits, subjective poverty and material deprivation) into the main model. Children living in reconstituted and lone-parent families were at a slight increased risk of poor health compared with those living with two natural parents. Adjusting for poverty tended to remove the elevated risk of poor physical health in children living in lone-parent and reconstituted families. However, for the mental health outcomes, poverty tended to remove the elevated risk for lone parents but not for reconstituted families. For example, the aRR for borderline-abnormal total difficulties fell from 1.45 (1.22 to 1.72) to 1.34 (1.13 to 1.59) in children living in reconstituted families and from 1.29 (1.14 to 1.45) to 1.05 (0.92 to 1.19) in those living with lone parents. Poor physical and mental health was slightly more prevalent in children living in lone-parent or reconstituted families. Poverty reduction may help to reduce these differences, especially for children living with lone parents; however, alternative mechanisms should be also explored, particularly for children living in reconstituted families.

Working alone.

PubMed

Tearle, Paul

2004-09-01

Employees may be found working alone in a wide range of occupations. Technological advance, rationalisation and automation mean that more and more frequently. one single person is in charge of several machines, pieces of equipment or different work activities. Employees will be found working alone during work carried out as 'overtime', as part of flexible working hours, on Saturdays, Sundays, Bank Holidays and other statutory leave days, or in situations where their work takes them away from a fixed base (mobile workers). A person may be considered to be 'working alone' whenever it is not possible to offer immediate assistance following an accident or in another critical situation. This article looks at the legal background to lone working and what an employer must do to ensure lone workers are at no greater risk to their health and safety than any other members of the workforce.

Atomic displacements in the charge ice pyrochlore Bi2Ti2O6O' studied by neutron total scattering

NASA Astrophysics Data System (ADS)

Shoemaker, Daniel P.; Seshadri, Ram; Hector, Andrew L.; Llobet, Anna; Proffen, Thomas; Fennie, Craig J.

2010-04-01

The oxide pyrochlore Bi2Ti2O6O' is known to be associated with large displacements of Bi and O' atoms from their ideal crystallographic positions. Neutron total scattering, analyzed in both reciprocal and real space, is employed here to understand the nature of these displacements. Rietveld analysis and maximum entropy methods are used to produce an average picture of the structural nonideality. Local structure is modeled via large-box reverse Monte Carlo simulations constrained simultaneously by the Bragg profile and real-space pair distribution function. Direct visualization and statistical analyses of these models show the precise nature of the static Bi and O' displacements. Correlations between neighboring Bi displacements are analyzed using coordinates from the large-box simulations. The framework of continuous symmetry measures has been applied to distributions of O'Bi4 tetrahedra to examine deviations from ideality. Bi displacements from ideal positions appear correlated over local length scales. The results are consistent with the idea that these nonmagnetic lone-pair containing pyrochlore compounds can be regarded as highly structurally frustrated systems.

One step synthesis of P-doped g-C3N4 with the enhanced visible light photocatalytic activity

NASA Astrophysics Data System (ADS)

Liu, Sen; Zhu, Honglei; Yao, Wenqing; Chen, Kai; Chen, Daimei

2018-02-01

In our work, P doped Graphitic nitride (g-C3N4) was prepared by the simple copolymerization of melamine and melamine phosphate. The melamine phosphate ester polymer is a complex of an s-triazine and phosphoric acid polymer, thus it will be favourable for P atom to incorporate into the Csbnd N network of g-C3N4. The doped P atoms may produce the delocalized lone electron and form the Lewis acid sites. The obtained P-doped g-C3N4 showed the higher photocatalytic activity in photodegradation of MB and 2,4-Dichlorophenol than g-C3N4. The optimum photocatatlytic activity of P-C3N4 with the weight ration of melamine phosphate and melamine at 0.06 is 2 times as higher as the pure g-C3N4 in MB photodegradation, and 1.5 times higher in 2,4-Dichlorophenol photodegradation. The enhancement of photodegradation efficiency is due to the delocalization effect of lone electron, promoting the separation of photogenerated charges, and the larger band gap of P doped g-C3N4.

Ae2Sb2X4F2 (Ae = Sr, Ba): new members of the homologous series Ae2M(1+n)X(3+n)F2 designed from rock salt and fluorite 2D building blocks.

PubMed

Kabbour, Houria; Cario, Laurent

2006-03-20

We have designed new compounds within the homologous series Ae2F2M(1+n)X(3+n) (Ae = Sr, Ba; M = main group metal; n = integer) built up from the stacking of 2D building blocks of rock salt and fluorite types. By incrementally increasing the size of the rock salt 2D building blocks, we have obtained two new n = 1 members of this homologous series, namely, Sr2F2Sb2Se4 and Ba2F2Sb2Se4. We then succeeded in synthesizing these compounds using a high-temperature ceramic method. The structure refinements from the powder or single-crystal X-ray diffraction data confirmed presence of the expected alternating stacking of fluorite [Ae2F2] (Ae = Sr, Ba) and rock salt [Sb2Se4] 2D building blocks. However the Ba derivative shows a strong distortion of the [Sb2Se4] block and a concomitant change of the Sb atom coordination likely related to the lone-pair activity.

Novel 3D bismuth-based coordination polymers: Synthesis, structure, and second harmonic generation properties

NASA Astrophysics Data System (ADS)

Wibowo, Arief C.; Smith, Mark D.; Yeon, Jeongho; Halasyamani, P. Shiv; zur Loye, Hans-Conrad

2012-11-01

Two new 3D bismuth containing coordination polymers are reported along with their single crystal structures and SHG properties. Compound 1: Bi2O2(pydc) (pydc=pyridine-2, 5-dicarboxylate), crystallizes in the monoclinic, polar space group, P21 (a=9.6479(9) Å, b=4.2349(4) Å, c=11.9615(11) Å, β=109.587(1)°), which contains Bi2O2 chains that are connected into a 3D structure via the pydc ligands. Compound 2: Bi4Na4(1R3S-cam)8(EtOH)3.1(H2O)3.4 (1R3S cam=1R3S-camphoric acid) crystallizes in the monoclinic, polar space group, P21 (a=19.0855(7) Å, b=13.7706(5) Å, c=19.2429(7) Å, β=90.701(1)°) and is a true 3D coordination polymer. These are two example of SHG compounds prepared using unsymmetric ligands (compound 1) or chiral ligands (compound 2), together with metals that often exhibit stereochemically-active lone pairs, such as Bi3+, a synthetic approach that resulted in polar, non-centrosymmetric, 3D metal-organic coordination polymer.

The isonitrile-nitrile isomerization: kinetic parameters, reaction mechanism and relative photoionization cross-section of the HOMO. A HeI photoelectron spectroscopy study

NASA Astrophysics Data System (ADS)

Wang, Dianxun; Qian, Ximei; Zhang, Qiyuan

1997-03-01

The isomerisation reactions from CH 3CH 2CH 2NC to CH 3CH 2CH 2CN, (CH 3) 2CHNC to (CH 3) 2CHCN and (CH 3) 3CNC to (CH 3) 3CCN are found to be of first order by using HeI photoelectron spectroscopy (PES). The activation energies obtained by PES for the isomerisation of RNC, where R is -CH 3, -CH 2CH 3, -CH 2CH 2CH 3, -CH(CH 3) 2, and -C(CH 3) 3 are similar. This can be explained by the breaking of the RN bond and the making of the RC bond in the isomerisation reaction from RNC to RCN being essentially synchronous. A transition state is proposed. The photoionization cross-sections of the HOMO for the RNC are deduced from the intercept values in the kinetic equations obtained using PES, and related to the weight of the carbon atom in the isocyano group, because the HOMOs of the RNC mainly embody the 2s lone-pair electron of the carbon atom in the isocyano group.

Exploring the low friction of diamond-like carbon films in carbon dioxide atmosphere by experiments and first-principles calculations

NASA Astrophysics Data System (ADS)

Huo, Lei; Wang, Shunhua; Pu, Jibin; Sun, Junhui; Lu, Zhibin; Ju, Pengfei; Wang, Liping

2018-04-01

The friction behavior and the mechanism of DLC films in CO2 atmosphere are rarely explored, which is a significant obstacle for the potential practical application of DLC films in primarily CO2 environment. Here, the experiments and first-principles calculations are performed to simultaneously investigate this theme. We find that DLC films in CO2 atmosphere exhibit astoundingly low friction coefficient compared with in ambient air and vacuum atmospheres. The XPS and Raman spectrums demonstrate the possibly activation of CO2 molecule in the shearing interfaces, which may be critical for the low friction of DLC films in CO2 atmosphere. The calculated results reveal that the lactone groups can easily form during the horizontally chemisorption of CO2 molecule on the DLC surface, which is energetic and is a favorable process under the interfacial stress. Because of the presence of the lone-pairs of the lactone group, the lactone-terminated surfaces appear to be responsible for the low friction of DLC films in CO2 atmosphere. The studies may open up the possibility for DLC films usage in Mars applications.

Loneliness: Its Correlates and Association with Health Behaviours and Outcomes in Nine Countries of the Former Soviet Union

PubMed Central

Stickley, Andrew; Koyanagi, Ai; Roberts, Bayard; Richardson, Erica; Abbott, Pamela; Tumanov, Sergei; McKee, Martin

2013-01-01

Background Research suggests that the prevalence of loneliness varies between countries and that feeling lonely may be associated with poorer health behaviours and outcomes. The aim of the current study was to examine the factors associated with loneliness, and the relationship between feeling lonely and health behaviours and outcomes in the countries of the former Soviet Union (FSU) – a region where loneliness has been little studied to date. Methods Using data from 18,000 respondents collected during a cross-sectional survey undertaken in nine FSU countries – Armenia, Azerbaijan, Belarus, Georgia, Kazakhstan, Kyrgyzstan, Moldova, Russia and Ukraine – in 2010/11, country-wise logistic regression analysis was conducted to determine: the factors associated with feeling lonely; the association between feeling lonely and alcohol consumption, hazardous drinking and smoking; and whether feeling lonely was linked to poorer health (i.e. poor self-rated health and psychological distress). Results The prevalence of loneliness varied widely among the countries. Being divorced/widowed and low social support were associated with loneliness in all of the countries, while other factors (e.g. living alone, low locus of control) were linked to loneliness in some of the countries. Feeling lonely was connected with hazardous drinking in Armenia, Kyrgyzstan and Russia but with smoking only in Kyrgyzstan. Loneliness was associated with psychological distress in all of the countries and poor self-rated health in every country except Kazakhstan and Moldova. Conclusions Loneliness is associated with worse health behaviours and poorer health in the countries of the FSU. More individual country-level research is now needed to formulate effective interventions to mitigate the negative effects of loneliness on population well-being in the FSU. PMID:23861843

Synthesis, Structure, Te Alloying, and Physical Properties of CuSbS 2

DOE PAGES

Hobbis, Dean; Wei, Kaya; Wang, Hsin; ...

2017-10-30

Materials with very low thermal conductivities continue to be of interest for a variety of applications. In this paper, we synthesized CuSbS 2 employing a mechanical alloying technique in order to investigate its physical properties. The trigonal pyramid arrangement of the S atoms around the Sb atoms allows for lone-pair electron formation that results in very low thermal conductivity. Finally, in addition to thermal properties, the structural, electrical, and optical properties, as well as compositional stability measurements, are also discussed. CuSbS 1.8Te 0.2 was similarly synthesized and characterized in order to compare its structural and transport properties with that ofmore » CuSbS 2, in addition to investigating the effect of Te alloying on these properties.« less

Synthesis, Structure, Te Alloying, and Physical Properties of CuSbS 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hobbis, Dean; Wei, Kaya; Wang, Hsin

Materials with very low thermal conductivities continue to be of interest for a variety of applications. In this paper, we synthesized CuSbS 2 employing a mechanical alloying technique in order to investigate its physical properties. The trigonal pyramid arrangement of the S atoms around the Sb atoms allows for lone-pair electron formation that results in very low thermal conductivity. Finally, in addition to thermal properties, the structural, electrical, and optical properties, as well as compositional stability measurements, are also discussed. CuSbS 1.8Te 0.2 was similarly synthesized and characterized in order to compare its structural and transport properties with that ofmore » CuSbS 2, in addition to investigating the effect of Te alloying on these properties.« less

A Triatomic Silicon(0) Cluster Stabilized by a Cyclic Alkyl(amino) Carbene.

PubMed

Mondal, Kartik Chandra; Roy, Sudipta; Dittrich, Birger; Andrada, Diego M; Frenking, Gernot; Roesky, Herbert W

2016-02-24

Reduction of the neutral carbene tetrachlorosilane adduct (cAAC)SiCl4 (cAAC=cyclic alkyl(amino) carbene :C(CMe2)2 (CH2)N(2,6-iPr2C6H3) with potassium graphite produces stable (cAAC)3Si3, a carbene-stabilized triatomic silicon(0) molecule. The Si-Si bond lengths in (cAAC)3Si3 are 2.399(8), 2.369(8) and 2.398(8) Å, which are in the range of Si-Si single bonds. Each trigonal pyramidal silicon atom of the triangular molecule (cAAC)3Si3 possesses a lone pair of electrons. Its bonding, stability, and electron density distributions were studied by quantum chemical calculations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of the physical properties of Ge-S-Ga glassy alloy

NASA Astrophysics Data System (ADS)

Rana, Anjli; Sharma, Raman

2018-05-01

In the present work, we have studied the effect of Ga doping on the physical properties of Ge20S80-xGax glassy alloy. The basic physical parameters which have important role in determining the structure and strength of the material viz. average coordination number, lone-pair electrons, mean bond energy, glass transition temperature, electro negativity, probabilities for bond distribution and cohesive energy have been computed theoretically for Ge-S-Ga glassy alloy. Here, the glass transition temperature and mean bond energy have been investigated using the Tichy-Ticha approach. The cohesive energy has been calculated by using chemical bond approach (CBA) method. It has been found that while average coordination number increases, all the other parameters decrease with the increase in Ga content in Ge-S-Ga system.

Comprehensive Mutation Scanning of LMNA in 268 Patients With Lone Atrial Fibrillation

PubMed Central

Brauch, Katharine M.; Chen, Lin Y.; Olson, Timothy M.

2009-01-01

Atrial fibrillation (AF) is a heritable, genetically heterogeneous disorder. To identify gene defects that cause or confer susceptibility to AF, a cohort of 268 unrelated patients with idiopathic forms of familial and sporadic AF was recruited. LMNA, encoding the nuclear membrane proteins, lamin A/C, was selected as a candidate gene for lone AF based on its established association with a syndrome of dilated cardiomyopathy, conduction system disease, and AF. Comprehensive mutation scanning identified only 1 potentially pathogenic mutation. In conclusion, LMNA mutations rarely cause lone AF and routine genetic testing of LMNA in these patients does not appear warranted. PMID:19427440

Investigating Hypervigilance for Social Threat of Lonely Children

ERIC Educational Resources Information Center

Qualter, Pamela; Rotenberg, Ken; Barrett, Louise; Henzi, Peter; Barlow, Alexandra; Stylianou, Maria; Harris, Rebecca A.

2013-01-01

The hypothesis that lonely children show hypervigilance for social threat was examined in a series of three studies that employed different methods including advanced eye-tracking technology. Hypervigilance for social threat was operationalized as hostility to ambiguously motivated social exclusion in a variation of the hostile attribution…

Therapeutic journery of nitrogen mustard as alkylating anticancer agents: Historic to future perspectives.

PubMed

Singh, Rajesh K; Kumar, Sahil; Prasad, D N; Bhardwaj, T R

2018-05-10

Cancer is considered as one of the most serious health problems today. The discovery of nitrogen mustard as an alkylating agent in 1942, opened a new era in the cancer chemotherapy. This valuable class of alkylating agent exerts its biological activity by binding to DNA, cross linking two strands, preventing DNA replication and ultimate cell death. At the molecular level, nitrogen lone pairs of nitrogen mustard generate a strained intermediate "aziridinium ion" which is very reactive towards DNA of tumor cell as well as normal cell resulting in various adverse side effects alogwith therapeutic implications. Over the last 75 years, due to its high reactivity and peripheral cytotoxicity, numerous modifications have been made in the area of nitrogen mustard to improve its efficacy as well as enhancing drug delivery specifically to tumor cells. This review mainly discusses the medicinal chemistry aspects in the development of various classes of nitrogen mustards (mechlorethamine, chlorambucil, melphalan, cyclophosphamide and steroidal based nitrogen mustards). The literature collection includes the historical and the latest developments in these areas. This comprehensive review also attempted to showcase the recent progress in the targeted delivery of nitrogen mustards that includes DNA directed nitrogen mustards, antibody directed enzyme prodrug therapy (ADEPT), gene directed enzyme prodrug therapy (GDEPT), nitrogen mustard activated by glutathione transferase, peptide based nitrogen mustards and CNS targeted nitrogen mustards. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Evaluation of DEET and eight essential oils for repellency against nymphs of the lone star tick, Amblyomma americanum (Acari: Ixodidae)

USDA-ARS?s Scientific Manuscript database

Eight commercially available essential oils (oregano, clove, thyme, vetiver, sandalwood, cinnamon, cedarwood, and peppermint) were evaluated for repellency against host-seeking nymphs of the lone star tick, Amblyomma americanum. Concentration- repellency response was established using the vertical ...

Relationship of liking of first names to birth order and loneliness.

PubMed

Joubert, C E

1990-06-01

Women who were first-born and only children reported liking their first names better than later-born women liked theirs. Also, women who liked their first names tended to be less lonely and have fewer siblings. Women with more siblings tended to be more lonely.

Functional and morphological analysis of putative chemoreception-related proteins in the lone star tick, Amblyomma americanum

USDA-ARS?s Scientific Manuscript database

Ehrlichiosis, a potentially fatal infection, is caused by rickettsial bacteria transmitted by the lone star tick, Amblyomma americanum. We previously analyzed the chemosensory appendage proteome of A. americanum as part of a project to develop new chemosensory-based vector control methods. Among the...

The structure of the L3 loop from the hepatitis delta virus ribozyme: a syn cytidine.

PubMed Central

Lynch, S R; Tinoco, I

1998-01-01

The structure of the L3 central hairpin loop isolated from the antigenomic sequence of the hepatitis delta virus ribozyme with the P2 and P3 stems from the ribozyme stacked on top of the loop has been determined by NMR spectroscopy. The 26 nt stem-loop structure contains nine base pairs and a 7 nt loop (5'-UCCUCGC-3'). This hairpin loop is critical for efficient catalysis in the intact ribozyme. The structure was determined using homonuclear and heteronuclear NMR techniques on non-labeled and15N-labeled RNA oligonucleotides. The overall root mean square deviation for the structure was 1.15 A (+/- 0.28 A) for the loop and the closing C.G base pair and 0.90 A (+/- 0.18 A) for the loop and the closing C.G base pair but without the lone purine in the loop, which is not well defined in the structure. The structure indicates a U.C base pair between the nucleotides on the 5'- and 3'-ends of the loop. This base pair is formed with a single hydrogen bond involving the cytosine exocyclic amino proton and the carbonyl O4 of the uracil. The most unexpected finding in the loop is a syn cytidine. While not unprecedented, syn pyrimidines are highly unusual. This one can be confidently established by intranucleotide distances between the ribose and the base determined by NMR spectroscopy. A similar study of the structure of this loop showed a somewhat different three-dimensional structure. A discussion of differences in the two structures, as well as possible sites of interaction with the cleavage site, will be presented. PMID:9461457

Reactivity of cyclopentadienyl molybdenum compounds towards formic acid: Structural characterization of CpMo(PMe 3)(CO) 2H, CpMo(PMe 3) 2(CO)H, [CpMo(μ-O)(μ-O 2CH)] 2, and [Cp*Mo(μ-O)(μ-O 2CH)] 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neary, Michelle C.; Parkin, Gerard

Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less

Comparison crystal structure conformations of two structurally related biphenyl analogues: 4,4′-bis­[3-(pyrrolidin-1-yl)prop-1-yn-1-yl]-1,1′-biphenyl and 4,4′-bis­{3-[(S)-2-methyl­pyrrolidin-1-yl]prop-1-yn-1-yl}-1,1′-biphen­yl

PubMed Central

Wan, Anqi; Penthala, Narsimha Reddy; Fifer, E. Kim; Parkin, Sean; Crooks, Peter A.

2015-01-01

The title compounds, C26H28N2, (I), and C28H32N2, (II), were designed based on the structure of the potent α9α10 nicotinic acetyl­choline receptor antagonist ZZ161C {1,1′-[[1,1′-biphen­yl]-4,4′-diylbis(prop-2-yne-3,1-di­yl)]bis­(3,4-di­methyl­pyridin-1-ium) bromide}. In order to improve the druglikeness properties of ZZ161C for potential oral administration, the title compounds (I) and (II) were prepared by coupling 4,4′-bis­(3-bromo­prop-1-yn-1-yl)-1,1′-biphenyl with pyrrol­idine, (I), and (S)-2-methyl­pyrrolidine, (II), respectively, in aceto­nitrile at room temperature. The asymmetric unit of (I) contains two half mol­ecules that each sit on sites of crystallographic inversion. As a result, the biphenyl ring systems in compound (I) are coplanar. The biphenyl ring system in compound (II), however, has a dihedral angle of 28.76 (11)°. In (I), the two independent mol­ecules differ in the orientation of the pyrrolidine ring (the nitro­gen lone pair points towards the biphenyl rings in one mol­ecule, but away from the rings in the other). The torsion angles about the ethynyl groups between the planes of the phenyl rings and the pyrrolidine ring N atoms are 84.15 (10) and −152.89 (10)°. In compound (II), the corresponding torsion angles are 122.0 (3) and 167.0 (3)°, with the nitro­gen lone pairs at both ends of the mol­ecule directed away from the central biphenyl rings. PMID:26594393

Reactivity of cyclopentadienyl molybdenum compounds towards formic acid: Structural characterization of CpMo(PMe 3)(CO) 2H, CpMo(PMe 3) 2(CO)H, [CpMo(μ-O)(μ-O 2CH)] 2, and [Cp*Mo(μ-O)(μ-O 2CH)] 2

DOE PAGES

Neary, Michelle C.; Parkin, Gerard

2017-01-19

Here, the molecular structures of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3)(CO) 2H and CpMo(PMe 3) 2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe 3) 3–x(CO) xH (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts formore » the release of H 2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [Cp RMo(μ-O)(μ-O 2CH)] 2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2CH)] 2 and [Cp*Mo(μ-O)(μ-O 2CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ 2δ *2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.« less

Reactivity of Cyclopentadienyl Molybdenum Compounds towards Formic Acid: Structural Characterization of CpMo(PMe3)(CO)2H, CpMo(PMe3)2(CO)H, [CpMo(μ-O)(μ-O2CH)]2, and [Cp*Mo(μ-O)(μ-O2CH)]2.

PubMed

Neary, Michelle C; Parkin, Gerard

2017-02-06

The molecular structures of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe 3 )(CO) 2 H and CpMo(PMe 3 ) 2 (CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H-Mo-CO moiety are displaced towards the hydride ligand. While Cp R Mo(PMe 3 ) 3-x (CO) x H (Cp R = Cp, Cp*; x = 1, 2, 3) are catalysts for the release of H 2 from formic acid, the carbonyl derivatives, Cp R Mo(CO) 3 H, are also observed to form dinuclear formate compounds, namely, [Cp R Mo(μ-O)(μ-O 2 CH)] 2 . The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O 2 CH)] 2 and [Cp*Mo(μ-O)(μ-O 2 CH)] 2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O 2 CH)] 2 correspond to metal-based δ* (HOMO) and σ (HOMO-1) orbitals. The σ 2 δ* 2 configuration thus corresponds to a formal direct Mo-Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo-Mo bond, whereas a Mo═Mo double bond is required in the absence of lone-pair donation.

Photophysics of Deoxycytidine and 5-Methyldeoxycytidine in Solution: A Comprehensive Picture by Quantum Mechanical Calculations and Femtosecond Fluorescence Spectroscopy.

PubMed

Martínez-Fernández, L; Pepino, A J; Segarra-Martí, J; Jovaišaitė, J; Vaya, I; Nenov, A; Markovitsi, D; Gustavsson, T; Banyasz, A; Garavelli, M; Improta, R

2017-06-14

The study concerns the relaxation of electronic excited states of the DNA nucleoside deoxycytidine (dCyd) and its methylated analogue 5-methyldeoxycytidine (5mdCyd), known to be involved in the formation of UV-induced lesions of the genetic code. Due to the existence of four closely lying and potentially coupled excited states, the deactivation pathways in these systems are particularly complex and have not been assessed so far. Here, we provide a complete mechanistic picture of the excited state relaxation of dCyd/5mdCyd in three solvents-water, acetonitrile, and tetrahydrofuran-by combining femtosecond fluorescence experiments, addressing the effect of solvent proticity on the relaxation dynamics of dCyd and 5mdCyd for the first time, and two complementary quantum mechanical approaches (CASPT2/MM and PCM/TD-CAM-B3LYP). The lowest energy ππ* state is responsible for the sub-picosecond lifetime observed for dCyd in all the solvents. In addition, computed excited state absorption and transient IR spectra allow one, for the first time, to assign the tens of picoseconds time constant, reported previously, to a dark state (n O π*) involving the carbonyl lone pair. A second low-lying dark state, involving the nitrogen lone pair (n N π*), does significantly participate in the excited state dynamics. The 267 nm excitation of dCyd leads to a non-negligible population of the second bright ππ* state, which affects the dynamics, acting mainly as a "doorway" state for the n O π* state. The solvent plays a key role governing the interplay between the different excited states; unexpectedly, water favors population of the dark states. In the case of 5mdCyd, an energy barrier present on the main nonradiative decay route explains the 6-fold lengthening of the excited state lifetime compared to that of dCyd, observed for all the examined solvents. Moreover, C5-methylation destabilizes both n O π* and n N π* dark states, thus preventing them from being populated.

Photo-Darkening Kinetics and Structural Anisotropic Modifications in the Chalcogenide Glass Arsenic Trisulfide: a Study of Kinetic X-Ray Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

Lee, Jay Min

1990-08-01

The purpose of the study is to investigate the mechanisms involved with photo-induced atomic structural modifications in the chalcogenide glass As_2 S_3. This glass exhibits the reversible effects of photo-darkening followed by thermal bleaching. We observed the time behavior of photo-induced properties under the influence of linearly polarized band -gap light. In a macroscopic optical investigation, we monitor optical changes in the photo-darkening process, and in a local structural probe we study kinetic (or time -resolved dispersive) x-ray absorption spectroscopy. Our observations center on kinetic phenomena and structural modifications induced by polarized excitation of lone-pair orbitals in the chalcogenide glass. Experimental results include the following observations: (i) The polarity of the optically induced anisotropy is critically dependent on the intensity and the polarization of the band-gap irradiation beam. (ii) The near edge peak height in x-ray absorption spectra shows subtle but sensitive change during the photo-darkening process. (iii) Photon intensity dependent dichroic kinetics reflect a connection between the optically probed macroscopic property and the x-ray probed local anisotropic structure. Analysis of the x-ray absorption results includes a computer simulation of the polarized absorption spectra. These results suggest that specific structural units tend to orient themselves with respect to the photon polarization. A substantial part of the analysis involves a major effort in dealing with the x-ray kinetic data manipulation and the experimental difficulties caused by a synchrotron instability problem. Based on our observations, we propose a possible mechanism for the observed photo-structural modifications. Through a model of computer relaxed photo-darkening kinetics, we support the notion that a twisting of a specific intermediate range order structure is responsible for local directional variations and global network distortions. In the course of this study, we refine knowledge of intermediate range order structural configurations and the bistabilities related to these configurations. The importance of the lone-pair orbital interactions in the chalcogenide glassy network is underscored.

Writing Creatively in a Museum: Tracing Lines through Persons, Art Objects and Texts

ERIC Educational Resources Information Center

Sabeti, Shari

2016-01-01

Creative writing is often thought of as an individual and solitary pursuit. This is partly owing to Romantic (and still popular) notions of "creativity" as residing in highly gifted individuals, but also to the widely held belief that "writing" is a lonely rather than a social activity. The research presented in this paper…

Logging truck noise near nesting northern goshawks

Treesearch

Teryl G. Grubb; Larry L. Pater; David K. Delaney

1998-01-01

We measured noise levels of four logging trucks as the trucks passed within approximately 500 m of two active northern goshawk (Accipiter gentilis) nests on the Kaibab Plateau in northern Arizona in 1997. Neither a brooding adult female nor a lone juvenile exhibited any discernable behavioral response to logging truck noise, which peaked at 53.4 and...

Insights into the Electronic Structure of Ozone and Sulfur Dioxide from Generalized Valence Bond Theory: Bonding in O3 and SO2.

PubMed

Takeshita, Tyler Y; Lindquist, Beth A; Dunning, Thom H

2015-07-16

There are many well-known differences in the physical and chemical properties of ozone (O3) and sulfur dioxide (SO2). O3 has longer and weaker bonds than O2, whereas SO2 has shorter and stronger bonds than SO. The O-O2 bond is dramatically weaker than the O-SO bond, and the singlet-triplet gap in SO2 is more than double that in O3. In addition, O3 is a very reactive species, while SO2 is far less so. These disparities have been attributed to variations in the amount of diradical character in the two molecules. In this work, we use generalized valence bond (GVB) theory to characterize the electronic structure of ozone and sulfur dioxide, showing O3 does indeed possess significant diradical character, whereas SO2 is effectively a closed shell molecule. The GVB results provide critical insights into the genesis of the observed difference in these two isoelectronic species. SO2 possesses a recoupled pair bond dyad in the a"(π) system, resulting in SO double bonds. The π system of O3, on the other hand, has a lone pair on the central oxygen atom plus a pair of electrons in orbitals on the terminal oxygen atoms that give rise to a relatively weak π interaction.

Lone-actor Terrorism and Impulsivity.

PubMed

Meloy, J Reid; Pollard, Jeffrey W

2017-11-01

In some recent cases of lone-actor terrorism, there is evidence the subject acted impulsively, often in response to a triggering event which contained a loss and humiliation. Evidence suggests the subjects acted precipitously, despite planning and preparation carried out in the preceding weeks or months, and their attacks failed to include the often considerable preparation that had been done. The pathway became a runway. The authors recommend the traditional assessment of impulsivity in persons of concern for lone acts of terrorism, as well as other proximal warning behaviors for targeted violence. Both indirect and direct assessment guidelines are proposed, with an emphasis upon self-report, psychological testing, collateral data gathering, and historical records. © 2017 American Academy of Forensic Sciences.

Comparisons of MN2S2vs. bipyridine as redox-active ligands to manganese and rhenium in (L-L)M'(CO)3Cl complexes.

PubMed

Lunsford, Allen M; Goldstein, Kristina F; Cohan, Matthew A; Denny, Jason A; Bhuvanesh, Nattamai; Ding, Shengda; Hall, Michael B; Darensbourg, Marcetta Y

2017-04-19

The bipyridine ligand is renowned as a photo- and redox-active ligand in catalysis; the latter has been particularly explored in the complex Re(bipy)(CO) 3 Cl for CO 2 reduction. We ask whether a bidentate, redox-active MN 2 S 2 metallodithiolate ligand in heterobimetallic complexes of Mn and Re might similarly serve as a receptor and conduit of electrons. In order to assess the electrochemical features of such designed bimetallics, a series of complexes featuring redox active MN 2 S 2 metallodithiolates, with M = Ni 2+ , {Fe(NO)} 2+ , and {Co(NO)} 2+ , bound to M'(CO) 3 X, where M' = Mn and Re, were synthesized and characterized using IR and EPR spectroscopies, X-ray diffraction, cyclic voltammetry, and density functional theory (DFT) computations. Butterfly type structures resulted from binding of the convergent lone pairs of the cis-sulfur atoms to the M'(CO) 3 X unit. Bond distances and angles are similar across the M' metal series regardless of the ligand attached. Electrochemical characterizations of [MN 2 S 2 ·Re(CO) 3 Cl] showed the redox potential of the Re is significantly altered by the identity of the metal in the N 2 S 2 pocket. DFT calculations proved useful to identify the roles played by the MN 2 S 2 ligands, upon reduction of the bimetallics, in altering the lability of the Re-Cl bond and the ensuing effect on the reduction of Re I to Re 0 .

Loneliness, Coping Strategies and Cognitive Styles of the Gifted Rural Adolescent.

ERIC Educational Resources Information Center

Woodward, John C.; Kalyan-Masih, Violet

1990-01-01

Investigated loneliness, coping, and cognitive styles of 52 gifted rural adolescents. Found that field independent (FI) adolescents were more lonely in a crowd, whereas field dependent (FD) adolescents were more lonely when not with others. FI adolescents showed more autonomy and self-reliance, while FD adolescents relied more on external sources…

Exploring the "Lone Wolf" Phenomenon in Student Teams

ERIC Educational Resources Information Center

Barr, Terri Feldman; Dixon, Andrea L.; Gassenheimer, Jule B.

2005-01-01

The proliferation of projects using student teams has motivated researchers to examine factors that affect both team process and outcomes. This research introduces an individual difference variable found in the business environment that has not been examined in a classroom context. The lone wolf appears to play a role in how teams function and…

United States Air Force 611th Air Support Group/Civil Engineering Squadron, Elmendorf AFB, Alaska. Risk assessment Point Lonely Radar Installation, Alaska. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karmi, S.

1996-04-01

This document contains the baseline human health risk assessment and the ecological risk assessment (ERA) for the Point Lonely Distant Early Warning (DEW) Line radar installation. Twelve sites at the Point Lonely radar installation underwent remedial investigations (RIs) during the summer of 1993. The Vehicle Storage Area (SS14) was combined with the Inactive Landfill because the two sites were essentially co-located and were sampled during the RI as a single unit. Therefore, 11 sites are discussed in this risk assessment. The presence of chemical contamination in the soil, sediments, and surface water at the installation was evaluated and reported inmore » the Point Lonely Remedial Investigation/Feasibility Study (RI/FS). The analytical data reported in the RI/FS form the basis for the human health and ecological risk assessments. The primary chemicals of concern (COCs) at the 11 sites are diesel and gasoline from past spills and/or leaks, chlorinated solvents, and manganese. The 11 sites investigated and the types of samples collected at each site are presented.« less

[Why are students lonely? Factors influencing loneliness in the school context].

PubMed

Klicpera, Barbara Gasteiger; Klicpera, Christian

2003-01-01

A significant amount of children and adolescents consider themselves as lonely because their essential social needs are not sufficiently met. The present study analyzes the contributions of group acceptance reflected by the social status, of social behaviors, reciprocal friendships, and family climate to the frequency and intensity of loneliness. About 1200 students of 6th and 8th grade of secondary school in Vienna were asked about their social experiences in school. Peers filled up questionnaires about the behavior of these students. A major part of the 11- and 13-year-old students had negative social experiences in school and about 15% were suffering from these experiences and considered themselves as lonely. Lack of acceptance in the group contributed to this self appraisal as well as a lack of friends and (according to the students) little support by the family. Social behavior of lonely students was remarkable for frequent victimizations and a low level of prosocial behavior. The impact of poor group acceptance on the feeling of loneliness was transmitted by these two features of social behavior.

Psychosocial group rehabilitation for lonely older people: favourable processes and mediating factors of the intervention leading to alleviated loneliness.

PubMed

Savikko, Niina; Routasalo, Pirkko; Tilvis, Reijo; Pitkälä, Kaisu

2010-03-01

Loneliness among community-dwelling older people is a common problem, with serious health consequences. The favourable processes and mediating factors of a psychosocial group rehabilitation intervention in alleviating older people's loneliness were evaluated. Altogether, 117 lonely, home-dwelling individuals (aged ≥75 years) participated in a psychosocial group rehabilitation intervention. The content comprised (i) art and inspiring activities, (ii) group exercise and discussions or (iii) therapeutic writing and group therapy. The psychosocial group rehabilitation intervention was evaluated from the group leaders' diaries and by observing the groups. Experiences of loneliness and social participation were collected by postintervention questionnaires from the participants. Data were analysed using methodological triangulation. Doing things together and sharing experiences with their peers inspired lively discussions, created a feeling of togetherness and led to participants' empowerment and increased self-esteem. The intervention socially activated the participants, and their feelings of loneliness had been alleviated during the intervention. Several common favourable processes and mediating factors were identified in the psychosocial group rehabilitation intervention that led to alleviation of loneliness among older people. Relevance to clinical practice.  The psychosocial group rehabilitation intervention gives nurses an effective tool to support older people's psychosocial resources by activating them and alleviating their loneliness. © 2009 Blackwell Publishing Ltd.

Latent Fairness in Adults’ Relationship-Based Moral Judgments

PubMed Central

Hao, Jian; Liu, Yanchun; Li, Jiafeng

2015-01-01

Can adults make fair moral judgments when individuals with whom they have different relationships are involved? The present study explored the fairness of adults’ relationship-based moral judgments in two respects by performing three experiments involving 999 participants. In Experiment 1, 65 adults were asked to decide whether to harm a specific person to save five strangers in the footbridge and trolley dilemmas in a within-subject design. The lone potential victim was a relative, a best friend, a person they disliked, a criminal or a stranger. Adults’ genetic relatedness to, familiarity with and affective relatedness to the lone potential victims varied. The results indicated that adults made different moral judgments involving the lone potential victims with whom they had different relationships. In Experiment 2, 306 adults responded to the footbridge and trolley dilemmas involving five types of lone potential victims in a within-subject design, and the extent to which they were familiar with and affectively related to the lone potential victim was measured. The results generally replicated those of Experiment 1. In addition, for close individuals, adults’ moral judgments were less deontological relative to their familiarity with or positive affect toward these individuals. For individuals they were not close to, adults made deontological choices to a larger extent relative to their unfamiliarity with or negative affect toward these individuals. Moreover, for familiar individuals, the extent to which adults made deontological moral judgments more closely approximated the extent to which they were familiar with the individual. The adults’ deontological moral judgments involving unfamiliar individuals more closely approximated their affective relatedness to the individuals. In Experiment 3, 628 adults were asked to make moral judgments with the type of lone potential victim as the between-subject variable. The results generally replicated those of the previous two experiments. Therefore, the present study shows that, in addition to apparent unfairness, latent fairness exists in adults’ relationship-based moral judgments. Moral judgments involving individuals with whom adults have different relationships have different cognitive and affective bases. PMID:26696935

Social provision and loneliness among older people suffering from chronic physical illness. A mixed-methods approach.

PubMed

Kvaal, Kari; Halding, Anne-Grethe; Kvigne, Kari

2014-03-01

To describe and compare the perceived social provision for a group reporting never feeling lonely with that of a group reporting feeling lonely and to explore the meaning of loneliness. Participants (N = 101) were recruited from geriatric wards. Inclusion criteria were as follows: aged 65 years or more, the absence of dementia, one or more chronic physical disorders and plans to be discharged from the hospital to their home. The mean age was 81.3 years (range: 65-96 years), 68% were women, and 66% lived alone. Assessments of social provisions and loneliness were collected by a subjective report using the Social Provision Scale (SPS), and the Montgomery-Aasberg Depression Rating Scale (MADRS) was used to assess depression. The participants were also asked whether they felt lonely and were then asked to describe the meaning of loneliness if they had indicated feeling lonely. Narratives were then condensed by the participants into short sentences. Seventy-five per cent of the participants reported feeling lonely, of these 54% were living alone, and 18% identified with depression. Three subscales of SPS scores were significantly lower in the lonely group: attachment (p < 0.001), a sense of reliable alliance (p = 0.001) and the obtaining of guidance (p = 0.01). The overall view of the experience of loneliness was dominated by emptiness and negative emotions. The following themes were identified: Emotions were dominated by sadness, anxiety and restlessness, anger and guilt. Relationships were dominated by being left alone, being confined and feeling useless. Existential dimensions were characterised by emptiness, endless boredom, isolation and the potential for change. The study shows that loneliness is prevalent among older people suffering from chronic physical illness and confirms the complexity of the concept. A mixed-methods design contributed to nuanced and detailed information about the meaning of loneliness. © 2013 Nordic College of Caring Science. Published by Blackwell Publishing Ltd.

Risk, Resiliency, and Coping in National Guard Families

DTIC Science & Technology

2014-10-01

situation? (e.g. help you to feel loved , less lonely, etc.) o Probe: Did you find that people were supportive of your situation? (Other parents...activity (i.e. participating more or less than usual)  Major change in social activities (i.e. clubs, movies , events, etc.)  Major change in...sleeping or eating habits  Violations of the law (i.e. traffic tickets, disturbing the peace, DUI, etc.)  Major change in usual type and/or amount

A comparative DFT study of interactions of Au and small gold clusters Aun (n = 2-4) with CH3S and CH2 radicals

NASA Astrophysics Data System (ADS)

Blaško, Martin; Rajský, Tomáš; Urban, Miroslav

2017-03-01

We compare DFT binding energies (BEs) of Au and small gold clusters interacting with CH3S and CH2 ligands (Aun-L complexes, n = 1-4). The spin state and the binding mechanism in Aun-L varies with the participation of singly occupied non-bonding orbitals or doubly occupied lone-pair orbitals of a ligand and on the number of atoms (even or odd) of Aun. The highest BE, 354 kJ/mol, exhibits the Au3-CH2 complex with the covalent bond in which participate two singly occupied orbitals of the triplet state of CH2. With CH3S the highest BE (277 kJ/mol) is calculated for Au3-SCH3 with the single Au-S bond.

Attaching Be or Mg to BH3 results in the formation of BeBH3 and MgBH3 molecules capable of forming stable anions

NASA Astrophysics Data System (ADS)

Anusiewicz, Iwona; Skurski, Piotr

2018-04-01

Stability of BeBH3 and MgBH3 molecules and their (BeBH3)- and (MgBH3)- anions is investigated on the basis of correlated ab initio calculations. The electronic and thermodynamic stability of all species is confirmed by estimating the excess electron binding energies of the anions and by evaluating the Gibbs free energies for various fragmentation paths. The bonding effects in BeBH3 and MgBH3 have been identified as the result of alkaline earth metal ns2 lone-pair donation to the empty 2p boron orbital. Adiabatic and vertical electronic stabilities of the (BeBH3)- and (MgBH3)- anions were found to span 1.114-1.301 and 0.675-0.744 eV range, respectively.

Photochemistry of transition-metal phthalocyanines. Mechanistic aspects of the photochemistry of the acido(phthalocyanine)rhodium(III) complexes investigated by continuous, flash, and laser flash photolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muralidharan, S.; Ferraudi, G.; Schmatz, K.

1982-08-01

Rh(ph)(CH/sub 3/OH)X, X = Cl, Br, or I, has been prepared and characterized. Continuous-wave irradiations of these phthalocyanines in the ultraviolet region of the spectrum, in acetonitrile and acetonitrile-isopropyl alcohol mixtures, result in the redox-induced substitution of the axially coordinated halide ions by the solvent. Even though the overall reaction was photosubstitution, the intermediates observed by conventional and laser flash photolysis were found to be rhodium(II) phthalocyanine and rhodium(III) phthalocyanine ligand radicals. The photoredox processes were attributed to the population of (n..pi..*) ligand-centered excited states that involve the lone electron pair from the bridge nitrogens of the phthalocyanine ligand. 9more » figures, 3 tables.« less

Amide Neighbouring-Group Effects in Peptides: Phenylalanine as Relay Amino Acid in Long-Distance Electron Transfer.

PubMed

Nathanael, Joses G; Gamon, Luke F; Cordes, Meike; Rablen, Paul R; Bally, Thomas; Fromm, Katharina M; Giese, Bernd; Wille, Uta

2018-05-04

In nature, proteins serve as media for long-distance electron transfer (ET) to carry out redox reactions in distant compartments. This ET occurs either by a single-step superexchange or through a multi-step charge hopping process, which uses side chains of amino acids as stepping stones. In this study we demonstrate that Phe can act as a relay amino acid for long-distance electron hole transfer through peptides. The considerably increased susceptibility of the aromatic ring to oxidation is caused by the lone pairs of neighbouring amide carbonyl groups, which stabilise the Phe radical cation. This neighbouring-amide-group effect helps improve understanding of the mechanism of extracellular electron transfer through conductive protein filaments (pili) of anaerobic bacteria during mineral respiration. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies of Water V. Five Phonons in Protonic Semiconductor Lattice Model of Pure Liquid Water

NASA Astrophysics Data System (ADS)

Jie, Binbin; Sah, Chihtang

2017-07-01

We report physics based confirmation (~1% RMS deviation), by existing experimental data, of proton-prohol (proton-hole) ion product (pH) and mobilities in pure liquid water (0-100{}{{o}}C, 1-atm pressure) anticipated from our melted-ice Hexagonal-Close-Packed (H{}2O){}4 Lattice Model. Five phonons are identified. (1) A propagating protonic phonon (520.9 meV from lone-pair-blue-shifted stretching mode of isolated water molecule) absorbed to generate a proton-prohol pair or detrap a tightly-bound proton. (2) Two (173.4 and 196.6 meV) bending-breathing protonic-proholic or protonic phonons absorbed during de-trapping-limited proton or proton-prohol mobilities. (3) Two propagating oxygenic-wateric Debye-Dispersive phonons (30.3 and 27.5 meV) absorbed during scattering-limited proton or proton-prohol mobilities. Summer School in Theoretical Physics funded by the National Natural Science Foundation of China, on Soft Materials Physics, hosted by the Physics Department of Xiamen University, China, during August 1 to 14, 2016. This was also just presented at the 2017 March Meeting (March 14 to 16) of the American Physical Society in New Orleans, USA.

Experimental and theoretical studies of 3-benzyloxy-2-nitropyridine

NASA Astrophysics Data System (ADS)

Sun, Wenting; Cui, Yu; Liu, Huimin; Zhao, Haitao; Zhang, Wenqin

2012-10-01

The structure of 3-benzyloxy-2-nitropyridine has been investigated both experimentally and theoretically. The X-ray crystallography results show that the nitro group is tilted out of the pyridine ring plane by 66.4(4)°, which is mainly attributed to the electron-electron repulsions of the lone pairs in O atom of the 3-benzyloxy moiety with O atom in nitro group. An interesting centrosymmetric π-stacking molecular pair has been found in the crystalline state, which results in the approximate coplanarity of the pyridine ring with the benzene ring. The calculated results show that the dihedral angle between the nitro group and pyridine ring from the X3LYP method is much closer to the experimental data than that from the M06-2X one. The existing two conformational isomers of 3-benzyloxy-2-nitropyridine with equal energy explain well the disorder of the nitro group at room temperature. In addition, the vibrational frequencies are also calculated by the X3LYP and M06-2X methods and compared with the experimental results. The prediction from the X3LYP method coincides with the locations of the experimental frequencies well.

Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments.

PubMed

Zhu, Tianyu; de Silva, Piotr; Van Voorhis, Troy

2018-01-09

Chemical bonding plays a central role in the description and understanding of chemistry. Many methods have been proposed to extract information about bonding from quantum chemical calculations, the majority of them resorting to molecular orbitals as basic descriptors. Here, we present a method called self-attractive Hartree (SAH) decomposition to unravel pairs of electrons directly from the electron density, which unlike molecular orbitals is a well-defined observable that can be accessed experimentally. The key idea is to partition the density into a sum of one-electron fragments that simultaneously maximize the self-repulsion and maintain regular shapes. This leads to a set of rather unusual equations in which every electron experiences self-attractive Hartree potential in addition to an external potential common for all the electrons. The resulting symmetry breaking and localization are surprisingly consistent with chemical intuition. SAH decomposition is also shown to be effective in visualization of single/multiple bonds, lone pairs, and unusual bonds due to the smooth nature of fragment densities. Furthermore, we demonstrate that it can be used to identify specific chemical bonds in molecular complexes and provides a simple and accurate electrostatic model of hydrogen bonding.

Lone-Parent Families. The Economic Challenge. OECD Social Policy Studies No. 8.

ERIC Educational Resources Information Center

Duskin, Elizabeth, Ed.

This volume is based on papers presented at a conference of social policy experts that looked at the growth in lone-parent families, the problems that have emerged, and their policy implications. Chapter 1 is an "Overview" (Duskin). Three chapters look at demographic trends over time and over the life-cycle; they are: "Demographic…

Lonely Days and Lonely Nights: Completing the Doctoral Dissertation.

ERIC Educational Resources Information Center

Germeroth, Darla

A study examined areas of the doctoral dissertation process that are often problematic for the Ph.D./Ed.D. candidate in the field of communication. Subjects, 250 randomly selected Speech Communication Association members holding a Ph.D. or an Ed.D. were surveyed. Of the 250 surveys mailed, 137 were returned, representing a 54.8% return rate.…

Forget the Alamo: Thinking about History in John Sayles' "Lone Star"

ERIC Educational Resources Information Center

Adams, Anna

2007-01-01

John Sayles' film "Lone Star" is an excellent vehicle for teaching about the production and interpretation of history in a high school or introductory level college history class. The film illustrates that history is subjective, that the sorting and arrangement of evidence is what makes history, and that history is not necessarily an inevitable…

"On the Level". Formative Evaluation: Alone vs. Lonely. Research Report 74.

ERIC Educational Resources Information Center

Agency for Instructional Television, Bloomington, IN.

A formative evaluation was conducted of the instructional television program "Alone vs. Lonely," from "On the Level," a series of 12 lessons designed to aid secondary school students in dealing with personal and social growth. The program is designed to teach that loneliness is normal and is felt by everyone, and to suggest…

Repellency and toxicity of five ant defensive compounds against the lone star tick, Amblyomma americanum (Acari: Ixodidae)

USDA-ARS?s Scientific Manuscript database

+ The lone star tick, Amblyomma americanum, is a vector of several important human and animal diseases. This tick species has rapidly expanded in its geographic distribution, and its aggressive behavior has increased the risk of tick-borne diseases in these new areas. Repellents are recommended by t...

Predicting Success: How Predictive Analytics Are Transforming Student Support and Success Programs

ERIC Educational Resources Information Center

Boerner, Heather

2015-01-01

Every year, Lone Star College in Texas hosts a "Men of Honor" program to provide assistance and programming to male students, but particularly those who are Hispanic and black, in hopes their academic performance will improve. Lone Star might have kept directing its limited resources toward these students--and totally missed the subset…

The Integration of Lone English Nouns into Bilingual Sonoran Spanish

ERIC Educational Resources Information Center

Bessett, Ryan M.

2017-01-01

Using data from Arizona, United States, the present study seeks to further our understanding of lone other language items (LOLIs) in bilingual discourse and their status as either borrowings or codeswitches by measuring the degree of incorporation that can indicate a LOLI's status as a borrowing or codeswitching. To accomplish this aim, nouns from…

Evaluation of four commercial natural products for repellency and toxicity against the lone star tick, Amblyomma americanum (Acari: Ixodidae)

USDA-ARS?s Scientific Manuscript database

Lone star ticks are aggressive ectoparasites of domestic and wild animals, as well as humans. These ticks can transmit many pathogens that cause disease including Erhlichia and tularemia. Common compounds used for personal protection and area sprays are N-diethyl-3-methyl benzamide (DEET) and permet...

Expression of bovine genes associated with a local and systemic immune response to infestation by the Lone Star tick, Amblyomma americanum

USDA-ARS?s Scientific Manuscript database

The Lone Star tick, Amblyomma americanum, causes considerable production losses to the Southern U.S. cattle industry due to reduced weight, infertility, secondary infections at bite wounds, damaged hides, and potentially death, as these ticks tend to infest livestock in large numbers. Chemical resid...

Botanical compound p-anisaldehyde repels larval lone star tick, Amblyomma americanum (L.) (Acari: Ixodidae), and halts reproduction by gravid adults

USDA-ARS?s Scientific Manuscript database

The lone star tick, Amblyomma americanum (L.), widely distributed across eastern, southeastern, and midwestern regions of the United States and south into Mexico, is an obligate blood feeder that attaches to three hosts during the larval, nymphal, and adult stages. White-tailed deer and wild turkey ...

Repellency of the Origanum onites L. Essential Oil and Constituents to the Lone Star Tick and Yellow Fever Mosquito

USDA-ARS?s Scientific Manuscript database

The oregano, Origanum onites L., essential oil (EO) was tested in laboratory behavioral bioassays for repellent activity against Amblyomma americanum (L.) and Aedes aegypti (L.). The O. onites EO was characterized using GC-FID and GC-MS. Carvacrol (75.70 %), linalool (9.0 %), p-cymene (4.33 %) and t...

The First Row Anomaly and Recoupled Pair Bonding in the Halides of the Late p-Block Elements

PubMed Central

2012-01-01

The dramatic differences between the properties of molecules formed from the late p-block elements of the first row of the periodic table (N–F) and those of the corresponding elements in subsequent rows is well recognized as the first row anomaly. Certain properties of the atoms, such as the relative energies and spatial extents of the ns and np orbitals, can explain some of these differences, but not others. In this Account, we summarize the results of our recent computational studies of the halides of the late p-block elements. Our studies point to a single underlying cause for many of these differences: the ability of the late p-block elements in the second and subsequent rows of the periodic table to form recoupled pair bonds and recoupled pair bond dyads with very electronegative ligands. Recoupled pair bonds form when an electron in a singly occupied ligand orbital recouples the pair of electrons in a doubly occupied lone pair orbital on the central atom, leading to a central atom-ligand bond. Recoupled pair bond dyads occur when a second ligand forms a bond with the orbital left over from the initial recoupled pair bond. Recoupled pair bonds and recoupled pair bond dyads enable the late p-block elements to form remarkably stable hypervalent compounds such as PF5 and SF6 and lead to unexpected excited states in smaller halides of the late p-block elements such as SF and SF2. Recoupled pair bonding also causes the Fn–1X–F bond energies to oscillate dramatically once the normal valences of the central atoms have been satisfied. In addition, recoupled pair bonding provides a lower-energy pathway for inversion in heavily fluorinated compounds (PF3 and PF2H, but not PH2F and PH3) and leads to unusual intermediates and products in reactions involving halogens and late p-block element compounds, such as (CH3)2S + F2. Although this Account focuses on the halides of the second row, late p-block elements, recoupled pair bonds and recoupled pair bond dyads are important in the chemistry of p-block elements beyond the second row (As, Se, and Br) and for compounds of these elements with other very electronegative ligands, such as OH and O. Knowledge of recoupled pair bonding is thus critical to understanding the properties and reactivity of molecules containing the late p-block elements beyond the first row. PMID:23151313

The first row anomaly and recoupled pair bonding in the halides of the late p-block elements.

PubMed

Dunning, Thom H; Woon, David E; Leiding, Jeff; Chen, Lina

2013-02-19

The dramatic differences between the properties of molecules formed from the late p-block elements of the first row of the periodic table (N-F) and those of the corresponding elements in subsequent rows is well recognized as the first row anomaly. Certain properties of the atoms, such as the relative energies and spatial extents of the ns and np orbitals, can explain some of these differences, but not others. In this Account, we summarize the results of our recent computational studies of the halides of the late p-block elements. Our studies point to a single underlying cause for many of these differences: the ability of the late p-block elements in the second and subsequent rows of the periodic table to form recoupled pair bonds and recoupled pair bond dyads with very electronegative ligands. Recoupled pair bonds form when an electron in a singly occupied ligand orbital recouples the pair of electrons in a doubly occupied lone pair orbital on the central atom, leading to a central atom-ligand bond. Recoupled pair bond dyads occur when a second ligand forms a bond with the orbital left over from the initial recoupled pair bond. Recoupled pair bonds and recoupled pair bond dyads enable the late p-block elements to form remarkably stable hypervalent compounds such as PF(5) and SF(6) and lead to unexpected excited states in smaller halides of the late p-block elements such as SF and SF(2). Recoupled pair bonding also causes the F(n-1)X-F bond energies to oscillate dramatically once the normal valences of the central atoms have been satisfied. In addition, recoupled pair bonding provides a lower-energy pathway for inversion in heavily fluorinated compounds (PF(3) and PF(2)H, but not PH(2)F and PH(3)) and leads to unusual intermediates and products in reactions involving halogens and late p-block element compounds, such as (CH(3))(2)S + F(2). Although this Account focuses on the halides of the second row, late p-block elements, recoupled pair bonds and recoupled pair bond dyads are important in the chemistry of p-block elements beyond the second row (As, Se, and Br) and for compounds of these elements with other very electronegative ligands, such as OH and O. Knowledge of recoupled pair bonding is thus critical to understanding the properties and reactivity of molecules containing the late p-block elements beyond the first row.

Welfare-to-work interventions and their effects on the mental and physical health of lone parents and their children

PubMed Central

Gibson, Marcia; Thomson, Hilary; Banas, Kasia; Lutje, Vittoria; McKee, Martin J; Martin, Susan P; Fenton, Candida; Bambra, Clare; Bond, Lyndal

2018-01-01

Background Lone parents in high-income countries have high rates of poverty (including in-work poverty) and poor health. Employment requirements for these parents are increasingly common. 'Welfare-to-work' (WtW) interventions involving financial sanctions and incentives, training, childcare subsidies and lifetime limits on benefit receipt have been used to support or mandate employment among lone parents. These and other interventions that affect employment and income may also affect people's health, and it is important to understand the available evidence on these effects in lone parents. Objectives To assess the effects of WtW interventions on mental and physical health in lone parents and their children living in high-income countries. The secondary objective is to assess the effects of welfare-to-work interventions on employment and income. Search methods We searched the Cochrane Central Register of Controlled Trials (CENTRAL), MEDLINE Ovid, Embase Ovid, PsycINFO EBSCO, ERIC EBSCO, SocINDEX EBSCO, CINAHL EBSCO, Econlit EBSCO, Web of Science ISI, Applied Social Sciences Index and Abstracts (ASSIA) via Proquest, International Bibliography of the Social Sciences (IBSS) via ProQuest, Social Services Abstracts via Proquest, Sociological Abstracts via Proquest, Campbell Library, NHS Economic Evaluation Database (NHS EED) (CRD York), Turning Research into Practice (TRIP), OpenGrey and Planex. We also searched bibliographies of included publications and relevant reviews, in addition to many relevant websites. We identified many included publications by handsearching. We performed the searches in 2011, 2013 and April 2016. Selection criteria Randomised controlled trials (RCTs) of mandatory or voluntary WtW interventions for lone parents in high-income countries, reporting impacts on parental mental health, parental physical health, child mental health or child physical health. Data collection and analysis One review author extracted data using a standardised extraction form, and another checked them. Two authors independently assessed risk of bias and the quality of the evidence. We contacted study authors to obtain measures of variance and conducted meta-analyses where possible. We synthesised data at three time points: 18 to 24 months (T1), 25 to 48 months (T2) and 49 to 72 months (T3). Main results Twelve studies involving 27,482 participants met the inclusion criteria. Interventions were either mandatory or voluntary and included up to 10 discrete components in varying combinations. All but one study took place in North America. Although we searched for parental health outcomes, the vast majority of the sample in all included studies were female. Therefore, we describe adult health outcomes as 'maternal' throughout the results section. We downgraded the quality of all evidence at least one level because outcome assessors were not blinded. Follow-up ranged from 18 months to six years. The effects of welfare-to-work interventions on health were generally positive but of a magnitude unlikely to have any tangible effects. At T1 there was moderate-quality evidence of a very small negative impact on maternal mental health (standardised mean difference (SMD) 0.07, 95% Confidence Interval (CI) 0.00 to 0.14; N = 3352; studies = 2)); at T2, moderate-quality evidence of no effect (SMD 0.00, 95% CI 0.05 to 0.05; N = 7091; studies = 3); and at T3, low-quality evidence of a very small positive effect (SMD −0.07, 95% CI −0.15 to 0.00; N = 8873; studies = 4). There was evidence of very small positive effects on maternal physical health at T1 (risk ratio (RR) 0.85, 95% CI 0.54 to 1.36; N = 311; 1 study, low quality) and T2 (RR 1.06, 95% CI 0.95 to 1.18; N = 2551; 2 studies, moderate quality), and of a very small negative effect at T3 (RR 0.97, 95% CI 0.91 to 1.04; N = 1854; 1 study, low quality). At T1, there was moderate-quality evidence of a very small negative impact on child mental health (SMD 0.01, 95% CI −0.06 to 0.09; N = 2762; studies = 1); at T2, of a very small positive effect (SMD −0.04, 95% CI −0.08 to 0.01; N = 7560; studies = 5), and at T3, there was low-quality evidence of a very small positive effect (SMD −0.05, 95% CI −0.16 to 0.05; N = 3643; studies = 3). Moderate-quality evidence for effects on child physical health showed a very small negative effect at T1 (SMD −0.05, 95% CI −0.12 to 0.03; N = 2762; studies = 1), a very small positive effect at T2 (SMD 0.07, 95% CI 0.01 to 0.12; N = 7195; studies = 3), and a very small positive effect at T3 (SMD 0.01, 95% CI −0.04 to 0.06; N = 8083; studies = 5). There was some evidence of larger negative effects on health, but this was of low or very low quality. There were small positive effects on employment and income at 18 to 48 months (moderate-quality evidence), but these were largely absent at 49 to 72 months (very low to moderate-quality evidence), often due to control group members moving into work independently. Since the majority of the studies were conducted in North America before the year 2000, generalisabilty may be limited. However, all study sites were similar in that they were high-income countries with developed social welfare systems. Authors' conclusions The effects of WtW on health are largely of a magnitude that is unlikely to have tangible impacts. Since income and employment are hypothesised to mediate effects on health, it is possible that these negligible health impacts result from the small effects on economic outcomes. Even where employment and income were higher for the lone parents in WtW, poverty was still high for the majority of the lone parents in many of the studies. Perhaps because of this, depression also remained very high for lone parents whether they were in WtW or not. There is a lack of robust evidence on the health effects of WtW for lone parents outside North America. How do welfare-to-work interventions for lone parents affect adult and child health? Lone parents in wealthy countries have disproportionately high levels of poverty and ill health. Governments argue that both poverty and health might improve if lone parents started working or worked more, while some researchers think that working at the same time as raising children alone could be stressful and make health worse. Welfare-to-work interventions (WtW) are designed to either encourage or require lone parents to look for work. Earnings top-ups, stopping or reducing benefits, training, helping to pay for child care and limits on how long benefits are paid have all been used to try to increase lone parent employment. In order to understand how requiring lone parents to take part in WtW programmes affects their and their children's health, we systematically reviewed studies that collected information on these effects. We found 12 studies involving 27,482 participants that compared groups of lone parents in WtW interventions with lone parents who continued to receive welfare benefits in the normal way. All of the studies were at high risk of bias because the staff who collected the data knew when respondents were in the intervention group. In some studies, lone parents who were not in the intervention group were affected by similar changes to welfare policy that applied to all lone parents. We used statistical techniques to combine the results of different studies.These analyses suggest that WtW does not have important effects on health. Employment and income were slightly higher 18 to 48 months after the start of the intervention, but there was little difference 49 to 72 months after the studies began. In a number of studies, lone parents who were not in WtW interventions found jobs by themselves over time. It is possible that effects on health were small because there was not much change in employment or income. Even when employment and income were higher for the lone parents in WtW, most participants continued to be poor. Perhaps because of this, depression also remained very high for lone parents whether they were in WtW or not. All but one of the studies took place in the United States or Canada before the year 2000. This means it is difficult to be sure whether WtW would have the same effects in different countries at other times. PMID:29480555

Influence of family type and parenting behaviours on teenage sexual behaviour and conceptions.

PubMed

Bonell, C; Allen, E; Strange, V; Oakley, A; Copas, A; Johnson, A; Stephenson, J

2006-06-01

Longitudinal data were used to explore relations between teenage pregnancy, sexual behaviour, and family type. The study examined whether students from lone parent and/or teenage mother initiated families more commonly report sex, lack of contraception at first sex, and/or conceptions by age 15/16, and whether such associations can be explained by low parental strictness, difficult parent-child communication, and/or low parental input into sex education. Up to date longitudinal UK research on family influences on conceptions is lacking, as is longitudinal research on family influences on sexual behaviour. No previous studies have comprehensively examined effects of parenting behaviours. Unlike previous research, this study tested theories suggesting that parenting deficits among lone parent and teenage initiated families increase risk of teenage pregnancy among their children. Secondary analysis of data from a trial of sex education. Girls and boys from lone parent families or having mothers who were teenagers when they were born were more likely to report sex but not lack of contraception at first sex by age 15/16. Girls and boys with mothers having them as teenagers, and boys but not girls from lone parent families, were more likely to report being involved in conceptions by age 15/16. Only the association between teenage mother family and girls' conceptions was reduced by adjusting for a parenting behaviour measure. Students from lone parent families or having mothers who were teenagers when they were born are more likely to report early sexual debut and conceptions by age 15/16, but this is not generally explained by parenting style.

Loneliness in older adults is associated with diminished cortisol output.

PubMed

Schutter, N; Holwerda, T J; Stek, M L; Dekker, J J M; Rhebergen, D; Comijs, H C

2017-04-01

Loneliness in older adults has been associated with increased mortality and health problems. One of the assumed underlying mechanisms is dysregulation of the hypothalamic-pituitary-adrenocortical axis (HPA-axis). The purpose of this study was to investigate whether loneliness in older adults is associated with HPA-axis dysregulation and whether this association differs between depressed and non-depressed persons. Cross-sectional data of 426 lonely and non-lonely older adults in the Netherlands Study of Depression in Older Persons (NESDO) were used. Linear regression analyses and multinominal logistic regression analyses were performed to examine the association between loneliness and morning cortisol, cortisol awakening response, diurnal slope and dexamethasone suppression ratio. In all analyses, confounders were introduced. In order to examine whether the association between loneliness and cortisol measures is different in depressed versus non-depressed persons, an interaction term for loneliness x depression diagnosis was tested. Cortisol output in the first hour after awakening and dexamethasone suppression ratio was lower in lonely participants. There were no significant interactions between loneliness and depression diagnosis in the association with the cortisol measures. This study is the first to investigate the association between the HPA-axis and loneliness in a large group of older adults aged 60-93years. We found lower cortisol output in the first hour after awakening and lower dexamethasone suppression ratio in lonely older depressed and non-depressed adults. Whether diminished cortisol output is the underlying mechanism that leads to health problems in lonely older adults is an interesting object for further study. Copyright © 2017 Elsevier Inc. All rights reserved.

Actions Speak Louder than Words: A Behavioral Analysis of 183 Individuals Convicted for Terrorist Offenses in the United States from 1995 to 2012.

PubMed

Horgan, John; Shortland, Neil; Abbasciano, Suzzette; Walsh, Shaun

2016-09-01

Involvement in terrorism has traditionally been discussed in relatively simplistic ways with little effort spent on developing a deeper understanding of what involvement actually entails, and how it differs from person to person. In this paper, we present the results of a three-year project focused on 183 individuals associated with the global jihadist movement who were convicted in the United States, for terrorist offenses, between 1995 and 2012. These data were developed by a large-scale, open-source data collection activity that involved a coding dictionary of more than 120 variables. We identify and explore the diversity of behaviors that constitute involvement in terrorism. We also compare lone actors and those who acted as part of a group, finding that lone actors differed from group-based actors in key demographic attributes and were more likely to be involved in attack execution behaviors. Implications for counterterrorism are then discussed. © 2016 American Academy of Forensic Sciences.

An alkaline tin(II) halide compound Na{sub 3}Sn{sub 2}F{sub 6}Cl: Synthesis, structure, and characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, Pifu; University of the Chinese Academy of Sciences, Beijing 100049; Luo, Siyang

A new alkali tin(II) halide compound, Na{sub 3}Sn{sub 2}F{sub 6}Cl, is synthesized by hydrothermal method. This compound crystallizes trigonally in space group of R-3c (167), and processes a zero-dimensional (0D) structure consisted of Na{sup +} cations, Cl{sup −} anions and the isolated [SnF{sub 3}]{sup -} trigonal pyramids in which the stereochemically active 5s{sup 2} lone pair electrons are attached to the Sn{sup 2+} cations. Interestingly, the [SnF{sub 3}]{sup −} trigonal pyramids are parallel arranged in the a-b plane, while oppositely arranged in line with rotation along the c- axis. Moreover, the energy bandgap, thermal stability and electronic structure of Na{submore » 3}Sn{sub 2}F{sub 6}Cl are characterized and the results reveal that this compound has and indirect bandgap of 3.88 eV and is stable under 270 °C. - Graphical abstract: A zero-dimensional alkaline tin halide compound, Na{sub 3}Sn{sub 2}F{sub 6}Cl, is synthesized by hydrothermal method. Interestingly, both the anions and cations coordinating polyhedra exhibit order arranged with the [SnF{sub 3}]{sup -} trigonal pyramids rotating along the c- axis.« less

Theoretical characterization of gas-phase thermolysis products of ethane-1,2-diol, 2-chloroethanol and 2-fluoroethanol

NASA Astrophysics Data System (ADS)

Osman, Osman I.; Elroby, Shabaan A. K.; Hilal, Rifaat H.; Aziz, Saadullah G.

2013-03-01

The transition structures and the activation energies for the possible thermal elimination of H2O, HF and HCl from ethane-1,2-diol, 2-fluoroethanol and 2-chloroethanol respectively, were investigated. The relative stabilities and associated barrier heights of syn and anti vinyl alcohol isomers and their acetaldehyde tautomer were estimated. HF, DFT/B3LYP and MP2 methods at 3-21G, 6-31+G(d), 6-311++G(d,p) and aug-cc-pvdz basis sets were applied to identify the stationary points of the studied systems. The optimized geometries and electronic energies of reactants, transition states and products were analyzed. The dependence of these properties upon the theoretical level was discussed. A concerted proton release and a hydroxide or halide ion expulsion mechanism was proposed to account for the thermal rearrangement of reactants to products. A thorough understanding of syn vinyl alcohol preference is provided by performing natural bond orbital (NBO) analysis. The oxygen atom lone pair (LP) and periplanar hyperconjugative effects are responsible for this preference. It was suggested that the LP hyperconjugative interactions with the C=C σ and π antibonds were the most important origin of the structural differences between the two vinyl alcohol isomers.

Synthesis and crystal structure of the solid solution Co3(SeO3)3-x(PO3OH)x(H2O) involving crystallographic split positions of Se4+ and P5+.

PubMed

Zimmermann, Iwan; Johnsson, Mats

2013-10-21

Three new cobalt selenite hydroxo-phosphates laying in the solid solution Co3(SeO3)3-x(PO3OH)x(H2O), with x = 0.8, x = 1.0, and x = 1.2 are reported. Single crystals were obtained by hydrothermal synthesis and the crystal structure was determined by single crystal X-ray diffraction. The structure can be described as a 3D framework having selenite and hydroxo-phosphate groups protruding into channels in the crystal structure. Se(4+) and P(5+) share a split position in the structure so that either SeO3 groups having a stereochemically active lone pair or tetrahedrally coordinated PO3OH groups are present. The OH-group is thus only present when the split position is occupied by P(5+). The crystal water is coordinated to a cobalt atom and TG and IR measurements show that the water and hydroxyl groups leave the structure at unusually high temperatures (>450 °C). Magnetic susceptibility measurements show antiferromagnetic coupling below 16 K and a magnetic moment of 4.02(3) μB per Co atom was observed.

Your Wildest Dreams: "No End in Sight", "The Astronaut Farmer", and Other American Follies

ERIC Educational Resources Information Center

Beck, Bernard

2008-01-01

Two recent movies, "No End in Sight" and "The Astronaut Farmer", exemplify a common kind of American movie: An intrepid lone individual pursues an impossible and outlandish goal against great odds and the opposition of many people, including dear ones. Although there are great costs and early failures, the lone hero is successful, and all doubts…

"The Lone Ranger" Rides Again: Recurring Images of the Justice Hero in "The Equalizer."

ERIC Educational Resources Information Center

Getz, Glenn

A study compared the two television series, "The Lone Ranger" and "The Equalizer" to see whether the protagonists conform to the American archetype of the justice hero--defined as the hero who deals with crime in society. A formula analysis of the two television texts reveals that both heroes are male, scrupulous, independent,…

Effects of two commercial neem-based insecticides on lone star tick, Amblyomma americanum (L.) (Acari: Ixodidae): deterrence, mortality, and reproduction

USDA-ARS?s Scientific Manuscript database

The lone star tick, Amblyomma americanum (L.), is a widely distributed three-host obligate blood-feeding parasite in the United States and Mexico. It mostly attaches to white-tailed deer, Odocoilus virginianus (Zimmerman) and wild turkey, Meleagris gallopavo L., as well as a wide variety of other do...

College Today, Part III: College Closings. Options in Education Transcript: Program No. 121.

ERIC Educational Resources Information Center

George Washington Univ., Washington, DC. Inst. for Educational Leadership.

The closing of a college is the topic of the third in a series of four transcripts of radio programs on college today. The dialogue includes: a press conference at Lone Mountain College, with a discussion of financial problems by the president and comments by Lone Mountain's student body president, college vice president, art department chairman,…

Learning from “Knocks in Life”: Food Insecurity among Low-Income Lone Senior Women

PubMed Central

Green-LaPierre, Rebecca J.; Williams, Patricia L.; Glanville, N. Theresa; Norris, Deborah; Hunter, Heather C.; Watt, Cynthia G.

2012-01-01

Building on earlier quantitative work where we showed that lone senior households reliant on public pensions in Nova Scotia (NS), Canada lacked the necessary funds for a basic nutritious diet, here we present findings from a qualitative study involving in-depth interviews with eight low-income lone senior women living in an urban area of NS. Using a phenomenological inquiry approach, in-depth interviews were used to explore lone senior women's experiences accessing food with limited financial resources. Drawing upon Bronfenbrenner's Ecological Systems Theory, we explored their perceived ability to access a nutritionally adequate and personally acceptable diet, and the barriers and enablers to do so; as well in light of our previous quantitative research, we explored their perceptions related to adequacy of income, essential expenses, and their strategies to manage personal finances. Seven key themes emerged: world view, income adequacy, transportation, health/health problems, community program use, availability of family and friends, and personal food management strategies. World view exerted the largest influence on seniors' personal perception of food security status. The implications of the findings and policy recommendations to reduce the nutritional health inequities among this vulnerable subset of the senior population are considered. PMID:22997580

Association between Noise Pollution and Prevalent Ischemic Heart Disease.

PubMed

Dzhambov, Angel M; Dimitrova, Donka D

2016-12-01

Noise pollution is considered a risk factor for ischemic heart disease (IHD). Both are highly prevalent in Bulgaria, but their association has not been studied sufficiently. The aim of the present study was to examine the risk of IHD associated with road traffic (Lden) and lifetime occupational noise exposure (LONE) in a Bulgarian sample. A cross-sectional survey was carried out among 513 residents of Plovdiv, Bulgaria. A questionnaire asked about doctor-diagnosed IHD, LONE and confounding factors. Lden was derived from official noise map after geocoding participants' addresses. In log-link Poisson regressions we investigated the relative risks of prevalent IHD. Sensitivity analyses examined subgroup differences. Lden ≥ 65 dB was associated with higher risk (RR=1.84, 95% CI: 0.61, 5.57) of IHD in long-term residents (≥ 20 years). LONE was associated with RR=1.76 (0.82, 3.78) for ever-exposed; and RR=2.35 (1.00, 5.52) for 15 - 47 years exposure. Exposure to Lden≥65 dB was associated with non-significantly higher risk of IHD. Longer LONE was consistently associated with higher risk. In some subgroups the effect of noise was more pronounced.

Learning from "Knocks in Life": Food Insecurity among Low-Income Lone Senior Women.

PubMed

Green-Lapierre, Rebecca J; Williams, Patricia L; Glanville, N Theresa; Norris, Deborah; Hunter, Heather C; Watt, Cynthia G

2012-01-01

Building on earlier quantitative work where we showed that lone senior households reliant on public pensions in Nova Scotia (NS), Canada lacked the necessary funds for a basic nutritious diet, here we present findings from a qualitative study involving in-depth interviews with eight low-income lone senior women living in an urban area of NS. Using a phenomenological inquiry approach, in-depth interviews were used to explore lone senior women's experiences accessing food with limited financial resources. Drawing upon Bronfenbrenner's Ecological Systems Theory, we explored their perceived ability to access a nutritionally adequate and personally acceptable diet, and the barriers and enablers to do so; as well in light of our previous quantitative research, we explored their perceptions related to adequacy of income, essential expenses, and their strategies to manage personal finances. Seven key themes emerged: world view, income adequacy, transportation, health/health problems, community program use, availability of family and friends, and personal food management strategies. World view exerted the largest influence on seniors' personal perception of food security status. The implications of the findings and policy recommendations to reduce the nutritional health inequities among this vulnerable subset of the senior population are considered.

Examining the functionality of the DeLone and McLean information system success model as a framework for synthesis in nursing information and communication technology research.

PubMed

Booth, Richard G

2012-06-01

In this review, studies examining information and communication technology used by nurses in clinical practice were examined. Overall, a total of 39 studies were assessed spanning a time period from 1995 to 2008. The impacts of the various health information and communication technology evaluated by individual studies were synthesized using the DeLone and McLean's six-dimensional framework for evaluating information systems success (ie, System Quality, Information Quality, Service Quality, Use, User Satisfaction, and Net Benefits). Overall, the majority of researchers reported results related to the overall Net Benefits (positive, negative, and indifferent) of the health information and communication technology used by nurses. Attitudes and user satisfaction with technology were also commonly measured attributes. The current iteration of DeLone and McLean model is effective at synthesizing basic elements of health information and communication technology use by nurses. Regardless, the current model lacks the sociotechnical sensitivity to capture deeper nurse-technology relationalities. Limitations and recommendations are provided for researchers considering using the DeLone and McLean model for evaluating health information and communication technology used by nurses.

Grandparenting and adolescent adjustment in two-parent biological, lone-parent, and step-families.

PubMed

Attar-Schwartz, Shalhevet; Tan, Jo-Pei; Buchanan, Ann; Flouri, Eirini; Griggs, Julia

2009-02-01

There is limited research on the links between grandparenting and adolescents' well-being, especially from the perspective of the adolescents. The study examined whether grandparent involvement varied in two-parent biological, lone-parent, and step-families and whether this had a different contribution to the emotional and behavioral adjustment of adolescents across different family structures. The study is based on a sample of 1,515 secondary school students (ages 11-16 years) from England and Wales who completed a structured questionnaire. Findings of hierarchical regression analyses showed that among the whole sample, greater grandparent involvement was associated with fewer emotional problems (p < .01) and with more prosocial behavior (p < .001). In addition, while there were no differences in the level of grandparent involvement across the different family structures, grandparent involvement was more strongly associated with reduced adjustment difficulties among adolescents from lone-parent and step-families than those from two-parent biological families. A possible implication is that the positive role of grandparent involvement in lone-parent and step- families should be more emphasized in family psychology. (PsycINFO Database Record (c) 2009 APA, all rights reserved).

Loneliness in Older Persons: A predictor of functional decline and death

PubMed Central

Perissinotto, Carla M; Cenzer, Irena Stijacic; Covinsky, Kenneth E.

2015-01-01

Background Loneliness is a common source of distress, suffering, and impaired quality of life in older persons. We examined the relationship between loneliness, functional decline and death in adults over age 60 in the United States. Methods This is a longitudinal cohort study of 1604 participants in the psychosocial module of the Health and Retirement Study (HRS), a nationally representative study of older persons. Baseline assessment was in 2002 and follow-up occurred every two years until 2008. Subjects were asked if they feel 1) Left Out 2) Isolated or 3) Lack Companionship. Subjects were categorized as not lonely if they responded hardly ever to all three questions and lonely if they responded some of the time or often to any of the three questions. The primary outcomes were time to death over 6 years, and functional decline over 6 years on 4 measures: difficulty on an increased number of activities of daily living (ADL), difficulty in an increased number of upper extremity tasks, decline in mobility, or increased difficulty in stair climbing. Multivariate analyses adjusted for demographic variables, socioeconomic status, living situation, depression, and various medical conditions. Results The mean age of subjects was 71 years, 59% were women, 81% White, 11% Black, 6% Hispanic, and 18% lived alone. 43% of elders reported feeling lonely. Loneliness was associated with all outcome measures. Lonely subjects were more likely to experience decline in ADLs, (24.8% vs. 12.5%, Adjusted Risk Ratio 1.59, 1.23-2.07); develop difficulties with upper extremity tasks (41.5% vs. 28.3%, ARR 1.28, 1.08-1.52); decline in mobility (38.1% v. 29.4%, ARR 1.18, 0.99-1.41); or difficulty in climbing (40.8% vs. 27.9%, ARR 1.31, 1.10-1.57). Loneliness was associated with an increased risk of death (22.8% vs. 14.2%, AHR 1.45, 1.11-1.88). Conclusions Among participants who were older than 60, loneliness was a predictor of functional decline and death. PMID:22710744

Methanol decomposition reactions over a boron-doped graphene supported Ru-Pt catalyst.

PubMed

Damte, Jemal Yimer; Lyu, Shang-Lin; Leggesse, Ermias Girma; Jiang, Jyh Chiang

2018-04-04

The decomposition of methanol is currently attracting research attention due to the potential widespread applications of its end products. In this work, density functional theory (DFT) calculations have been performed to investigate the adsorption and decomposition of methanol on a Ru-Pt/boron doped graphene surface. We find that the most favorable reaction pathway is methanol (CH3OH) decomposition through O-H bond breaking to form methoxide (CH3O) as the initial step, followed by further dehydrogenation steps which generate formaldehyde (CH2O), formyl (CHO), and carbon monoxide (CO). The calculations illustrate that CH3OH and CO groups prefer to adsorb at the Ru-top sites, while CH2OH, CH3O, CH2O, CHO, and H2 groups favor the Ru-Pt bridge sites, indicating the preference of Ru atoms to adsorb the active intermediates or species having lone-pair electrons. Based on the results, it is found that the energy barrier for CH3OH decomposition through the initial O-H bond breaking is less than its desorption energy of 0.95 eV, showing that CH3OH prefers to undergo decomposition to CH3O rather than direct desorption. The study provides in-depth theoretical insights into the potentially enhanced catalytic activity of Ru-Pt/boron doped graphene surfaces for methanol decomposition reactions, thereby contributing to the understanding and designing of an efficient catalyst under optimum conditions.

Conductivity study and fourier transform infrared (FTIR) characterization of methyl cellulose solid polymer electrolyte with sodium iodide conducting ion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abiddin, Jamal Farghali Bin Zainal; Ahmad, Azizah Hanom; Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam, Selangor D.E.

2015-08-28

Sodium ion (Na{sup +}) based solid polymer electrolyte (SPE) has been prepared using solution cast technique with distilled water as solvent and Methylcellulose (MC) as a polymer host. Methylcellulose polymer was chosen as the polymer host due to the abundance of lone pair electrons in the carbonyl and C-O-C constituents, which in turn provide multiple hopping sites for the Na{sup +} conducting ions. Variable compositions of sodium iodide (NaI) salt were prepared to investigate the optimum MC-NaI weight ratio. Results from Electrical Impedance Spectroscopy (EIS) technique show that pure methylcellulose has a low conductivity of 3.61 × 10{sup −11} S/cm.Themore » conductivity increases as NaI content increases up to optimum NaIcomposition of 40 wt%, which yields an average conductivity of 2.70 × 10{sup −5} S/cm.« less

Conductivity study and fourier transform infrared (FTIR) characterization of methyl cellulose solid polymer electrolyte with sodium iodide conducting ion

NASA Astrophysics Data System (ADS)

Abiddin, Jamal Farghali Bin Zainal; Ahmad, Azizah Hanom

2015-08-01

Sodium ion (Na+) based solid polymer electrolyte (SPE) has been prepared using solution cast technique with distilled water as solvent and Methylcellulose (MC) as a polymer host. Methylcellulose polymer was chosen as the polymer host due to the abundance of lone pair electrons in the carbonyl and C-O-C constituents, which in turn provide multiple hopping sites for the Na+ conducting ions. Variable compositions of sodium iodide (NaI) salt were prepared to investigate the optimum MC-NaI weight ratio. Results from Electrical Impedance Spectroscopy (EIS) technique show that pure methylcellulose has a low conductivity of 3.61 × 10-11 S/cm.The conductivity increases as NaI content increases up to optimum NaIcomposition of 40 wt%, which yields an average conductivity of 2.70 × 10-5 S/cm.

A first-principles study on second-order ferroelectric phase transition in two-dimensional puckered group V materials

NASA Astrophysics Data System (ADS)

Lee, Sang-Hoon; Jhi, Seung-Hoon

We study two-dimensional group V materials (P, As, Sb, and Bi) in puckered honeycomb structure using first-principles calculations. Two factors, the degree of puckering and buckling characterize not only the atomic structure but also the electronic structure and its topological phase. By analyzing the lone-pair character of constituent elements and the softening of the phonon mode, we clarify the origin of the buckling. We show that the phonon softening leads the second-order type structural phase transition from a flat to a buckled configuration. The inversion symmetry breaking associated with the structural transition induces the spontaneous polarization in these homogenous materials. Our calculations suggest that external strains or n-type doping are effective methods to control the degree of buckling. We find that the ferroelectric and non-trivial topological phase can coexist in puckered Bi when tensile strains are applied.

Hexadecylamine Adsorption at the Iron Oxide–Oil Interface

PubMed Central

2013-01-01

The adsorption behavior of a model additive, hexadecylamine, onto an iron surface from hexadecane oil has been characterized using polarized neutron reflectometry, sum-frequency generation spectroscopy, solution depletion isotherm, and X-ray photoelectron spectroscopy (XPS). The amine showed a strong affinity for the metal surface, forming a dense monolayer at relatively low concentrations; a layer thickness of 16 (±3) Å at low concentrations, increasing to 20 (±3) Å at greater amine concentrations, was determined from the neutron data. These thicknesses suggest that the molecules in the layer are tilted. Adsorption was also indicated by sum-frequency generation spectroscopy and XPS, the latter indicating that the most dominant amine–surface interaction was via electron donation from the nitrogen lone pair to the positively charged iron ions. Sum-frequency generation spectroscopy was used to determine the alkyl chain conformation order and orientation on the surface. PMID:24106786

Characterization of newly synthesized pyrimidine derivatives for corrosion inhibition as inferred from computational chemical analysis

NASA Astrophysics Data System (ADS)

El-Taib Heakal, F.; Rizk, S. A.; Elkholy, A. E.

2018-01-01

Corrosion of metallic constructions is a serious problem in most industries worldwide that can be controlled via addition of special chemicals having adsorption capability on metal surfaces and hence isolating it from the aggressive environment. These chemicals are characterized by being rich in functional groups containing free lone pairs of electrons and/or π-electrons. In the present study four newly imidazole-pyrimidine based ionic derivatives have been synthesized and their structures were characterized by means of elemental analysis and different spectroscopic techniques. Quantum chemical calculations were carried out to give insights into the structural and electronic characteristics of these fabricated compounds. Monte Carlo simulation was also applied to shed the light on our prepared corrosion inhibitor molecules by examining their aptitude to adsorb on iron surface. Our ultimate goal is to help industries in fighting corrosion by providing them with a cheap and efficient anti-corrosion molecules.

Red/blue shifting hydrogen bonds in acetonitrile-dimethyl sulphoxide solutions: FTIR and theoretical studies

NASA Astrophysics Data System (ADS)

Kannan, P. P.; Karthick, N. K.; Mahendraprabu, A.; Shanmugam, R.; Elangovan, A.; Arivazhagan, G.

2017-07-01

FTIR spectra of neat acetonitrile (AN), dimethyl sulphoxide (DMSO) and their binary solutions at various mole fractions have been recorded at room temperature. Theoretical calculations have also been carried out on acetonitrile (monomer, dimer), dimethyl sulphoxide (monomer, dimer) and AN - DMSO complex molecules. 1:2 (AN:DMSO) and 2:1 complexation through the red shifting (AN) C - H ⋯ O = S(DMSO) and blue shifting (DMSO) C - H ⋯ N ≡ C(AN) hydrogen bonds has been identified. The experimental and theoretical studies favour the presence of both the monomer and dimer in liquid AN, but only closed dimers in DMSO. The dipole-dipole interactions existed in AN and DMSO dimers disappear in the complex molecules. Partial π bond between S and O atoms, and three lone pair of electrons on oxygen atom of DMSO have been noticed theoretically.

Experimental and theoretical IR study of methyl thioglycolate, CH3OC(O)CH2SH, in different phases: Evidence of a dimer formation

NASA Astrophysics Data System (ADS)

Bava, Yanina B.; Tamone, Luciana M.; Juncal, Luciana C.; Seng, Samantha; Tobón, Yeny A.; Sobanska, Sophie; Picone, A. Lorena; Romano, Rosana M.

2017-07-01

The IR spectrum of methyl thioglycolate (MTG) was studied in three different phases, and interpreted with the aid of DFT calculations. The gas phase IR spectrum was explainable by the presence of the most stable conformer (syn-gauche-(-)gauche) only, while the IR spectrum of the liquid reveals strong intermolecular interactions, coincident with the formation of a dimeric form. The matrix-isolated spectra allow the identification of the second conformer (syn-gauche-gauche), in addition to the most stable form. The MTG dimer was also isolated by increasing the proportion of MTG in the matrix. The theoretical most stable structure of the dimer, which calculated IR spectrum agrees very well with the experimental one, is stabilized by a double interaction of the lone pair of the O atom of each of the Cdbnd O groups with the antibonding orbitals σ* (Ssbnd H).

The role of radial nodes of atomic orbitals for chemical bonding and the periodic table.

PubMed

Kaupp, Martin

2007-01-15

The role of radial nodes, or of their absence, in valence orbitals for chemical bonding and periodic trends is discussed from a unified viewpoint. In particular, we emphasize the special role of the absence of a radial node whenever a shell with angular quantum number l is occupied for the first time (lack of "primogenic repulsion"), as with the 1s, 2p, 3d, and 4f shells. Although the consequences of the very compact 2p shell (e.g. good isovalent hybridization, multiple bonding, high electronegativity, lone-pair repulsion, octet rule) are relatively well known, it seems that some of the aspects of the very compact 3d shell in transition-metal chemistry are less well appreciated, e.g., the often weakened and stretched bonds at equilibrium structure, the frequently colored complexes, and the importance of nondynamical electron-correlation effects in bonding. Copyright (c) 2006 Wiley Periodicals, Inc.

Stationary states of fermions in a sign potential with a mixed vector–scalar coupling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Castilho, W.M., E-mail: castilho.w@gmail.com; Castro, A.S. de, E-mail: castro@pq.cnpq.br

2014-01-15

The scattering of a fermion in the background of a sign potential is considered with a general mixing of vector and scalar Lorentz structures with the scalar coupling stronger than or equal to the vector coupling under the Sturm–Liouville perspective. When the vector coupling and the scalar coupling have different magnitudes, an isolated solution shows that the fermion under a strong potential can be trapped in a highly localized region without manifestation of Klein’s paradox. It is also shown that the lonely bound-state solution disappears asymptotically as one approaches the conditions for the realization of spin and pseudospin symmetries. --more » Highlights: •Scattering of fermions in a sign potential assessed under a Sturm–Liouville perspective. •An isolated bounded solution. •No pair production despite the high localization. •No bounded solution under exact spin and pseudospin symmetries.« less

Doping-stabilized two-dimensional black phosphorus.

PubMed

Xuan, Xiaoyu; Zhang, Zhuhua; Guo, Wanlin

2018-05-03

Two-dimensional (2D) black phosphorus (BP) has attracted broad interests but remains to be synthesized. One of the issues lies in its large number of 2D allotropes with highly degenerate energies, especially 2D blue phosphorus. Here, we show that both nitrogen and hole-carrier doping can lift the energy degeneracy and locate 2D BP in a deep global energy minimum, while arsenic doping favours the formation of 2D blue phosphorus, attributed to a delicate interplay between s-p overlapping and repulsion of lone pairs. Chemically inert substrates, e.g. graphene and hexagonal boron nitride, can be synergic with carrier doping to stabilize the BP further over other 2D allotropes, while frequently used metal substrates severely reduce the stability of 2D BP. These results not only offer new insight into the structural stability of 2D phosphorus but also suggest a promising pathway towards the chemical synthesis of 2D BP.

Study of p-diaminobenzene Adsorption on Au(111) by Scanning Tunneling Microscopy

NASA Astrophysics Data System (ADS)

Zhou, Hui; Hu, Zonghai; Eom, Daejin; Rim, Kwang; Liu, Li; Flynn, George; Venkataraman, Latha; Morgante, Alberto; Heinz, Tony

2008-03-01

From the well-defined conductivity obtained for various individual diamino-substituted molecules spanning two gold contacts, as well as from theoretical analysis [1], researchers have suggested that amines adsorb preferentially to coordinatively unsaturated surface Au atoms through the N lone pair. To understand the nature of the amine binding, we have applied ultrahigh vacuum scanning tunneling microscope (STM) to investigate the adsorption of p-diaminobenzene molecules on the reconstructed Au(111) surface. The STM topography images (taken at 4 K) show that the molecules adsorb preferentially to step edges, corresponding to sites of reduced Au atom coordination. The adsorbed molecules are found to display a distinctive orientation along the step edges. The two-lobe topographic structure of each molecule seen by STM is compatible with the previously calculated charge density of the HOMO level. [1] L. Venkataraman at el., Nano Lett. 7, 502 (2007).

Unraveling cellulose microfibrils: a twisted tale.

PubMed

Hadden, Jodi A; French, Alfred D; Woods, Robert J

2013-10-01

Molecular dynamics (MD) simulations of cellulose microfibrils are pertinent to the paper, textile, and biofuels industries for their unique capacity to characterize dynamic behavior and atomic-level interactions with solvent molecules and cellulase enzymes. While high-resolution crystallographic data have established a solid basis for computational analysis of cellulose, previous work has demonstrated a tendency for modeled microfibrils to diverge from the linear experimental structure and adopt a twisted conformation. Here, we investigate the dependence of this twisting behavior on computational approximations and establish the theoretical basis for its occurrence. We examine the role of solvent, the effect of nonbonded force field parameters [partial charges and van der Waals (vdW) contributions], and the use of explicitly modeled oxygen lone pairs in both the solute and solvent. Findings suggest that microfibril twisting is favored by vdW interactions, and counteracted by both intrachain hydrogen bonds and solvent effects at the microfibril surface. Copyright © 2013 Wiley Periodicals, Inc.

Unraveling Cellulose Microfibrils: A Twisted Tale

PubMed Central

Hadden, Jodi A.; French, Alfred D.; Woods, Robert J.

2014-01-01

Molecular dynamics (MD) simulations of cellulose microfibrils are pertinent to the paper, textile, and biofuels industries for their unique capacity to characterize dynamic behavior and atomic-level interactions with solvent molecules and cellulase enzymes. While high-resolution crystallographic data have established a solid basis for computational analysis of cellulose, previous work has demonstrated a tendency for modeled microfibrils to diverge from the linear experimental structure and adopt a twisted conformation. Here, we investigate the dependence of this twisting behavior on computational approximations and establish the theoretical basis for its occurrence. We examine the role of solvent, the effect of nonbonded force field parameters [partial charges and van der Waals (vdW) contributions], and the use of explicitly modeled oxygen lone pairs in both the solute and solvent. Findings suggest that microfibril twisting is favored by vdW interactions, and counteracted by both intrachain hydrogen bonds and solvent effects at the microfibril surface. PMID:23681971

Photoelectron Spectroscopy of Free Polyoxoanions Mo6O19 2- and W6O19 2- in the Gas Phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Infante, Ivan A.; Visscher, Lucas; Wang, Xue B.

2004-09-22

Two doubly charged polyoxoanions, Mo6O19 2- and W6O19 2-, were observed in the gas phase using electrospray ionization. Their electronic structures were investigated using photoelectron spectroscopy and quasi-relativistic density functional calculations. Each dianion was found to be highly stable despite the presence of strong intramolecular coulomb repulsion, estimated to be about 2 eV for each system. The valence detachment features were all shown to originate from electronic excitations involving oxygen lone-pair type orbitals. Their observed energies were in excellent agreement with the theoretical vertical detachment energies calculated using time-dependent density functional theory. Despite being multiply charged, polyoxometalate oxide clusters canmore » be studied in the gas phase, providing the opportunity for detailed benchmark theoretical studies on the electronic structures of these important transition-metal oxide systems.« less

Fluorine and Fluorinated Motifs in the Design and Application of Bioisosteres for Drug Design.

PubMed

Meanwell, Nicholas A

2018-02-05

The electronic properties and relatively small size of fluorine endow it with considerable versatility as a bioisostere and it has found application as a substitute for lone pairs of electrons, the hydrogen atom, and the methyl group while also acting as a functional mimetic of the carbonyl, carbinol, and nitrile moieties. In this context, fluorine substitution can influence the potency, conformation, metabolism, membrane permeability, and P-gp recognition of a molecule and temper inhibition of the hERG channel by basic amines. However, as a consequence of the unique properties of fluorine, it features prominently in the design of higher order structural metaphors that are more esoteric in their conception and which reflect a more sophisticated molecular construction that broadens biological mimesis. In this Perspective, applications of fluorine in the construction of bioisosteric elements designed to enhance the in vitro and in vivo properties of a molecule are summarized.

Electron transport in NH3/NO2 sensed buckled antimonene

NASA Astrophysics Data System (ADS)

Srivastava, Anurag; Khan, Md. Shahzad; Ahuja, Rajeev

2018-04-01

The structural and electronic properties of buckled antimonene have been analysed using density functional theory based ab-initio approach. Geometrical parameters in terms of bond length and bond angle are found close to the single ruffle mono-layer of rhombohedral antimony. Inter-frontier orbital analyses suggest localization of lone pair electrons at each atomic centre. Phonon dispersion along with high symmetry point of Brillouin zone does not signify any soft mode. With an electronic band gap of 1.8eV, the quasi-2D nano-surface has been further explored for NH3/NO2 molecules sensing and qualities of interaction between NH3/NO2 gas and antimonene scrutinized in terms of electronic charges transfer. A current-voltage characteristic has also been analysed, using Non Equilibrium Green's function (NEGF), for antimonene, in presence of incoming NH3/NO2 molecules.

Structural investigations and the effect of strain on lead based double perovskites

NASA Astrophysics Data System (ADS)

Abbett, Brian; Fennie, Craig J.

2014-03-01

The A2 BB' O6 double perovskite structure, in which the B and B' ions are ordered (typically in a rocksalt configuration), provides a versatile platform to realize new properties such as multiferroicity. In particular, compounds with a lone-pair cation on the A-site, such as A=Pb2+, and magnetic B=Co, Mn, and diamagnetic B'= Te, Mo, W, Re, cations have been investigated experimentally, but as of yet none have been found to display ferroelectricity, although several are known to be antiferroelectric. Here we present a first-principles study of the structural and dielectric properties of this family of compounds. We resolve any conflicting reports in the literature as to the ground state structure of compounds and predict the ground state structure when no structural data is available. Additionally, we investigate the effect of epitaxial strain on the structural and magnetic properties.

Thermoelectric properties of Bi1-xSnxCuSeO solid solutions.

PubMed

Yang, Yuqing; Liu, Xiaocun; Liang, Xin

2017-02-21

We report the enhanced thermoelectric properties of p-type BiCuSeO by tin doping on bismuth sites. Powder X-ray diffraction analysis and Hall measurements indicated effective tin doping in all samples. We found that the doping efficiency of Sn is lower than expected, as seen from the measured carrier concentration. First-principles calculations indicate that the Sn lone pair modifies the band structure at the Fermi level, with the consequent effect observed in the electrical transport and Seebeck coefficient measurements. An enhanced thermoelectric power factor of ∼2.5 μW cm -1 K -2 was reached at 773 K. No significant effect of Sn doping on the thermal conductivity was found; a thermoelectric figure of merit value (ZT) of 0.3 at 773 K is achieved for Bi 0.9 Sn 0.1 CuSeO, which is more than twice that of the pristine BiCuSeO.

Applied Hypergame Theory for Network Defense

DTIC Science & Technology

2013-06-01

information technology infrastructure as they are perhaps the most wired country on the planet . Government websites, banking systems, and even media...a long way from the simple lone youth down in the basement causing mischief. Organized swaths of intelligent computer savvy attackers now exist and...out of the five hypergames choose the hyperstrategy that is the same as the full game MSNE, with the Mid-Level defender being the lone difference. Thus

Shaping the Future: Security Cooperation to Shape Chinese Diplomacy in the South Pacific

DTIC Science & Technology

2008-10-31

New Zealand ( Lonely Planet , 2006), 701. http://books.google.com...Miller, Sally O’Brien, and Charles Rawlings-Way. New Zealand . Lonely Planet , 2006. http://books.google.com/books?id=FHxJ4zuemtcC&dq=carolyn+baine... New Zealand (NZ), the total region covers 20 million square miles of ocean and 117,000 square miles of land with Papua New Guinea (PNG) accounting

Assessing eLearning Systems Success in Nigeria: An Application of the DeLone and McLean Information Systems Success Model

ERIC Educational Resources Information Center

Yakubu, M. Nasiru; Dasuki, Salihu Ibrahim

2018-01-01

Aim/Purpose: This study is based on the DeLone and McLean's Information Systems Success (D&M ISS) model, which was modified to determine the success factors responsible for the acceptance of an e-learning system called Canvas by students of a Nigerian University. Background: The adoption of eLearning has been under studied within the context…

Dynamic use of wetlands by black ducks and mallards: evidence against competitive exclusion

USGS Publications Warehouse

McAuley, D.G.; Clugston, D.A.; Longcore, J.R.

2004-01-01

The decline of the American black duck (Anas rubripes) has been attributed to competition from mallards (A. platyrhynchos) that led to exclusive use of fertile wetlands by mallards. Data from annual breeding waterfowl surveys provide instantaneous, single observations of breeding pairs, which are used to estimate breeding population size and evaluate the condition of habitat. Data from these surveys have been used to document habitat use by black ducks and mallards. We used quiet-observation surveys from elevated platforms to study sympatric black ducks and mallards in northern Maine during the breeding season. Our objectives were to document occupancy of wetlands by breeding black ducks and mallards throughout the day during prenesting and early nesting periods to determine whether 1) wetlands were occupied by only a single species, 2) pairs of the same species occupied wetlands throughout the period, and 3) single observations of short duration adequately determine numbers and species using a wetland. We observed ducks at 5-minute intervals from elevated platforms on wetland margins to determine numbers and species of indicated pairs using each wetland over time. We visited 80% of the wetlands >2 times, with mean total time per wetland averaging 267 minutes. For each wetland we determined the most frequently observed grouping of black ducks and mallards from all combinations recorded during all intervals (e.g., 1 black duck [BO] pair during 9 intervals; 2 mallard [MA] pairs and 1 BO pair during 22 intervals; 0 pairs during 3 intervals). A single pair, a lone male, or no ducks were recorded during 34% of the 5-minute intervals. For wetlands with >2 hours of observations (n=65), all but 2 were used by >2 different combinations of ducks. On most wetlands, the most frequent grouping was observed during 2 hours were used by both species, random visits detected both species on only 27 wetlands. Our data do not support assertions that the mallard has caused the decline of black ducks through interspecific competition for habitat, or that wetlands are occupied continuously by single pairs that aggressively exclude conspecifics. Our data indicated that single, short-duration visits with disturbance to wetlands are unreliable and inappropriate to document seasonal use of wetlands by breeding black ducks and mallards.

DoD Security Assistance Management Manual

DTIC Science & Technology

1988-10-01

IDSS Administrator for U.S. Army Training Activities: TSASS Database Manager SATFA Attn: ATFA-I 2017 Cunningham Drive, 4th Floor Hampton VA 23666 DSN...Depot, Chambersburg, PA J. School of Engineering and Logistics, Red River Army Depot, Texarkana , "TX K. Lone Star Ammunition Plant, Texarkana , TX L...Electronics Command, Ft. Monmouth, NJ U. Red River Army Depot, Texarkana , TX V. Army Aviation Research and Development Command, St. Louis, MO W

Commensal orthologs of the human autoantigen Ro60 as triggers of autoimmunity in lupus | Center for Cancer Research

Cancer.gov

Lupus: No Longer a Lone Wolf. Lupus (represented by the wolf, Canis lupus) is a chronic autoimmune disorder that progresses over decades. Greiling et al. analyzed commensal bacteria in lupus patients and identified species with Ro60 proteins similar to human Ro60, an early autoantigen in lupus. Bacterial Ro60 could activate patient lymphocytes, and colonization of mice with

Hydrogen bonds in concreto and in computro: the sequel

NASA Astrophysics Data System (ADS)

Stouten, Pieter F. W.; Van Eijck, Bouke P.; Kroon, Jan

1991-02-01

In the framework of our comparative research concerning hydrogen bonding in the crystalline and liquid phases we have carried out molecular dynamics (MD) simulations of liquid methanol. Six different rigid three site models are compared. Five of them had been reported in the literature and one (OM2) we developed by a fit to the experimental molar volume, heat of vaporization and neutron weighted radial distribution function. In general the agreement with experiment is satisfactory for the different models. None of the models has an explicit hydrogen bond potential, but five of the six models show a degree of hydrogen bonding comparable to experiments on liquid methanol. The analysis of the simulation hydrogen bonds indicates that there is a distinct preference of the O⋯O axis to lie in the acceptor lone pairs plane, but hardly any for the lone pair directions. Ab initio calculations and crystal structure statistics of OH⋯O hydrogen bonds agree with this observation. The O⋯O hydrogen bond length distributions are similar for most models. The crystal structures show a sharper O⋯O distribution. Explicit introduction of harmonic motion with a quite realistic root mean square amplitude of 0.08 Å to the thermally averaged crystal distribution results in a distribution comparable to OM2 although the maximum of the former is found at shorter distance. On the basis of the analysis of the static properties of all models we conclude that our OM2, Jorgenson's OPLS and Haughney, Ferrario and McDonald's HFM1 models are good candidates for simulations of liquid methanol under isothermal, isochoric conditions. Partly flexible and completely rigid OM2 are simulated at constant pressure and with fixed volume. The flexible simulations give essentially the same (correct) results under both conditions, which is not surprising because the flexible form was fitted under both conditions. Rigid OM2 has a similar potential energy but larger pressure in the isochoric case and larger energy and far larger volume in the isobaric case. Radial distribution functions and hydrogen bond geometries are very similar for all four cases. Only in the case of the osobaric rigid methanol does the volume expansion seem to be accompanied by a slight preference for tetrahedrality around the oxygen atom.

The bright future of unconventional σ/π-hole interactions.

PubMed

Bauzá, Antonio; Mooibroek, Tiddo J; Frontera, Antonio

2015-08-24

Non-covalent interactions play a crucial role in (supramolecular) chemistry and much of biology. Supramolecular forces can indeed determine the structure and function of a host-guest system. Many sensors, for example, rely on reversible bonding with the analyte. Natural machineries also often have a significant non-covalent component (e.g. protein folding, recognition) and rational interference in such 'living' devices can have pharmacological implications. For the rational design/tweaking of supramolecular systems it is helpful to know what supramolecular synthons are available and to understand the forces that make these synthons stick to one another. In this review we focus on σ-hole and π-hole interactions. A σ- or π-hole can be seen as positive electrostatic potential on unpopulated σ* or π(() *()) orbitals, which are thus capable of interacting with some electron dense region. A σ-hole is typically located along the vector of a covalent bond such as XH or XHlg (X=any atom, Hlg=halogen), which are respectively known as hydrogen and halogen bond donors. Only recently it has become clear that σ-holes can also be found along a covalent bond with chalcogen (XCh), pnictogen (XPn) and tetrel (XTr) atoms. Interactions with these synthons are named chalcogen, pnigtogen and tetrel interactions. A π-hole is typically located perpendicular to the molecular framework of diatomic π-systems such as carbonyls, or conjugated π-systems such as hexafluorobenzene. Anion-π and lone-pair-π interactions are examples of named π-hole interactions between conjugated π-systems and anions or lone-pair electrons respectively. While the above nomenclature indicates the distinct chemical identity of the supramolecular synthon acting as Lewis acid, it is worth stressing that the underlying physics is very similar. This implies that interactions that are now not so well-established might turn out to be equally useful as conventional hydrogen and halogen bonds. In summary, we describe the physical nature of σ- and π-hole interactions, present a selection of inquiries that utilise σ- and π-holes, and give an overview of analyses of structural databases (CSD/PDB) that demonstrate how prevalent these interactions already are in solid-state structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic Signatures and Structural Motifs of Dopamine: a Computational Study

NASA Astrophysics Data System (ADS)

Srivastava, Santosh Kumar; Singh, Vipin Bahadur

2016-06-01

Dopamine (DA) is an essential neurotransmitter in the central nervous system and it plays integral role in numerous brain functions including behaviour, cognition, emotion, working memory and associated learning. In the present work the conformational landscapes of neutral and protonated dopamine have been investigated in the gas phase and in aqueous solution by MP2 and DFT (M06-2X, ωB97X-D, B3LYP and B3LYP-D3) methods. Twenty lowest energy structures of neutral DA were subjected to geometry optimization and the gauche conformer, GIa, was found to be the lowest gas phase structure at the each level of theory in agreement with the experimental rotational spectroscopy. All folded gauche conformers (GI) where lone electron pair of the NH2 group is directed towards the π system of the aromatic ring ( 'non up' ) are found more stable in the gas phase. While in aqueous solution, all those gauche conformers (GII) where lone electron pair of the NH2 group is directed opposite from the π system of the aromatic ring ('up' structures) are stabilized significantly.Nine lowest energy structures, protonated at the amino group, are optimized at the same MP2/aug-cc-pVDZ level of theory. In the most stable gauche structures, g-1 and g+1, mainly electrostatic cation - π interaction is further stabilized by significant dispersion forces as predicted by the substantial differences between the DFT and dispersion corrected DFT-D3 calculations. In aqueous environment the intra-molecular cation- π distance in g-1 and g+1 isomers, slightly increases compared to the gas phase and the magnitude of the cation- π interaction is reduced relative to the gas phase, because solvation of the cation decreases its interaction energy with the π face of aromatic system. The IR intensity of the bound N-H+ stretching mode provides characteristic 'IR spectroscopic signatures' which can reflect the strength of cation- π interaction energy. The CC2 lowest lying S1 ( 1ππ* ) excited state of neutral dopamine is significantly red shifted upon protonation at amino site. E. Dragicevic, J. Schiemann and B. Liss, Neuroscience, 2015, 284, 798. Y. T. Chien et al. Science, 2010, 330, 1091. Cabezas etal., J. Phys. Chem. Lett. 2013, 4, 486.

Spectroscopically determined force field for water dimer: physically enhanced treatment of hydrogen bonding in molecular mechanics energy functions.

PubMed

Mannfors, Berit; Palmo, Kim; Krimm, Samuel

2008-12-11

Our ab initio transformed spectroscopically determined force field (SDFF) methodology emphasizes, in addition to accurate structure and energy performance, comparable prediction of vibrational properties in order to improve reproduction of interaction forces. It is now applied to the determination of a molecular mechanics (MM) force field for the water monomer and dimer as an initial step in developing a more physically based treatment of the hydrogen bonding that not only underlies condensed-phase water but also must be important in molecular-level protein-water interactions. Essential electrical components of the SDFF for monomer water are found to be the following: an off-plane charge distribution, this distribution consisting of four off-atom charge sites in traditional lone pair (LP) but also in inverted lone pair (ILP) positions; allowance for a diffuse size to these off-atom sites; and the incorporation of charge fluxes (i.e., the change in charge with change in internal coordinate). Parametrization of such an LP/ILP model together with the SDFF analytically transformed valence force field results in essentially exact agreement with ab initio (in this case MP2/6-31++G(d,p)) structure, electrical, and vibrational properties. Although we demonstrate that the properties of this monomer electrical model together with its van der Waals and polarization interactions are transferable to the dimer, this is not sufficient in reproducing comparable dimer properties, most notably the huge increase in infrared intensity of a donor OH stretch mode. This deficiency, which can be eliminated by a large dipole-derivative-determined change in the effective charge flux of the donor hydrogen-bonded OH bond, is not accounted for by the charge flux change in this bond due to the induction effects of the acceptor electric field alone, and can only be fully removed by an added bond flux associated with the extent of overlap of the wave functions of the two molecules. We show that this overlap charge flux (OCF) emulates an actual O-H...LP-O intermolecular dipole flux, reflecting the unitary nature of the hydrogen-bonded system in the context of MM-separable molecules. The effectiveness of incorporating the OCF noncanonical character demonstrates that a distinctively QM-unique property can be substantively represented in MM energy functions.

Lone-Wolf Terrorist Radicalization and the Prisoner’s Dilemma: Ensuring Mutual Cooperation Between at-Risk Muslim Americans and Local Communities

DTIC Science & Technology

2015-09-01

for public release; distribution is unlimited 12b. DISTRIBUTION CODE A 13. ABSTRACT While scholars study the radicalization process that...the degree of MASTER OF ARTS IN SECURITY STUDIES (HOMELAND SECURITY AND DEFENSE) from the NAVAL POSTGRADUATE SCHOOL September 2015...Affairs iv THIS PAGE INTENTIONALLY LEFT BLANK v ABSTRACT While scholars study the radicalization process that produces lone-wolf terrorists

Detection of Ehrlichia chaffeensis in adult and nymphal stage lone star ticks (Amblyomma americanum) from Long Island, New York

USGS Publications Warehouse

Mixson, T.R.; Ginsberg, H.S.; Campbell, S.R.; Sumner, J.W.; Paddock, C.D.

2004-01-01

The lone star tick, Amblyomma americanum (L.), has increased in abundance in several regions of the northeastern United States, including areas of Long Island, NY. Adult and nymphal stage A. americanum collected from several sites on Long Island were evaluated for infection with Ehrlichia chaffeensis, the causative agent of human monocytic ehrlichiosis (HME), by using a nested polymerase chain reaction assay. Fifty-nine (12.5%) of ,17.3 adults and eight of 11.3 pools of five nymphs each (estimated minimum prevalence of infection 1.4%) contained DNA of E. chaffeensis. These data, coupled with the documented expansion of lone star tick populations in the northeastern United States, confirm that E. chaffeensis is endemic to many areas of Long Island and that HME should be considered among the differential diagnoses of the many distinct tick-borne diseases that occur in this region.

Contiguous triple spinal dysraphism associated with Chiari malformation Type II and hydrocephalus: an embryological conundrum between the unified theory of Pang and the unified theory of McLone.

PubMed

Dhandapani, Sivashanmugam; Srinivasan, Anirudh

2016-01-01

Triple spinal dysraphism is extremely rare. There are published reports of multiple discrete neural tube defects with intervening normal segments that are explained by the multisite closure theory of primary neurulation, having an association with Chiari malformation Type II consistent with the unified theory of McLone. The authors report on a 1-year-old child with contiguous myelomeningocele and lipomyelomeningocele centered on Type I split cord malformation with Chiari malformation Type II and hydrocephalus. This composite anomaly is probably due to select abnormalities of the neurenteric canal during gastrulation, with a contiguous cascading impact on both dysjunction of the neural tube and closure of the neuropore, resulting in a small posterior fossa, probably bringing the unified theory of McLone closer to the unified theory of Pang.

Lonely people are no longer lonely on social networking sites: the mediating role of self-disclosure and social support.

PubMed

Lee, Kyung-Tag; Noh, Mi-Jin; Koo, Dong-Mo

2013-06-01

Most previous studies assert the negative effect of loneliness on social life and an individual's well-being when individuals use the Internet. To expand this previous research tradition, the current study proposes a model to test whether loneliness has a direct or indirect effect on well-being when mediated by self-disclosure and social support. The results show that loneliness has a direct negative impact on well-being but a positive effect on self-disclosure. While self-disclosure positively influences social support, self-disclosure has no impact on well-being, and social support positively influences well-being. The results also show a full mediation effect of social support in the self-disclosure to well-being link. The results imply that even if lonely people's well-being is poor, their well-being can be enhanced through the use of SNSs, including self-presentation and social support from their friends.

A lone desert Joshua tree greeted the arrival of Space Shuttle Endeavour at Edwards Air Force Base,

NASA Technical Reports Server (NTRS)

2001-01-01

A lone desert Joshua tree greeted the arrival of Space Shuttle Endeavour at Edwards Air Force Base, California, May 1, 2001. A large drag chute helped slow Endeavour on the runway. After mounting the shuttle on a converted 747 airliner at NASA's Dryden Flight Research Center, Endeavour will be carried back to the Kennedy Space Center for its next mission. Weather in Florida necessitated landing in California.

A Framework for Violence: Clarifying the Role of Motivation in Lone-Actor Terrorism

DTIC Science & Technology

2017-03-01

Within the timeframe included in this study , there was, on average, just over one case of lone-actor terrorism per year.60 Spaaij expanded his...informants and sting operations.63 Within the Becker study , twelve out of eighty-four attacks, relied on confidential informants.64 In certain cases , the...indicators of personal or ideological grievances. The data used for this research are publicly available and largely based on two case studies compiled

Modeling the present and future geographic distribution of the Lone star tick, Amblyomma americanum (Ixodida: Ixodidae), in the continental United States

USGS Publications Warehouse

Springer, Yuri P.; Jarnevich, Catherine S.; Barnett, David T.; Monaghan, Andrew J.; Eisen, Rebecca J.

2015-01-01

The Lone star tick (Amblyomma americanum L.) is the primary vector for pathogens of significant public health importance in North America, yet relatively little is known about its current and potential future distribution. Building on a published summary of tick collection records, we used an ensemble modeling approach to predict the present-day and future distribution of climatically suitable habitat for establishment of the Lone star tick within the continental United States. Of the nine climatic predictor variables included in our five present-day models, average vapor pressure in July was by far the most important determinant of suitable habitat. The present-day ensemble model predicted an essentially contiguous distribution of suitable habitat extending to the Atlantic coast east of the 100th western meridian and south of the 40th northern parallel, but excluding a high elevation region associated with the Appalachian Mountains. Future ensemble predictions for 2061–2080 forecasted a stable western range limit, northward expansion of suitable habitat into the Upper Midwest and western Pennsylvania, and range contraction along portions of the Gulf coast and the lower Mississippi river valley. These findings are informative for raising awareness of A. americanum-transmitted pathogens in areas where the Lone Star tick has recently or may become established.

Covalent triazine framework supported non-noble metal nanoparticles with superior activity for catalytic hydrolysis of ammonia borane: from mechanistic study to catalyst design† †Electronic supplementary information (ESI) available: 11B NMR spectra, XRD patterns, results of BET and ICP, XPS spectra, TOF values and activation energies E a of the non-noble metal catalysts, time versus volume of H2, catalytic activities and TEM images of 5% Co/CNT, 3% Co/CNT, 1% Co/CNT, the plot of hydrogen generation rate versus the concentration of Co and AB, kinetic isotope effect and TEM image of 5% Co/CTF-1 after reaction. See DOI: 10.1039/c6sc02456d Click here for additional data file.

PubMed Central

Li, Zhao; Liu, Lin; Chen, Weidong; Zhang, Miao; Wu, Guotao; Chen, Ping

2017-01-01

Development of non-noble metal catalysts with similar activity and stability to noble metals is of significant importance in the conversion and utilization of clean energy. The catalytic hydrolysis of ammonia borane (AB) to produce 3 equiv. of H2, as an example of where noble metal catalysts significantly outperform their non-noble peers, serves as an excellent test site for the design and optimization of non-noble metal catalysts. Our kinetic isotopic effect measurements reveal, for the first time, that the kinetic key step of the hydrolysis is the activation of H2O. Deducibly, a transition metal with an optimal electronic structure that bonds H2O and –OH in intermediate strengths would favor the hydrolysis of AB. By employing a covalent triazine framework (CTF), a newly developed porous material capable of donating electrons through the lone pairs on N, the electron densities of nano-sized Co and Ni supported on CTF are markedly increased, as well as their catalytic activities. Specifically, Co/CTF exhibits a total turnover frequency of 42.3 molH2 molCo –1 min–1 at room temperature, which is superior to all peer non-noble metal catalysts ever reported and even comparable to some noble metal catalysts. PMID:28451227

Loneliness in middle and old age: demographics, perceived health, and social satisfaction as predictors.

PubMed

Ferreira-Alves, José; Magalhães, Paula; Viola, Lara; Simoes, Ricardo

2014-01-01

(a) To identify the degree of much loneliness reported in the Portuguese population over 50 years of age and (b) test whether loneliness can be predicted by socio-demographic, health related or social characteristic of the sample other than age. 1174 late middle age and older adults were interviewed face to face by different interviewers across the country; after the informed consent was signed, we asked the participants several socio-demographic and health-related questions; finally we asked "How often do you feel lonely?" and participants responded according to a five point Likert scale. The results showed that 12% of participants reporting feeling lonely often or always, whereas 40% reporting never feeling lonely. The remaining 48% self-reported they felt lonely seldom or sometimes. Additionally, results show that, when taken together, variables such as marital status, type of housing, residence settings, health conditions, social satisfaction, social isolation, lack of interest, transportation, and age were predictors of loneliness. (1) The association of loneliness with advanced age has been greatly exaggerated by mass media and common sense; (2) But although our findings did not confirm the most alarmist views, the 12% of older adults reporting that they are feeling lonely always or often should be cause for attention and concern. It is necessary to understand the meaning, reasons and level of suffering implied on those feelings of loneliness. (3) Our findings suggest that it makes no sense to construe age as a singular feature or cause for feelings of loneliness. Instead, age and also a number of other features combine to predict feelings of loneliness. But even with our predictor variables there was a substantial of variance left unexplained. Therefore it is necessary to continue exploring how feelings of loneliness arise from the experience of living and how they can be changed. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Optical properties of a new Bi38Mo7O78 semiconductor with fluorite-type δ-Bi2O3 structure

NASA Astrophysics Data System (ADS)

Wang, Zuoshan; Bi, Shala; Wan, Yingpeng; Huang, Pengjie; Zheng, Min

2017-03-01

Bi3+-containing inorganic materials usually show rich optical and electronic properties due to the hybridization between 6s and 6p electronic components together with the lone pair in Bi3+ ions. In this work, a new semiconductor of bismuth molybdate Bi38Mo7O78 (19Bi2O3·7MoO3) was synthesized by the sol-gel film coating and the following heat process. The samples developed into nanoparticles with average size of 40 nm. The phase formation was verified via the XRD Rietveld structural refinement. Orthorhombic Bi38Mo7O78 can be regarded to be derived from the cubic δ-phase Bi2O3 structure. The microstructure was investigated by SEM, EDX, TEM, BET and XPS measurements. The UV-vis absorption spectra showed that the band gap of Bi38Mo7O78 (2.38 eV) was greatly narrowed in comparison with Bi2O3 (2.6 eV). This enhances the efficient absorption of visible light. Meanwhile, the conduction band of is wider and shows more dispersion, which greatly benefits the mobility of the light-induced charges taking part in the photocatalytic reactions. Bi38Mo7O78 nanoparticles possess efficient activities on the photodegradation of methylene blue (MB) solutions under the excitation of visible-light. The photocatalysis activities and mechanisms were discussed on the crystal structure characteristics and the measurements such as photoluminescence, exciton lifetime and XPS results.

A lone desert Joshua tree greeted the arrival of Space Shuttle Endeavour at Edwards Air Force Base, California, on May 1, 2001

NASA Image and Video Library

2001-05-01

A lone desert Joshua tree greeted the arrival of Space Shuttle Endeavour at Edwards Air Force Base, California, May 1, 2001. A large drag chute helped slow Endeavour on the runway. After mounting the shuttle on a converted 747 airliner at NASA's Dryden Flight Research Center, Endeavour will be carried back to the Kennedy Space Center for its next mission. Weather in Florida necessitated landing in California.

The Death of the Capital Ship: Is There a Place for Supercarriers in Modern Navies

DTIC Science & Technology

2013-04-01

tons with the lone exception of the Russian carrier the Admiral Kuznetsov which displaces 67,500 tons.3 This allows the supercarriers to load more...from land bases more easily and cheaply than from a carrier. However, unlike other nations, as the world’s lone superpower the United States has...first reason and foremost reason why only one nation (with the largest defense budget on the planet ) has a fleet of supercarriers is the cost to

MX Siting Investigation. Gravity Survey - Big Smokey Valley, Nevada.

DTIC Science & Technology

1980-11-28

Monte Cristo Range, on the south by Lone Mountain arid Tonopah, Nevada, and on the north by the T1i7 ,abhv i a7e. True area covered by this report lies...Royston Hills and Monte Cristo Range) are chiefly Tertiary tuffs, rhyolites, andesites, and basalts. Basin-fill deposits within the valley reach combined...east of Royston Hills and Monte Cristo Range. At the southern end where the valley bifurcates, faults are interpreted to be near both flanks of Lone

Impact of social relationships on Alzheimer's memory impairment: mechanistic studies.

PubMed

Hsiao, Ya-Hsin; Chang, Chih-Hua; Gean, Po-Wu

2018-01-11

Alzheimer's disease (AD) is characterized by progressive memory and neuronal loss culminating in cognitive impairment that not only affects a person's living ability but also becomes a society's as well as a family's economic burden. AD is the most common form of dementia in older persons. It is expected that the number of people with AD dementia will increase dramatically in the next 30 years, projecting to 75 million in 2030 and 131.5 million in 2050 worldwide. So far, no sufficient evidence is available to support that any medicine is able to prevent or reverse the progression of the disease. Early studies have shown that social environment, particularly social relationships, can affect one's behavior and mental health. A study analyzing the correlation between loneliness and risk of developing AD revealed that lonely persons had higher risk of AD compared with persons who were not lonely. On the other hand, it has been reported that we can prevent cognitive decline and delay the onset of AD if we keep mentally active and frequently participate in social activities. In this review, we focus on the impact of social behaviors on the progression of cognitive deficit in animal models of AD with a particular emphasis on a mechanistic scheme that explains how social isolation exacerbates cognitive impairment and how social interaction with conspecifics rescues AD patients' memory deficit.

Department of Defense Base Structure Report (A Summary of DoD’s Real Property Inventory) Fiscal Year 2006 Baseline

DTIC Science & Technology

2006-01-01

438 1,964,339 7,6767,117 762.7 28 0 0Navy Active NMCRC Miami Miami 2 62,752 2017 10.7 1,215 2 0Navy Reserve NS Mayport FL Mayport 646 3,822,934 16...3,746 724403 17.8AF Active Lone Star AAP Texarkana 876 3,264,503 15,69915,699 841.3 1 18 0Army Active C Lonestar Pecos Electronic Scoring Site Pecos 2...1,183.5 3,201 5,355 0AF Active R Red River Army Depot Texarkana 1,125 7,555,228 18 173,594 18,31618,316 1,558.5 144 1,894 1,838Army Active R Saginaw

The Experience of Older Women Living with Loneliness and Chronic Conditions in Appalachia

PubMed Central

Theeke, Laurie A.; Mallow, Jennifer; Gianni, Chelsea; Legg, Kacie; Glass, Christy

2015-01-01

This phenomenological qualitative study explored the experience of living with loneliness and multiple chronic conditions for rural older women in Appalachia. The study took place in 2012 in Northern West Virginia. Participants were 14 older women who were chronically ill, community dwelling, and lonely (Score of 40 or higher on the Revised 20-item UCLA Loneliness Scale). Thematic content analysis revealed four categories that contained thirteen themes: (a) negative emotions of loneliness, which included themes of sadness, disconnection, fear, anger, and worry; (b) positive emotions when not lonely, which included themes of joy with others and pride in self; (c) loss of independence and loneliness, which included themes of functional decline contributes to loneliness, burden, and gratitude for help; and (d) ways of managing loneliness, which included remembering holidays and happier moments, staying busy, and getting out. The study contributes new knowledge about the experience of anger, fear, and worry when lonely. These emotions have not extensively been identified as significant to loneliness. Future studies exploring the links between loneliness and anger, fear, worry, and negative physical health outcomes could enhance knowledge of mechanisms by which loneliness contributes to health decline. Additionally, knowing that positive emotions such as joy are described as being linked to less lonely times could inform future work that aims to diminish loneliness and enhance positive emotional states. Finally, understanding that functional impairment is described as contributing to loneliness in this population reinforces the need to assess for and address functional limitations. PMID:26594267

[CH(3)(CH(2))(11)NH(3)]SnI(3): a hybrid semiconductor with MoO(3)-type tin(II) iodide layers.

PubMed

Xu, Zhengtao; Mitzi, David B

2003-10-20

The organic-inorganic hybrid [CH(3)(CH(2))(11)NH(3)]SnI(3) presents a lamellar structure with a Sn-I framework isotypic to that of MoO(3). The SnI(3)(-) layer consists of edge and corner-sharing SnI(6) octahedra in which one of the six Sn-I bonds is distinctly elongated (e.g., 3.62 A), indicating lone-pair stereoactivity for the Sn(II) atom. The overall electronic character remains comparable with that of the well-studied SnI(4)(2)(-)-based perovskite semiconductors, such as [CH(3)(CH(2))(11)NH(3)](2)SnI(4), with a red-shifted and broadened exciton peak associated with the band gap, apparently due to the increased dimensionality of the Sn-I framework. The title compound offers, aside from the hybrid perovskites, a new type of solution-processable Sn-I network for potential applications in semiconductive devices.

Remote Substituent Effects on the Structures and Stabilities of P═E π-Stabilized Diphosphatetrylenes (R2P)2E (E = Ge, Sn).

PubMed

Izod, Keith; Evans, Peter; Waddell, Paul G; Probert, Michael R

2016-10-17

A rare P-E π interaction between the lone pair of a planar P center and the vacant p orbital at the Ge or Sn center provides efficient stabilization for P-substituted tetrylenes (R 2 P) 2 E (E = Ge, Sn) and enables isolation of the first example of a compound with a crystallographically authenticated P═Sn bond. Subtle changes in the electronic properties of the bulky aryl substituents in these compounds change the preference for planar versus pyramidal P centers in the solid state; however, variable-temperature NMR spectroscopy indicates that in solution these species are subject to a dynamic equilibrium, which interconverts the planar and pyramidal P centers. Consistent with this, density functional theory studies suggest that there is only a small energy difference between the planar and pyramidal forms of these compounds and reveal a small singlet-triplet energy separation, suggesting potentially interesting reactivities.

Spin Exchange Interaction in Substituted Copper Phthalocyanine Crystalline Thin Films

NASA Astrophysics Data System (ADS)

Rawat, Naveen; Pan, Zhenwen; Lamarche, Cody J.; Wetherby, Anthony; Waterman, Rory; Tokumoto, Takahisa; Cherian, Judy G.; Headrick, Randall L.; McGill, Stephen A.; Furis, Madalina I.

2015-11-01

The origins of spin exchange in crystalline thin films of Copper Octabutoxy Phthalocyanine (Cu-OBPc) are investigated using Magnetic Circular Dichroism (MCD) spectroscopy. These studies are made possible by a solution deposition technique which produces highly ordered films with macroscopic grain sizes suitable for optical studies. For temperatures lower than 2 K, the contribution of a specific state in the valence band manifold originating from the hybridized lone pair in nitrogen orbitals of the Phthalocyanine ring, bears the Brillouin-like signature of an exchange interaction with the localized d-shell Cu spins. A comprehensive MCD spectral analysis coupled with a molecular field model of a σπ - d exchange analogous to sp-d interactions in Diluted Magnetic Semiconductors (DMS) renders an enhanced Zeeman splitting and a modified g-factor of -4 for the electrons that mediate the interaction. These studies define an experimental tool for identifying electronic states involved in spin-dependent exchange interactions in organic materials.

Equilibrium structure of δ-Bi(2)O(3) from first principles.

PubMed

Music, Denis; Konstantinidis, Stephanos; Schneider, Jochen M

2009-04-29

Using ab initio calculations, we have systematically studied the structure of δ-Bi(2)O(3) (fluorite prototype, 25% oxygen vacancies) probing [Formula: see text] and combined [Formula: see text] and [Formula: see text] oxygen vacancy ordering, random distribution of oxygen vacancies with two different statistical descriptions as well as local relaxations. We observe that the combined [Formula: see text] and [Formula: see text] oxygen vacancy ordering is the most stable configuration. Radial distribution functions for these configurations can be classified as discrete (ordered configurations) and continuous (random configurations). This classification can be understood on the basis of local structural relaxations. Up to 28.6% local relaxation of the oxygen sublattice is present in the random configurations, giving rise to continuous distribution functions. The phase stability obtained may be explained with the bonding analysis. Electron lone-pair charges in the predominantly ionic Bi-O matrix may stabilize the combined [Formula: see text] and [Formula: see text] oxygen vacancy ordering.

Analysis of the bonding in XH3Cu+ (XB, Al, Ga) complexes

NASA Astrophysics Data System (ADS)

Corral, Inés; Mó, Otilia; Yáñez, Manuel

High-level density functional theory (DFT) calculations on XH3Cu+ (XB, Al, Ga) complexes show that the attachment of the metal cation to the base takes place through agostic-type interactions. These interactions that can be viewed as dative bonds from the σXH bonding orbitals of the base toward low-lying empty 4s orbitals of the metal cation, and back-donations from the lone pairs of the metal into the σ *XH antibonding orbitals of the neutral, are particularly favored when the XH bonds have a high X+δH-δ polarity. Accordingly, the AlH3 and GaH3 Cu+ binding energies are very similar, but much larger than that of BH3. Depopulation of the σXH bonding orbital and the concomitant population of the σ *XH antibonding orbital involved in the agostic interaction result in a significant weakening of the corresponding XH linkages, whose bond length increases and whose stretching frequency appears red-shifted.

A parallel implementation of the Wuchty algorithm with additional experimental filters to more thoroughly explore RNA conformational space.

PubMed

Stone, Jonathan W; Bleckley, Samuel; Lavelle, Sean; Schroeder, Susan J

2015-01-01

We present new modifications to the Wuchty algorithm in order to better define and explore possible conformations for an RNA sequence. The new features, including parallelization, energy-independent lonely pair constraints, context-dependent chemical probing constraints, helix filters, and optional multibranch loops, provide useful tools for exploring the landscape of RNA folding. Chemical probing alone may not necessarily define a single unique structure. The helix filters and optional multibranch loops are global constraints on RNA structure that are an especially useful tool for generating models of encapsidated viral RNA for which cryoelectron microscopy or crystallography data may be available. The computations generate a combinatorially complete set of structures near a free energy minimum and thus provide data on the density and diversity of structures near the bottom of a folding funnel for an RNA sequence. The conformational landscapes for some RNA sequences may resemble a low, wide basin rather than a steep funnel that converges to a single structure.

A DFT study of ethanol adsorption and decomposition on α-Al2O3(0 0 0 1) surface

NASA Astrophysics Data System (ADS)

Chiang, Hsin-Ni; Nachimuthu, Santhanamoorthi; Cheng, Ya-Chin; Damayanti, Nur Pradani; Jiang, Jyh-Chiang

2016-02-01

Ethanol adsorption and decomposition on the clean α-Al2O3(0 0 0 1) surface have been systematically investigated by density functional theory calculations. The nature of the surface-ethanol bonding has studied through the density of states (DOS) and the electron density difference (EDD) contour plots. The DOS patterns confirm that the lone pair electrons of EtOH are involved in the formation of a surface Alsbnd O dative bond and the EDD plots provide evidences for the bond weakening/forming, which are consistent with the DOS analysis. Our ethanol decomposition results indicate that ethanol dehydration to ethylene (CH3CH2OH(a) → C2H4(g) + OH(a) + H(a)), is the main reaction pathway with the energy barrier of 1.46 eV. Although the cleavage of the hydroxyl group of ethanol has lower energy barrier, the further decomposition of ethoxy owns much higher energy barrier.

Lewis acid-base interactions in weakly bound formaldehyde complexes with CO2, HCN, and FCN: considerations on the cooperative H-bonding effects.

PubMed

Rivelino, Roberto

2008-01-17

Ab initio quantum chemistry calculations reveal that HCN and mainly FCN can form Lewis acid-base complexes with formaldehyde associated with cooperative H bonds, as first noticed by Wallen et al. (Blatchford, M. A.; Raveendran, P.; Wallen, S. L. J. Am. Chem. Soc. 2002, 124, 14818-14819) for CO2-philic materials under supercritical conditions. The present results, obtained with MP2(Full)/aug-cc-pVDZ calculations, show that the degeneracy of the nu(2) mode in free HCN or FCN is removed upon complexation in the same fashion as that of CO2. The splitting of these bands along with the electron structure analysis provides substantial evidence of the interaction of electron lone pairs of the carbonyl oxygen with the electron-deficient carbon atom of the cyanides. Also, this work investigates the role of H bonds acting as additional stabilizing interactions in the complexes by performing the energetic and geometric characterization.

A computational study of dimers and trimers of nitrosyl hydride: Blue shift of NH bonds that are involved in H-bond and orthogonal interactions

NASA Astrophysics Data System (ADS)

Solimannejad, Mohammad; Massahi, Shokofeh; Alkorta, Ibon

2009-07-01

Ab initio calculations at MP2/aug-cc-pVTZ level were used to analyze the interactions between nitrosyl hydride (HNO) dimers and trimers. The structures obtained have been analyzed with the Atoms in Molecules (AIMs) and Natural Bond Orbital (NBO) methodologies. Four minima were located on the potential energy surface of the dimers. Nine different structures have been obtained for the trimers. Three types of interactions are observed, NH⋯N and NH⋯O hydrogen bonds and orthogonal interaction between the lone pair of the oxygen with the electron-deficient region of the nitrogen atom. Stabilization energies of dimers and trimers including BSSE and ZPE are in the range 4-8 kJ mol -1 and 12-19 kJ mol -1, respectively. Blue shift of NH bond upon complex formation in the ranges between 30-80 and 14,114 cm -1 is predicted for dimers and trimers, respectively.

Spin Exchange Interaction in Substituted Copper Phthalocyanine Crystalline Thin Films

PubMed Central

Rawat, Naveen; Pan, Zhenwen; Lamarche, Cody J.; Wetherby, Anthony; Waterman, Rory; Tokumoto, Takahisa; Cherian, Judy G.; Headrick, Randall L.; McGill, Stephen A.; Furis, Madalina I.

2015-01-01

The origins of spin exchange in crystalline thin films of Copper Octabutoxy Phthalocyanine (Cu-OBPc) are investigated using Magnetic Circular Dichroism (MCD) spectroscopy. These studies are made possible by a solution deposition technique which produces highly ordered films with macroscopic grain sizes suitable for optical studies. For temperatures lower than 2 K, the contribution of a specific state in the valence band manifold originating from the hybridized lone pair in nitrogen orbitals of the Phthalocyanine ring, bears the Brillouin-like signature of an exchange interaction with the localized d-shell Cu spins. A comprehensive MCD spectral analysis coupled with a molecular field model of a σπ − d exchange analogous to sp-d interactions in Diluted Magnetic Semiconductors (DMS) renders an enhanced Zeeman splitting and a modified g-factor of −4 for the electrons that mediate the interaction. These studies define an experimental tool for identifying electronic states involved in spin-dependent exchange interactions in organic materials. PMID:26559337

Spin Exchange Interaction in Substituted Copper Phthalocyanine Crystalline Thin Films.

PubMed

Rawat, Naveen; Pan, Zhenwen; Lamarche, Cody J; Wetherby, Anthony; Waterman, Rory; Tokumoto, Takahisa; Cherian, Judy G; Headrick, Randall L; McGill, Stephen A; Furis, Madalina I

2015-11-12

The origins of spin exchange in crystalline thin films of Copper Octabutoxy Phthalocyanine (Cu-OBPc) are investigated using Magnetic Circular Dichroism (MCD) spectroscopy. These studies are made possible by a solution deposition technique which produces highly ordered films with macroscopic grain sizes suitable for optical studies. For temperatures lower than 2 K, the contribution of a specific state in the valence band manifold originating from the hybridized lone pair in nitrogen orbitals of the Phthalocyanine ring, bears the Brillouin-like signature of an exchange interaction with the localized d-shell Cu spins. A comprehensive MCD spectral analysis coupled with a molecular field model of a σπ - d exchange analogous to sp-d interactions in Diluted Magnetic Semiconductors (DMS) renders an enhanced Zeeman splitting and a modified g-factor of -4 for the electrons that mediate the interaction. These studies define an experimental tool for identifying electronic states involved in spin-dependent exchange interactions in organic materials.

Antiprismatic Coordination about Xenon: The Structure of Nitrosonium Octafluoroxenate(VI).

PubMed

Peterson, S W; Holloway, J H; Coyle, B A; Williams, J M

1971-09-24

The structure of nitrosonium octafluoroxenate(VI), 2NOF . XeF(6), has been determined by means of single-crystal x-ray counter methods (R-index = 0.046, weighted R-index = 0.042). The space group is Pnma, with a = 8.914(10) angstroms, b = 5.945(10) angstroms, and c = 12.83(2) angstroms (the numbers in parentheses are the standard deviations to the least significant digit or digits); the calculated density (rho) is 3.354 grams per cubic centimeter, and there are four formula units per unit cell. The material consists of well-separated NO(+) and (XeF(8))(2-) ions; the structural formula is thus (NO)(2) (XeF(8)). The anion configuration is that of a slightly distorted Archimedean antiprism. The observed distortion appears incompatible with a lone-pair repulsion model. Xenon-fluorine bond lengths of 1.971(7), 1.946(5), 1.958(7), 2.052(5), and 2.099(5) angstroms were found.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuz'mina, L. G.; Fedorova, O. A.; Andryukhina, E. N.

A comparative study of the molecular geometry and crystal packing of crown-containing styryl heterocycles and their dimethoxy substituted analogues is performed. It is established that all the compounds exhibit an identical type of distortions of the geometry of the central styryl fragment. These are the localization of the {pi}-electron density at the ethylene bond and the bond alternation in a half of the phenyl ring due to the conjugation of lone electron pairs of the oxygen substituents with the chromophore system of the molecule. A comparative analysis of the crystal packings of the compounds reveals extended separate hydrophilic and hydrophobicmore » regions. The hydrophilic regions are built of crown ether fragments, and the hydrophobic regions consist of {pi}-conjugated and aromatic molecular fragments. The hydrophobic regions are characterized by a wide variety of packing motifs, among which stacking packing is absent. For two compounds, the formation of sandwich dimers that are preorganized to enter into the photochemical [2 + 2]cycloaddition reaction is observed.« less

Theoretical study of adsorption of organic phosphines on transition metal surfaces

NASA Astrophysics Data System (ADS)

Lou, Shujie; Jiang, Hong

2018-04-01

The adsorption properties of organic phosphines on transition metal (TM) surfaces (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) have been studied to explore the possibility of building novel heterogeneous chiral catalytic systems based on organic phosphines. Preferred adsorption sites, adsorption energies and surface electronic structures of a selected set of typical organic phosphines adsorbed on TM surfaces are calculated with density-functional theory to obtain a systematic understanding on the nature of adsorption interactions. All organic phosphines considered are found to chemically adsorb on these TM surfaces with the atop site as the most preferred one, and the TM-P bond is formed via the lone-pair electrons of the P atom and the directly contacted TM atom. These findings imply that it is indeed possible to build heterogeneous chiral catalytic systems based on organic phosphines adsorbed on TM surfaces, which, however, requires a careful design of molecular structure of organic phosphines.

A new force field including charge directionality for TMAO in aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Usui, Kota; Nagata, Yuki, E-mail: sulpizi@uni-mainz.de, E-mail: nagata@mpip-mainz.mpg.de; Hunger, Johannes

We propose a new force field for trimethylamine N-oxide (TMAO), which is designed to reproduce the long-lived and highly directional hydrogen bond between the TMAO oxygen (O{sub TMAO}) atom and surrounding water molecules. Based on the data obtained by ab initio molecular dynamics simulations, we introduce three dummy sites around O{sub TMAO} to mimic the O{sub TMAO} lone pairs and we migrate the negative charge on the O{sub TMAO} to the dummy sites. The force field model developed here improves both structural and dynamical properties of aqueous TMAO solutions. Moreover, it reproduces the experimentally observed dependence of viscosity upon increasingmore » TMAO concentration quantitatively. The simple procedure of the force field construction makes it easy to implement in molecular dynamics simulation packages and makes it compatible with the existing biomolecular force fields. This paves the path for further investigation of protein-TMAO interaction in aqueous solutions.« less

Structural transition and amorphization in compressed α - Sb 2 O 3

DOE PAGES

Zhao, Zhao; Zeng, Qiaoshi; Zhang, Haijun; ...

2015-05-27

Sb₂O₃-based materials are of broad interest in materials science and industry. High-pressure study using diamond anvil cells shows promise in obtaining new crystal and electronic structures different from their pristine states. Here, we conducted in situ angle dispersive synchrotron x-ray-diffraction and Raman spectroscopy experiments on α-Sb₂O₃ up to 50 GPa with neon as the pressure transmitting medium. A first-order structural transition was observed in between 15 and 20 GPa, where the cubic phase I gradually transformed into a layered tetragonal phase II through structural distortion and symmetry breaking. To explain the dramatic changes in sample color and transparency, we performedmore » first-principles calculations to track the evolution of its density of states and electronic structure under pressure. At higher pressure, a sluggish amorphization was observed. Our results highlight the structural connections among the sesquioxides, where the lone electron pair plays an important role in determining the local structures.« less

Regioselectivity of pyridine deprotonation in the gas phase.

PubMed

Schafman, Bonnie S; Wenthold, Paul G

2007-03-02

The regioselective deprotonation of pyridine in the gas phase has been investigated by using chemical reactivity studies. The mixture of regioisomers, trapped as carboxylates, formed in an equilibrium mixture is determined to result from 70-80% deprotonation in the 4-position, and 20-30% deprotonation at the 3-position. The ion formed by deprotonation in the 2-position is not measurably deprotonated at equilibrium because the ion is destabilized by lone-pair repulsion. From the composition of the mixture, the gas-phase acidities (DeltaH degrees acid) at the 4-, 3-, and 2-positions are determined to be 389.9 +/- 2.0, 391.2-391.5, and >391.5 kcal/mol, respectively. The relative acidities of the 4- and 3-positions are explained by using Hammett-Taft parameters, derived by using the measured gas-phase acidities of pyridine carboxylic acids. The values of sigmaF and sigmaR are -0.18 and 0.74, respectively, showing the infused nitrogen in pyridine to have a strong pi electron-withdrawing effect, but with little sigma-inductive effect.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trump, Benjamin A., E-mail: btrump1@jhu.edu; Department of Physics and Astronomy, Institute for Quantum Matter, Johns Hopkins University, Baltimore, MD 21218; McQueen, Tyrel M., E-mail: mcqueen@jhu.edu

The synthesis and physical properties of the new distorted-Hollandite PbIr{sub 4}Se{sub 8} are reported. Powder X-ray diffraction and transmission electron microscopy show that the structure consists of edge- and corner-sharing IrSe{sub 6} octahedra, with one-dimensional channels occupied by Pb. The structure contains Se-Se anion-anion bonding, leading to an electron count of Pb{sup 2+}(Ir{sup 3+}){sub 4}(Se{sub 2}){sup 2-}(Se{sup 2−}){sub 6}, confirmed by bond-valence sums and diamagnetic behavior. Structural and heat capacity measurements demonstrate disorder on the Pb site, due to the combination of lone-pair effects and the large size of the one-dimensional channels. Comparisons are made to known Hollandite and pseudo-Hollanditemore » structures, which demonstrates that the anion-anion bonding in PbIr{sub 4}Se{sub 8} distorts its structure, to accommodate the Ir{sup 3+} state. An electronic structure calculation indicates semiconductor character with a band gap of 0.76(11) eV.« less

Ontology aided modeling of organic reaction mechanisms with flexible and fragment based XML markup procedures.

PubMed

Sankar, Punnaivanam; Aghila, Gnanasekaran

2007-01-01

The mechanism models for primary organic reactions encoding the structural fragments undergoing substitution, addition, elimination, and rearrangements are developed. In the proposed models, each and every structural component of mechanistic pathways is represented with flexible and fragment based markup technique in XML syntax. A significant feature of the system is the encoding of the electron movements along with the other components like charges, partial charges, half bonded species, lone pair electrons, free radicals, reaction arrows, etc. needed for a complete representation of reaction mechanism. The rendering of reaction schemes described with the proposed methodology is achieved with a concise XML extension language interoperating with the structure markup. The reaction scheme is visualized as 2D graphics in a browser by converting them into SVG documents enabling the desired layouts normally perceived by the chemists conventionally. An automatic representation of the complex patterns of the reaction mechanism is achieved by reusing the knowledge in chemical ontologies and developing artificial intelligence components in terms of axioms.

Prediction of the electron redundant SinNn fullerenes

NASA Astrophysics Data System (ADS)

Yang, Huihui; Song, Yan; Zhang, Yan; Chen, Hongshan

2018-05-01

The stabilities and electronic structures of SimAln-mNn and SinNn (n = 16, 20, m = 12 and n = 24, m = 16) fullerene-like cages have been investigated using density functional method B3LYP and the second-order perturbation theory MP2. The results show that the SimAln-mNn and SinNn fullerenes are more stable than the AlN counterparts. Comparing with the corresponding AlnNn cages, one silicon atom in each Si2N2 square protrudes and the excess electrons reside as lone pair electrons at the outside of the protrudent Si atoms. Analyses on the electronic structures suggest that the Sisbnd N bonds are covalent bonding with strong polarity. The ELF (electron localization function) shows large electron pair probability between Si and N atoms. The orbital interactions between Si and N are stronger than that between Al and N atoms; the overlap integral is 0.40 per Sisbnd N bond in SinNn and 0.34 per Alsbnd N bond in AlnNn. The AIM (atoms in molecule) charges on the Al atoms in AlnNn and SimAln-mNn are 2.37 and 2.40. The charges on the in-plane and protrudent Si atoms are about 2.88 and 1.50 respectively. Considering the large local dipole moments around the protrudent Si atoms, the electrostatic interactions are also favorable to the SiN cages.

Reengaging the Indonesian Kopassus; Looking at the Long-Term Approach and Getting it Right

DTIC Science & Technology

2013-06-13

as the U.S.S.R. collapsed leaving the U.S. as the world’s lone super-power. The Kopassus reorganized under a model fashioned after the British SAS in...of war, as the U.S. has been integrally involved in the Middle East. The biggest point Haass makes is that the U.S. has been a lone super power...fourth most populous country on the planet , Indonesia’s economic importance is on the rise as well. Indonesia’s economy continues to grow, not yet

Lone Propeller

NASA Image and Video Library

2017-09-15

This view of Saturn's A ring features a lone "propeller" -- one of many such features created by small moonlets embedded in the rings as they attempt, unsuccessfully, to open gaps in the ring material. The image was taken by NASA's Cassini spacecraft on Sept. 13, 2017. It is among the last images Cassini sent back to Earth. The view was taken in visible light using the Cassini spacecraft wide-angle camera at a distance of 420,000 miles (676,000 kilometers) from Saturn. Image scale is 2.3 miles (3.7 kilometers). https://photojournal.jpl.nasa.gov/catalog/PIA21894

Sex differences in Portuguese lonely hearts advertisements.

PubMed

Neto, Félix

2005-10-01

Advertisements from "Lonely Hearts" columns in the major daily Portuguese newspaper (Jornal de Notícias) were used to test hypotheses about the mate preferences of men and women. A total of 484 advertisements were coded for demographic descriptors and offers of and appeals for attractiveness, financial security, sincerity, expressiveness, and instrumentality, e.g., intelligence and ambition. Some results supported social exchange and evolutionary predictions: men sought younger women and offered security; women sought older men with status and resources. However, other results challenged such predictions: attractiveness and expressiveness did not differ by sex.

Loneliness and Social Internet Use: Pathways to Reconnection in a Digital World?

PubMed

Nowland, Rebecca; Necka, Elizabeth A; Cacioppo, John T

2018-01-01

With the rise of online social networking, social relationships are increasingly developed and maintained in a digital domain. Drawing conclusions about the impact of the digital world on loneliness is difficult because there are contradictory findings, and cross-sectional studies dominate the literature, making causation difficult to establish. In this review, we present our theoretical model and propose that there is a bidirectional and dynamic relationship between loneliness and social Internet use. When the Internet is used as a way station on the route to enhancing existing relationships and forging new social connections, it is a useful tool for reducing loneliness. But when social technologies are used to escape the social world and withdraw from the "social pain" of interaction, feelings of loneliness are increased. We propose that loneliness is also a determinant of how people interact with the digital world. Lonely people express a preference for using the Internet for social interaction and are more likely to use the Internet in a way that displaces time spent in offline social activities. This suggests that lonely people may need support with their social Internet use so that they employ it in a way that enhances existing friendships and/or to forge new ones.

Transcription of All amoC Copies Is Associated with Recovery ofNitrosomonas europaea from Ammonia Starvation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berube, Paul M.; Samudrala, Ram; Stahl, David A.

2007-09-21

The chemolithotrophic ammonia-oxidizing bacteriumNitrosomonas europaea is known to be highly resistant to starvationconditions. The transcriptional response of N. europaea to ammoniaaddition following short- and long-term starvation was examined by primerextension and S1 nuclease protection analyses of genes encoding enzymesfor ammonia oxidation (amoCAB operons) and CO2 fixation (cbbLS), a third,lone copy of amoC (amoC3), and two representative housekeeping genes(glyA and rpsJ). Primer extension analysis of RNA isolated from growing,starved, and recovering cells revealed two differentially regulatedpromoters upstream of the two amoCAB operons. The distal sigma 70 typeamoCAB promoter was constitutively active in the presence of ammonia, butthe proximal promoter was onlymore » active when cells were recovering fromammonia starvation. The lone, divergent copy of amoC (amoC3) wasexpressed only during recovery. Both the proximal amoC1,2 promoter andthe amoC3 promoter are similar to gram-negative sigma E promoters, thusimplicating sigma E in the regulation of the recovery response. Althoughmodeling of subunit interactions suggested that a nonconservative prolinesubstitution in AmoC3 may modify the activity of the holoenzyme,characterization of a Delta amoC3 strain showed no significant differencein starvation recovery under conditions evaluated. In contrast to the amotranscripts, a delayed appearance of transcripts for a gene required forCO2 fixation (cbbL) suggested that its transcription is retarded untilsufficient energy is available. Overall, these data revealed a programmedexit from starvation likely involving regulation by sigma E and thecoordinated regulation of catabolic and anabolic genes.« less

Childhood adversity, parental vulnerability and disorder: examining inter-generational transmission of risk.

PubMed

Bifulco, A; Moran, P M; Ball, C; Jacobs, C; Baines, R; Bunn, A; Cavagin, J

2002-11-01

An investigation of intergenerational factors associated with psychiatric disorder in late adolescence/early adulthood was undertaken to differentiate influences from maternal disorder, maternal poor psychosocial functioning and poor parenting, on offspring. The sample comprised an intensively studied series of 276 mother-offspring pairs in a relatively deprived inner-city London area with high rates of lone parenthood and socio-economic disadvantage. The paired sample was collected over two time periods: first a consecutively screened series of mothers and offspring in 1985-90 (n = 172 pairs) and second a 'vulnerable' series of mothers and offspring in 1995-99 (n = 104 pairs). The vulnerable mothers were selected for poor interpersonal functioning and/or low self-esteem and the consecutive series were used for comparison. Rates of childhood adversity and disorder in the offspring were examined in the two groups. Maternal characteristics including psychosocial vulnerability and depression were then examined in relation to risk transmission. Offspring of vulnerable mothers had a fourfold higher rate of yearly disorder than those in the comparison series (43% vs. 11%, p < .001). They were twice as likely as those in the comparison series to have experienced childhood adversity comprising either severe neglect, physical or sexual abuse before age 17. Physical abuse, in particular, perpetrated either by mother or father/surrogate father was significantly raised in the vulnerable group. Analysis of the combined series showed that maternal vulnerability and neglect/abuse of offspring provided the best model for offspring disorder. Maternal history of depression had no direct effect on offspring disorder; its effects were entirely mediated by offspring neglect/abuse. Maternal childhood adversity also had no direct effect. Results are discussed in relation to psychosocial models of risk transmission for disorder. Maternal poor psychosocial functioning needs to be identified as a factor requiring intervention in order to stem escalation of risk across generations.

Intramolecular competition between n-pair and π-pair hydrogen bonding: Microwave spectrum and internal dynamics of the pyridine–acetylene hydrogen-bonded complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mackenzie, Rebecca B.; Dewberry, Christopher T.; Leopold, Kenneth R., E-mail: A.C.Legon@bristol.ac.uk, E-mail: david.tew@bristol.ac.uk, E-mail: kleopold@umn.edu

2015-09-14

a-type rotational spectra of the hydrogen-bonded complex formed from pyridine and acetylene are reported. Rotational and {sup 14}N hyperfine constants indicate that the complex is planar with an acetylenic hydrogen directed toward the nitrogen. However, unlike the complexes of pyridine with HCl and HBr, the acetylene moiety in HCCH—NC{sub 5}H{sub 5} does not lie along the symmetry axis of the nitrogen lone pair, but rather, forms an average angle of 46° with the C{sub 2} axis of the pyridine. The a-type spectra of HCCH—NC{sub 5}H{sub 5} and DCCD—NC{sub 5}H{sub 5} are doubled, suggesting the existence of a low lying pairmore » of tunneling states. This doubling persists in the spectra of HCCD—NC{sub 5}H{sub 5}, DCCH—NC{sub 5}H{sub 5}, indicating that the underlying motion does not involve interchange of the two hydrogens of the acetylene. Single {sup 13}C substitution in either the ortho- or meta-position of the pyridine eliminates the doubling and gives rise to separate sets of spectra that are well predicted by a bent geometry with the {sup 13}C on either the same side (“inner”) or the opposite side (“outer”) as the acetylene. High level ab initio calculations are presented which indicate a binding energy of 1.2 kcal/mol and a potential energy barrier of 44 cm{sup −1} in the C{sub 2v} configuration. Taken together, these results reveal a complex with a bent hydrogen bond and large amplitude rocking of the acetylene moiety. It is likely that the bent equilibrium structure arises from a competition between a weak hydrogen bond to the nitrogen (an n-pair hydrogen bond) and a secondary interaction between the ortho-hydrogens of the pyridine and the π electron density of the acetylene.« less

Providing web-based mental health services to at-risk women

PubMed Central

2011-01-01

Background We examined the feasibility of providing web-based mental health services, including synchronous internet video conferencing of an evidence-based support/education group, to at-risk women, specifically poor lone mothers. The objectives of this study were to: (i) adapt a face-to-face support/education group intervention to a web-based format for lone mothers, and (ii) evaluate lone mothers' response to web-based services, including an online video conferencing group intervention program. Methods Participating mothers were recruited through advertisements. To adapt the face-to-face intervention to a web-based format, we evaluated participant motivation through focus group/key informant interviews (n = 7), adapted the intervention training manual for a web-based environment and provided a computer training manual. To evaluate response to web-based services, we provided the intervention to two groups of lone mothers (n = 15). Pre-post quantitative evaluation of mood, self-esteem, social support and parenting was done. Post intervention follow up interviews explored responses to the group and to using technology to access a health service. Participants received $20 per occasion of data collection. Interviews were taped, transcribed and content analysis was used to code and interpret the data. Adherence to the intervention protocol was evaluated. Results Mothers participating in this project experienced multiple difficulties, including financial and mood problems. We adapted the intervention training manual for use in a web-based group environment and ensured adherence to the intervention protocol based on viewing videoconferencing group sessions and discussion with the leaders. Participant responses to the group intervention included decreased isolation, and increased knowledge and confidence in themselves and their parenting; the responses closely matched those of mothers who obtained same service in face-to-face groups. Pre-and post-group quantitative evaluations did not show significant improvements on measures, although the study was not powered to detect these. Conclusions We demonstrated that an evidence-based group intervention program for lone mothers developed and evaluated in face-to-face context transferred well to an online video conferencing format both in terms of group process and outcomes. PMID:21854563

Providing web-based mental health services to at-risk women.

PubMed

Lipman, Ellen L; Kenny, Meghan; Marziali, Elsa

2011-08-19

We examined the feasibility of providing web-based mental health services, including synchronous internet video conferencing of an evidence-based support/education group, to at-risk women, specifically poor lone mothers. The objectives of this study were to: (i) adapt a face-to-face support/education group intervention to a web-based format for lone mothers, and (ii) evaluate lone mothers' response to web-based services, including an online video conferencing group intervention program. Participating mothers were recruited through advertisements. To adapt the face-to-face intervention to a web-based format, we evaluated participant motivation through focus group/key informant interviews (n = 7), adapted the intervention training manual for a web-based environment and provided a computer training manual. To evaluate response to web-based services, we provided the intervention to two groups of lone mothers (n = 15). Pre-post quantitative evaluation of mood, self-esteem, social support and parenting was done. Post intervention follow up interviews explored responses to the group and to using technology to access a health service. Participants received $20 per occasion of data collection. Interviews were taped, transcribed and content analysis was used to code and interpret the data. Adherence to the intervention protocol was evaluated. Mothers participating in this project experienced multiple difficulties, including financial and mood problems. We adapted the intervention training manual for use in a web-based group environment and ensured adherence to the intervention protocol based on viewing videoconferencing group sessions and discussion with the leaders. Participant responses to the group intervention included decreased isolation, and increased knowledge and confidence in themselves and their parenting; the responses closely matched those of mothers who obtained same service in face-to-face groups. Pre-and post-group quantitative evaluations did not show significant improvements on measures, although the study was not powered to detect these. We demonstrated that an evidence-based group intervention program for lone mothers developed and evaluated in face-to-face context transferred well to an online video conferencing format both in terms of group process and outcomes.

Density functional investigation of the adsorption effects of PH3 and SH2 on the structure stability of the Au55 and Pt55 nanoclusters

NASA Astrophysics Data System (ADS)

Guedes-Sobrinho, Diego; Chaves, Anderson S.; Piotrowski, Maurício J.; Da Silva, Juarez L. F.

2017-04-01

Although several studies have been reported for Pt55 and Au55 nanoclusters, our atomistic understanding of the interplay between the adsorbate-surface interactions and the mechanisms that lead to the formation of the distorted reduced core (DRC) structures, instead of the icosahedron (ICO) structure in gas phase, is still far from satisfactory. Here, we report a density functional theory (DFT) investigation of the role of the adsorption effects of PH3 (one lone pair of electrons) and SH2 (two lone pairs) on the relative stability of the Pt55 and Au55 nanoclusters. In gas phase, we found that the DRC structures with 7 and 9 atoms in the core region are about 5.34 eV (Pt55) and 2.20 eV (Au55) lower in energy than the ICO model with Ih symmetry and 13 atoms in the core region. However, the stability of the ICO structure increases by increasing the number of adsorbed molecules from 1 to 18, in which both DRC and ICO structures are nearly degenerate in energy at the limit of 18 ligands, which can be explained as follows. In gas phase, there is a strong compression of the cationic core region by the anionic surface atoms induced by the attractive Coulomb interactions (core+-surface-), and hence, the strain release is obtained by reducing the number of atoms in the cationic core region, which leads to the 55 atoms distorted reduced core structures. Thus, the Coulomb interactions between the core+ and surface- contribute to break the symmetry in the ICO55 structure. On the other hand, the addition of ligands on the anionic surface reduces the charge transfer between the core and surface, which contributes to decrease the Coulomb interactions and the strain on the core region of the ICO structure, and hence, it stabilizes a compact ICO structure. The same conclusion is obtained by adding van der Waals corrections to the plain DFT calculations. Similar results are obtained by the addition of steric effects, which are considered through the adsorption of triphenylphosphine (PPh3) molecules on Au55, in which the relative stability between ICO and DRC is the same as for PH3 and SH2. However, for Pt55, we found an inversion of stability due to the PPh3 ligand effects, where ICO has higher stability than DRC by 2.40 eV. Our insights are supported by several structural, electronic, and energetic analyses.

Density functional investigation of the adsorption effects of PH3 and SH2 on the structure stability of the Au55 and Pt55 nanoclusters.

PubMed

Guedes-Sobrinho, Diego; Chaves, Anderson S; Piotrowski, Maurício J; Da Silva, Juarez L F

2017-04-28

Although several studies have been reported for Pt 55 and Au 55 nanoclusters, our atomistic understanding of the interplay between the adsorbate-surface interactions and the mechanisms that lead to the formation of the distorted reduced core (DRC) structures, instead of the icosahedron (ICO) structure in gas phase, is still far from satisfactory. Here, we report a density functional theory (DFT) investigation of the role of the adsorption effects of PH 3 (one lone pair of electrons) and SH 2 (two lone pairs) on the relative stability of the Pt 55 and Au 55 nanoclusters. In gas phase, we found that the DRC structures with 7 and 9 atoms in the core region are about 5.34 eV (Pt 55 ) and 2.20 eV (Au 55 ) lower in energy than the ICO model with I h symmetry and 13 atoms in the core region. However, the stability of the ICO structure increases by increasing the number of adsorbed molecules from 1 to 18, in which both DRC and ICO structures are nearly degenerate in energy at the limit of 18 ligands, which can be explained as follows. In gas phase, there is a strong compression of the cationic core region by the anionic surface atoms induced by the attractive Coulomb interactions (core + -surface - ), and hence, the strain release is obtained by reducing the number of atoms in the cationic core region, which leads to the 55 atoms distorted reduced core structures. Thus, the Coulomb interactions between the core + and surface - contribute to break the symmetry in the ICO 55 structure. On the other hand, the addition of ligands on the anionic surface reduces the charge transfer between the core and surface, which contributes to decrease the Coulomb interactions and the strain on the core region of the ICO structure, and hence, it stabilizes a compact ICO structure. The same conclusion is obtained by adding van der Waals corrections to the plain DFT calculations. Similar results are obtained by the addition of steric effects, which are considered through the adsorption of triphenylphosphine (PPh 3 ) molecules on Au 55 , in which the relative stability between ICO and DRC is the same as for PH 3 and SH 2 . However, for Pt 55 , we found an inversion of stability due to the PPh 3 ligand effects, where ICO has higher stability than DRC by 2.40 eV. Our insights are supported by several structural, electronic, and energetic analyses.

Structural mechanism of enoyl-CoA hydratase: three atoms from a single water are added in either an E1cb stepwise or concerted fashion.

PubMed

Bahnson, Brian J; Anderson, Vernon E; Petsko, Gregory A

2002-02-26

We have determined the crystal structure of the enzyme enoyl-CoA hydratase (ECH) from rat liver with the bound substrate 4-(N,N-dimethylamino)cinnamoyl-CoA using X-ray diffraction data to a resolution of 2.3 A. In addition to the thiolester substrate, the catalytic water, which is added in the hydration reaction, has been modeled into well-defined electron density in each of the six active sites of the physiological hexamer within the crystallographic asymmetric unit. The catalytic water bridges Glu(144) and Glu(164) of the enzyme and has a lone pair of electrons poised to react with C(3) of the enzyme-bound alpha,beta-unsaturated thiolester. The water molecule, which bridges two glutamate residues, is reminiscent of the enolase active site. However, unlike enolase, which has a lysine available to donate a proton, there are no other sources of protons available from other active site residues in ECH. Furthermore, an analysis of the hydrogen-bonding network of the active site suggests that both Glu(144) and Glu(164) are ionized and carry a negative charge with no reasonable place to have a protonated carboxylate. This lack of hydrogen-bonding acceptors that could accommodate a source of a proton, other than from the water molecule, leads to a hypothesis that the three atoms from a single water molecule are added across the double bond to form the hydrated product. The structural results are discussed in connection with details of the mechanism, which have been elucidated from kinetics, site-directed mutagenesis, and spectroscopy of enzyme-substrate species, in presenting an atomic-resolution mechanism of the reaction. Contrary to the previous interpretation, the structure of the E-S complex together with previously determined kinetic isotope effects is consistent with either a concerted mechanism or an E1cb stepwise mechanism.

Loneliness in senior housing communities.

PubMed

Taylor, Harry Owen; Wang, Yi; Morrow-Howell, Nancy

2018-05-23

There are many studies on loneliness among community-dwelling older adults; however, there is limited research examining the extent and correlates of loneliness among older adults who reside in senior housing communities. This study examines the extent and correlates of loneliness in three public senior housing communities in the St. Louis area. Data for this project was collected with survey questionnaires with a total sample size of 148 respondents. Loneliness was measured using the Hughes 3-item loneliness scale. Additionally, the questionnaire contained measures on socio-demographics, health/mental health, social engagement, and social support. Missing data for the hierarchical multivariate regression models were imputed using multiple imputation methods. Results showed approximately 30.8% of the sample was not lonely, 42.7% was moderately lonely, and 26.6% was severely lonely. In the multivariate analyses, loneliness was primarily associated with depressive symptoms. Contrary to popular opinion, our study found the prevalence of loneliness was high in senior housing communities. Nevertheless, senior housing communities could be ideal locations for reducing loneliness among older adults. Interventions should focus on concomitantly addressing both an individual's loneliness and mental health.

Lone star tick abundance, fire, and bison grazing in tall-grass prairie

USGS Publications Warehouse

Cully, J.F.

1999-01-01

Lone star ticks (Amblyomma americanum L.) were collected by drag samples of 1 km transects on 12 watersheds at Konza Prairie Research Natural Area near Manhattan, Kans., during summer 1995-1996. Watersheds were treated to 2 experimental treatments: 3 burn intervals (1-year, 4-year, and 20-year) and 2 grazing treatments (grazed by bison (Bos bison L.) or ungrazed). The objectives were to determine whether fire interval, time since most recent burn, and the presence of large ungulate grazers would cause changes in lone star tick abundance in tallgrass prairie in central Kansas. Watersheds burned at 1-year intervals had fewer larvae and adults than watersheds burned at 4-year or 20-year intervals. Watersheds burned during the year of sampling had fewer ticks than watersheds burned one or more years in the past. For watersheds burned 1 or more years in the past there was no effect from time since burn. The presence of bison did not affect tick abundance. Spring burning is an effective method to reduce tick populations in tallgrass prairie during the year of the burn.

Investigating hypervigilance for social threat of lonely children.

PubMed

Qualter, Pamela; Rotenberg, Ken; Barrett, Louise; Henzi, Peter; Barlow, Alexandra; Stylianou, Maria; Harris, Rebecca A

2013-02-01

The hypothesis that lonely children show hypervigilance for social threat was examined in a series of three studies that employed different methods including advanced eye-tracking technology. Hypervigilance for social threat was operationalized as hostility to ambiguously motivated social exclusion in a variation of the hostile attribution paradigm (Study 1), scores on the Children's Rejection-Sensitivity Questionnaire (Study 2), and visual attention to socially rejecting stimuli (Study 3). The participants were 185 children (11 years-7 months to 12 years-6 months), 248 children (9 years-4 months to 11 years-8 months) and 140 children (8 years-10 months to 12 years-10 months) in the three studies, respectively. Regression analyses showed that, with depressive symptoms covaried, there were quadratic relations between loneliness and these different measures of hypervigilance to social threat. As hypothesized, only children in the upper range of loneliness demonstrated elevated hostility to ambiguously motivated social exclusion, higher scores on the rejection sensitivity questionnaire, and disengagement difficulties when viewing socially rejecting stimuli. We found that very lonely children are hypersensitive to social threat.

Multiple pruritic papules from lone star tick larvae bites.

PubMed

Fisher, Emily J; Mo, Jun; Lucky, Anne W

2006-04-01

Ticks are the second most common vectors of human infectious diseases in the world. In addition to their role as vectors, ticks and their larvae can also produce primary skin manifestations. Infestation by the larvae of ticks is not commonly recognized, with only 3 cases reported in the literature. The presence of multiple lesions and partially burrowed 6-legged tick larvae can present a diagnostic challenge for clinicians. We describe a 51-year-old healthy woman who presented to our clinic with multiple erythematous papules and partially burrowed organisms 5 days after exposure to a wooded area in southern Kentucky. She was treated with permethrin cream and the lesions resolved over the following 3 weeks without sequelae. The organism was later identified as the larva of Amblyomma species, the lone star tick. Multiple pruritic papules can pose a diagnostic challenge. The patient described herein had an unusually large number of pruritic papules as well as tick larvae present on her skin. Recognition of lone star tick larvae as a cause of multiple bites may be helpful in similar cases.

Single parents of children with chronic illness: an understudied phenomenon.

PubMed

Brown, Ronald T; Wiener, Lori; Kupst, Mary Jo; Brennan, Tara; Behrman, Richard; Compas, Bruce E; David Elkin, T; Fairclough, Diane L; Friebert, Sarah; Katz, Ernest; Kazak, Anne E; Madan-Swain, Avi; Mansfield, Nancy; Mullins, Larry L; Noll, Robert; Patenaude, Andrea Farkas; Phipps, Sean; Sahler, O J; Sourkes, Barbara; Zeltzer, Lonnie

2008-05-01

To examine the chronic illness literature and evaluate the impact on single parenting and children and adolescents with chronic illness. We conducted literature reviews of relevant research pertaining to single-parent families on PubMed, Medline, and PsychINFO and also surveyed pertinent book chapters and all of the articles from the Journal of Pediatric Psychology since 1987 for articles, specifically examining the potential associations of single (lone) parenting versus two-parent households on children's psychosocial functioning and the impact of the child's illness on caregiver functioning. While the literature has examined and discussed the stressors associated with parenting a child with an illness, including the impact of illness on finances, family roles, and caregiver burden, few studies have examined single parents of children and adolescents with chronic illnesses and related stressors stemming from being a lone caregiver. There is a dearth of studies examining the association between lone parenting and psychosocial functioning among children and adolescents with chronic illnesses. Specific questions necessitating future investigation are summarized and recommendations are made for future research in this important area of inquiry.

Loneliness at the Top: Ten Ways Medical Practice Administrators Can Manage the Isolation of Leadership.

PubMed

Hills, Laura

2016-01-01

Medical practice.managers spend their days surrounded by people, so the last thing they may expect to feel is lonely. Yet for many, being the manager of a medical practice can lead to feelings of isolation from the rest of the staff, and loneliness. This article explores the many reasons that managing a medical practice can be a lonely business. It considers the risks when a practice manager's loneliness goes unchecked, both to the individual and to the practice. It suggests 10 effective and healthy strategies for preventing and managing the leadership loneliness that medical practice managers sometimes experience. Next, this article argues that acceptance is the first step in overcoming loneliness in the workplace. It offers guidance for medical practice managers who wish to help lonely members of their teams. It describes the benefits of having a confidant to help support the medical practice manager, and the characteristics of an ideal confidant. Finally, this article suggests a strategy for combatting loneliness by interacting with the staff more frequently.

A mediation model linking dispatcher leadership and work ownership with safety climate as predictors of truck driver safety performance.

PubMed

Zohar, Dov; Huang, Yueng-hsiang; Lee, Jin; Robertson, Michelle

2014-01-01

The study was designed to test the effect of safety climate on safety behavior among lone employees whose work environment promotes individual rather than consensual or shared climate perceptions. The paper presents a mediation path model linking psychological (individual-level) safety climate antecedents and consequences as predictors of driving safety of long-haul truck drivers. Climate antecedents included dispatcher (distant) leadership and driver work ownership, two contextual attributes of lone work, whereas its proximal consequence included driving safety. Using a prospective design, safety outcomes, consisting of hard-braking frequency (i.e. traffic near-miss events) were collected six months after survey completion, using GPS-based truck deceleration data. Results supported the hypothesized model, indicating that distant leadership style and work ownership promote psychological safety climate perceptions, with subsequent prediction of hard-braking events mediated by driving safety. Theoretical and practical implications for studying safety climate among lone workers in general and professional drivers in particular are discussed. Copyright © 2013 Elsevier Ltd. All rights reserved.

Molecular docking, TG/DTA, molecular structure, harmonic vibrational frequencies, natural bond orbital and TD-DFT analysis of diphenyl carbonate by DFT approach

NASA Astrophysics Data System (ADS)

Xavier, S.; Periandy, S.; Carthigayan, K.; Sebastian, S.

2016-12-01

Vibrational spectral analysis of Diphenyl Carbonate (DPC) is carried out by using FT-IR and FT-Raman spectroscopic techniques. It is found that all vibrational modes are in the expected region. Gaussian computational calculations were performed using B3LYP method with 6-311++G (d, p) basis set. The computed geometric parameters are in good agreement with XRD data. The observation shows that the structure of the carbonate group is unsymmetrical by ∼5° due to the attachment of the two phenyl rings. The stability of the molecule arising from hyperconjugative interaction and charge delocalization are analyzed by Natural Bond Orbital (NBO) study and the results show the lone pair transition has higher stabilization energy compared to all other. The 1H and 13C NMR chemical shifts are calculated using the Gauge-Including Atomic Orbital (GIAO) method with B3LYP/6-311++G (d, p) method. The chemical shifts computed theoretically go very closer to the experimental results. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies and Molecular electrostatic potential (MEP) exhibit the high reactivity nature of the molecule. The non-linear optical property of the DPC molecule predicted theoretically found to be good candidate for NLO material. TG/DTA analysis was made and decomposition of the molecule with respect to the temperature was studied. DPC having the anthelmintic activity is docked in the Hemoglobin of Fasciola hepatica protein. The DPC has been screened to antimicrobial activity and found to exhibit antibacterial effects.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neu, Mary Patricia

The coordination chemistry and solution behavior of the toxic ions lead(II) and plutonium(IV, V, VI) have been investigated. The ligand pK as and ligand-lead(II) stability constants of one hydroxamic acid and four thiohydroaxamic acids were determined. Solution thermodynamic results indicate that thiohydroxamic acids are more acidic and slightly better lead chelators than hydroxamates, e.g., N-methylthioaceto-hydroxamic acid, pK a = 5.94, logβ 120 = 10.92; acetohydroxamic acid, pK a = 9.34, logβ 120 = 9.52. The syntheses of lead complexes of two bulky hydroxamate ligands are presented. The X-ray crystal structures show the lead hydroxamates are di-bridged dimers with irregular five-coordinatemore » geometry about the metal atom and a stereochemically active lone pair of electrons. Molecular orbital calculations of a lead hydroxamate and a highly symmetric pseudo octahedral lead complex were performed. The thermodynamic stability of plutonium(IV) complexes of the siderophore, desferrioxamine B (DFO), and two octadentate derivatives of DFO were investigated using competition spectrophotometric titrations. The stability constant measured for the plutonium(IV) complex of DFO-methylterephthalamide is logβ 120 = 41.7. The solubility limited speciation of 242Pu as a function of time in near neutral carbonate solution was measured. Individual solutions of plutonium in a single oxidation state were added to individual solutions at pH = 6.0, T = 30.0, 1.93 mM dissolved carbonate, and sampled over intervals up to 150 days. Plutonium solubility was measured, and speciation was investigated using laser photoacoustic spectroscopy and chemical methods.« less

Direct Growth of CuO Nanorods on Graphitic Carbon Nitride with Synergistic Effect on Thermal Decomposition of Ammonium Perchlorate.

PubMed

Tan, Linghua; Xu, Jianhua; Li, Shiying; Li, Dongnan; Dai, Yuming; Kou, Bo; Chen, Yu

2017-05-02

Novel graphitic carbon nitride/CuO (g-C₃N₄/CuO) nanocomposite was synthesized through a facile precipitation method. Due to the strong ion-dipole interaction between copper ions and nitrogen atoms of g-C₃N₄, CuO nanorods (length 200-300 nm, diameter 5-10 nm) were directly grown on g-C₃N₄, forming a g-C₃N₄/CuO nanocomposite, which was confirmed via X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS). Finally, thermal decomposition of ammonium perchlorate (AP) in the absence and presence of the prepared g-C₃N₄/CuO nanocomposite was examined by differential thermal analysis (DTA), and thermal gravimetric analysis (TGA). The g-C₃N₄/CuO nanocomposite showed promising catalytic effects for the thermal decomposition of AP. Upon addition of 2 wt % nanocomposite with the best catalytic performance (g-C₃N₄/20 wt % CuO), the decomposition temperature of AP was decreased by up to 105.5 °C and only one decomposition step was found instead of the two steps commonly reported in other examples, demonstrating the synergistic catalytic activity of the as-synthesized nanocomposite. This study demonstrated a successful example regarding the direct growth of metal oxide on g-C₃N₄ by ion-dipole interaction between metallic ions, and the lone pair electrons on nitrogen atoms, which could provide a novel strategy for the preparation of g-C₃N₄-based nanocomposite.

Big wigs and small wigs: Time, sex, size and shelter affect cohabitation in the maritime earwig (Anisolabis maritima).

PubMed

Hack, Nicole L; Iyengar, Vikram K

2017-01-01

Animal aggregations can occur for a variety of abiotic factors, such as resource limitation, or biotic factors, including group foraging and protection from predators. In our study, we examined whether time, sex, body size or shelter availability affected aggregation behavior of the maritime earwig, Anisolabis maritima (Order Dermaptera), an insect found globally at high densities under driftwood. Specifically, we monitored the distribution of two individuals in arenas with either two shelters (no habitat limitation) or one shelter (habitat limitation) to determine their propensity for cohabitation at times of peak activity and times of quiescence. Females, whose high levels of aggression are often associated with maternal care, were particularly averse to cohabitation, whereas males were generally more tolerant of other earwigs. Females initially preferred not to cohabitate when placed with a male, but were more tolerant of cohabitation later, regardless of the number of shelters. Same-sex pairs, on the other hand, were less likely to cohabitate with only one shelter present, but males were again more tolerant of conspecifics than females regardless of habitat limitation. When competition for one shelter did not lead to cohabitation, the lone occupant was more likely to be the larger individual in same-sex trials and females in mixed-sex trials. Understanding the tolerance for close proximity under these varying conditions may provide insight into aggregative behavior and spatial distribution patterns in the maritime earwig.

Coordination geometry of lead carboxylates - spectroscopic and crystallographic evidence.

PubMed

Catalano, Jaclyn; Murphy, Anna; Yao, Yao; Yap, Glenn P A; Zumbulyadis, Nicholas; Centeno, Silvia A; Dybowski, Cecil

2015-02-07

Despite their versatility, only a few single-crystal X-ray structures of lead carboxylates exist, due to difficulties with solubility. In particular, the structures of long-chain metal carboxylates have not been reported. The lone electron pair in Pb(ii) can be stereochemically active or inactive, leading to two types of coordination geometries commonly referred to as hemidirected and holodirected structures, respectively. We report (13)C and (207)Pb solid-state NMR and infrared spectra for a series of lead carboxylates, ranging from lead hexanoate (C6) to lead hexadecanoate (C18). The lead carboxylates based on consistent NMR parameters can be divided in two groups, shorter-chain (C6, C7, and C8) and longer-chain (C9, C10, C11, C12, C14, C16, and C18) carboxylates. This dichotomy suggests two modes of packing in these solids, one for the short-chain lead carboxylates and one for long-chain lead carboxylates. The consistency of the (13)C and (207)Pb NMR parameters, as well as the IR data, in each group suggests that each motif represents a structure characteristic of each subgroup. We also report the single-crystal X-ray diffraction structure of lead nonanoate (C9), the first single-crystal structure to have been reported for the longer-chain subgroup. Taken together the evidence suggests that the coordination geometry of C6-C8 lead carboxylates is hemidirected, and that of C9-C14, C16 and C18 lead carboxylates is holodirected.

Presentations to the Emergency Department Following Cannabis use--a Multi-Centre Case Series from Ten European Countries.

PubMed

Dines, Alison M; Wood, David M; Galicia, Miguel; Yates, Christopher M; Heyerdahl, Fridtjof; Hovda, Knut Erik; Giraudon, Isabelle; Sedefov, Roumen; Dargan, Paul I

2015-12-01

Cannabis is the most commonly used illicit drug in Europe, and is generally regarded as having low acute toxicity. We present the findings of the first 6 months of data collection from the Euro-DEN project on presentations related to cannabis use to further understand the acute toxicity related to the use of cannabis. Data was extracted on clinical features, treatment and outcome from the Euro-DEN minimum dataset for all cases of acute recreational drug toxicity reported 1st October 2013 to 31st March 2014 for all cannabis-related presentations. Of 2198 presentations reported by 14 of the 16 Euro-DEN centres, 356 (16.2 %) involved cannabis either alone or together with other drugs/alcohol. There were 36 that involved lone use of cannabis (1.6 % of all presentations). Of the 35 non-fatal lone cannabis presentations, the most commonly reported features were neuro-behavioural (agitation/aggression 8 (22.9 %), psychosis 7 (20.0 %), anxiety 7 (20.0 %)) and vomiting 6 (17.1 %). Most patients (25, 71.4 %) received no treatment and 30 (85.7 %) were discharged/self-discharged from the ED. There was one fatality amongst these lone-cannabis cases: an 18-year-old male collapsed with an asystolic cardiac arrest whilst smoking cannabis and suffered hypoxic brain injury related to prolonged cardiac arrest. THC was detected in a urine sample taken at ED arrival; no other drugs were detected. Lone acute cannabis toxicity was typically associated with neuro-behavioural symptoms and vomiting. Although uncommon, severe toxicity including cardiovascular toxicity and death may be under-recognised, and it is important that Emergency Physicians are aware of this.

Do low-income lone mothers compromise their nutrition to feed their children?

PubMed Central

McIntyre, Lynn; Glanville, N. Theresa; Raine, Kim D.; Dayle, Jutta B.; Anderson, Bonnie; Battaglia, Noreen

2003-01-01

Background Women who live in disadvantaged circumstances in Canada exhibit dietary intakes below recommended levels, but their children often do not. One reason for this difference may be that mothers modify their own food intake to spare their children nutritional deprivation. The objective of our study was to document whether or not low-income lone mothers compromise their own diets to feed their children. Methods We studied 141 low-income lone mothers with at least 2 children under the age of 14 years who lived in Atlantic Canada. Women were identified through community organizations using a variety of recruitment strategies. The women were asked weekly for 1 month to recall their food intake over the previous 24 hours; they also reported their children's (n = 333) food intake. Mothers also completed a questionnaire about “food insecurity,” that is, a lack of access to adequate, nutritious food through socially acceptable means, during each interview. Results Household food insecurity was reported by 78% of mothers during the study month. Mothers' dietary intakes and the adequacy of intake were consistently poorer than their children's intake overall and over the course of a month. The difference in adequacy of intake between mothers and children widened from Time 1, when the family had the most money to purchase food, to Time 4, when the family had the least money. The children experienced some improvement in nutritional intake at Time 3, which was possibly related to food purchases for them associated with receipt of the Child Tax Benefit Credit or the Goods and Services Tax Credit. Interpretation Our study demonstrates that low-income lone mothers compromise their own nutritional intake in order to preserve the adequacy of their children's diets. PMID:12642423

Comparison of Atrial Fibrillation in the Young versus That in the Elderly: A Review

PubMed Central

Sankaranarayanan, Rajiv; Kirkwood, Graeme; Dibb, Katharine; Garratt, Clifford J.

2013-01-01

The incidence and prevalence of atrial fibrillation (AF) are projected to increase significantly worldwide, imposing a significant burden on healthcare resources. The disease itself is extremely heterogeneous in its epidemiology, pathophysiology, and treatment options based on individual patient characteristics. Whilst ageing is well recognised to be an independent risk factor for the development of AF, this condition also affects the young in whom the condition is frequently symptomatic and troublesome. Traditional thinking suggests that the causal factors and pathogenesis of the condition in the young with structurally normal atria but electrophysiological “triggers” in the form of pulmonary vein ectopics leading to lone AF are in stark contrast to that in the elderly who have AF primarily due to an abnormal substrate consisting of fibrosed and dilated atria acting in concert with the pulmonary vein triggers. However, there can be exceptions to this rule as there is increasing evidence of structural and electrophysiological abnormalities in the atrial substrate in young patients with “lone AF,” as well as elderly patients who present with idiopathic AF. These reports seem to be blurring the distinction in the pathophysiology of so-called idiopathic lone AF in the young versus that in the elderly. Moreover with availability of improved and modern investigational and diagnostic techniques, novel causes of AF are being reported thereby seemingly consigning the diagnosis of “lone AF” to a rather mythical existence. We shall also elucidate in this paper the differences seen in the epidemiology, causes, pathogenesis, and clinical features of AF in the young versus that seen in the elderly, thereby requiring clearly defined management strategies to tackle this arrhythmia and its associated consequences. PMID:23401843

Examining rare and low-frequency genetic variants previously associated with lone or familial forms of atrial fibrillation in an electronic medical record system: a cautionary note.

PubMed

Weeke, Peter; Denny, Joshua C; Basterache, Lisa; Shaffer, Christian; Bowton, Erica; Ingram, Christie; Darbar, Dawood; Roden, Dan M

2015-02-01

Studies in individuals or small kindreds have implicated rare variants in 25 different genes in lone and familial atrial fibrillation (AF) using linkage and segregation analysis, functional characterization, and rarity in public databases. Here, we used a cohort of 20 204 patients of European or African ancestry with electronic medical records and exome chip data to compare the frequency of AF among carriers and noncarriers of these rare variants. The exome chip included 19 of 115 rare variants, in 9 genes, previously associated with lone or familial AF. Using validated algorithms querying a combination of clinical notes, structured billing codes, ECG reports, and procedure codes, we identified 1056 AF cases (>18 years) and 19 148 non-AF controls (>50 years) with available genotype data on the Illumina HumanExome BeadChip v.1.0 in the Vanderbilt electronic medical record-linked DNA repository, BioVU. Known correlations between AF and common variants at 4q25 were replicated. None of the 19 variants previously associated with AF were over-represented among AF cases (P>0.1 for all), and the frequency of variant carriers among non-AF controls was >0.1% for 14 of 19. Repeat analyses using non-AF controls aged >60 (n=14 904), >70 (n=9670), and >80 (n=4729) years did not influence these findings. Rare variants previously implicated in lone or familial forms of AF present on the exome chip are detected at low frequencies in a general population but are not associated with AF. These findings emphasize the need for caution when ascribing variants as pathogenic or causative. © 2014 American Heart Association, Inc.

Refuge or predation risk? Alternate ways to perceive hiker disturbance based on maternal state of female caribou.

PubMed

Lesmerises, Frédéric; Johnson, Chris J; St-Laurent, Martin-Hugues

2017-02-01

Human presence in natural environments is often a source of stress that is perceived by large ungulates as an increased risk of predation. Alternatively, disturbance induced by hikers creates a relatively predator-free space that may serve as a refuge. We measured the behavioral responses of female caribou to disturbance associated with the presence of hikers during summer in the Gaspésie National Park. We used those data to determine whether caribou responded negatively to human activity (i.e., the predation risk hypothesis ) or whether human activity resulted in a decrease in the magnitude of perceived risk (i.e., the refuge hypothesis ). Female caribou with a calf spent nearly half of their time feeding, regardless of the presence of a trail or the number of hikers. They also decreased their vigilance near trails when the number of hikers increased. Conversely, lone females fed less frequently and almost doubled the time invested in vigilance under the same circumstances. However, both groups of females moved away from trails during the day, especially in the presence of hikers. We demonstrated that risk avoidance was specific to the maternal state of the individual. Lactating females accommodated the presence of hikers to increase time spent foraging and nutritional intake, providing support for the refuge hypothesis. Alternatively, lone females with lower energetic requirements and no maternal investment in a vulnerable calf appeared less tolerant to risk, consistent with the predation risk hypothesis. Synthesis and applications : Hikers influenced the vigilance-feeding trade-off in caribou, underlining the importance of appropriate management of linear structures and human activities, especially across the critical habitat of endangered species. Even if some individuals seemed to benefit from human presence, this behavioral adaptation was not sufficient to reduce annual calf mortality associated with predation.

[THE ROLE OF SOCIAL WORK IN PROVIDING LIVELIHOODS AND VITAL ACTIVITY OF OLDER PEOPLE IN RURAL AREAS OF THE REPUBLIC OF KAZAKHSTAN].

PubMed

Zhilibaev, F P; Dzhunusova, Zh Kh

2015-01-01

Forms of improvement of domestic conditions of elderly citizens, the organization of their medical and social care, rest and leisure are analyzed in the article. It is necessary to expand a network of non-stationary establishments and social care services to aged citizens and disabled people, to improve their support and involve the new forms of service. Foreign experience, in particular on the creation of social houses for lonely elderly citizens and married couples of senior age is offered to use.

Boxer crabs induce asexual reproduction of their associated sea anemones by splitting and intraspecific theft.

PubMed

Schnytzer, Yisrael; Giman, Yaniv; Karplus, Ilan; Achituv, Yair

2017-01-01

Crabs of the genus Lybia have the remarkable habit of holding a sea anemone in each of their claws. This partnership appears to be obligate, at least on the part of the crab. The present study focuses on Lybia leptochelis from the Red Sea holding anemones of the genus Alicia (family Aliciidae). These anemones have not been found free living, only in association with L. leptochelis . In an attempt to understand how the crabs acquire them, we conducted a series of behavioral experiments and molecular analyses. Laboratory observations showed that the removal of one anemone from a crab induces a "splitting" behavior, whereby the crab tears the remaining anemone into two similar parts, resulting in a complete anemone in each claw after regeneration. Furthermore, when two crabs, one holding anemones and one lacking them, are confronted, the crabs fight, almost always leading to the "theft" of a complete anemone or anemone fragment by the crab without them. Following this, crabs "split" their lone anemone into two. Individuals of Alicia sp. removed from freshly collected L. leptochelis were used for DNA analysis. By employing AFLP (Fluorescence Amplified Fragments Length Polymorphism) it was shown that each pair of anemones from a given crab is genetically identical. Furthermore, there is genetic identity between most pairs of anemone held by different crabs, with the others showing slight genetic differences. This is a unique case in which one animal induces asexual reproduction of another, consequently also affecting its genetic diversity.

Barriers to Social Participation among Lonely Older Adults: The Influence of Social Fears and Identity

PubMed Central

Goll, Johanna C.; Charlesworth, Georgina; Scior, Katrina; Stott, Joshua

2015-01-01

Introduction Loneliness among older adults is a major public health problem that may be associated with processes of social participation and identity. This study therefore sought to examine the relationship between social participation and identity in a sample of lonely older adults living independently in London, England. Method An inductive qualitative approach, based on semi-structured interviews and thematic analysis, was employed. Results Participants commonly spoke of barriers to social participation that have been reported elsewhere, including illness/disability, loss of contact with friends/relatives, lack of a supportive community, and lack of acceptable social opportunities. However, novel findings were also derived. In particular, participants commonly minimised the difficulties they faced alone, and described attempts to avoid social opportunities. These behaviours were linked to fears about engaging in social participation opportunities, including fears of social rejection and/or exploitation, and fears of losing valued aspects of identity. Discussion It is concluded that social participation amongst lonely older people will not improve through the removal of previously reported barriers alone; instead, older peoples’ beliefs, fears and identities must be addressed. Suggestions for implementing these findings within community organisations are provided. PMID:25706933

Using participatory research to challenge the status quo for women's cardiovascular health.

PubMed

Young, Lynne; Wharf Higgins, Joan

2010-12-01

Cardiovascular health research has been dominated by medical and patriarchal paradigms, minimizing a broader perspective of causes of disease. Socioeconomic status as a risk for cardiovascular disease is well established by research, yet these findings have had little influence. Participatory research (PR) that frames mixed method research has potential to bring contextualized clinically relevant findings into program planning and policy-making arenas toward developing meaningful health and social policies relevant to primary prevention. In this article we provide an overview of a PR program that included two quantitative and one qualitative studies and then we discuss lessons learned. The PR process we found was empowering for lone mothers, and transformative for lone mothers and researchers. Further, PR as an approach to research opened spaces in practice and policy-making arenas to raise upstream issues relevant to the health of low income lone mothers. We conclude that while PR is an effective approach to social determinants research, as a time-intensive endeavor, and one that does not easily align with research tradition, researchers must consider the strengths and drawbacks of PR when planning to implement such an approach. © 2010 Blackwell Publishing Ltd.

Post-incarceration Recidivism of Lone versus Group Juvenile Homicide Offenders.

PubMed

Khachatryan, Norair; Heide, Kathleen M; Rad, Jordyn; Hummel, Erich V

2016-11-01

Killings by juvenile homicide offenders (JHOs) who use accomplices have been increasing since the 1980s and currently represent approximately half of juvenile arrests for murder in the United States. Nevertheless, prior research has not compared JHOs who kill alone with JHOs who kill in groups. The present research followed up 30 years later on a sample of 59 male murderers and attempted murderers sentenced to adult prison. This study was designed to analyze whether lone and group JHOs differed on pre-incarceration, incarceration, and post-incarceration variables. Significant findings indicated that compared with lone offenders, group JHOs had a higher mean of pre-homicide arrests and were more likely to be Black, have a pre-homicide delinquent record, commit a crime-related homicide offense, and target a stranger. With respect to post-homicide variables, group JHOs were more likely to be released from prison and more likely to be rearrested. The two types of JHOs did not differ significantly in relation to the number of post-release violent offenses. Preliminary implications of the findings and avenues for future investigation are discussed. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Work–Family Trajectories and the Higher Cardiovascular Risk of American Women Relative to Women in 13 European Countries

PubMed Central

van Hedel, Karen; Mejía-Guevara, Iván; Avendaño, Mauricio; Sabbath, Erika L.; Berkman, Lisa F.; Mackenbach, Johan P.

2016-01-01

Objectives. To investigate whether less-healthy work–family life histories contribute to the higher cardiovascular disease prevalence in older American compared with European women. Methods. We used sequence analysis to identify distinct work–family typologies for women born between 1935 and 1956 in the United States and 13 European countries. Data came from the US Health and Retirement Study (1992–2006) and the Survey of Health, Aging, and Retirement in Europe (2004–2009). Results. Work–family typologies were similarly distributed in the United States and Europe. Being a lone working mother predicted a higher risk of heart disease, stroke, and smoking among American women, and smoking for European women. Lone working motherhood was more common and had a marginally stronger association with stroke in the United States than in Europe. Simulations indicated that the higher stroke risk among American women would only be marginally reduced if American women had experienced the same work–family trajectories as European women. Conclusions. Combining work and lone motherhood was more common in the United States, but differences in work–family trajectories explained only a small fraction of the higher cardiovascular risk of American relative to European women. PMID:27310346

Work-Family Trajectories and the Higher Cardiovascular Risk of American Women Relative to Women in 13 European Countries.

PubMed

van Hedel, Karen; Mejía-Guevara, Iván; Avendaño, Mauricio; Sabbath, Erika L; Berkman, Lisa F; Mackenbach, Johan P; van Lenthe, Frank J

2016-08-01

To investigate whether less-healthy work-family life histories contribute to the higher cardiovascular disease prevalence in older American compared with European women. We used sequence analysis to identify distinct work-family typologies for women born between 1935 and 1956 in the United States and 13 European countries. Data came from the US Health and Retirement Study (1992-2006) and the Survey of Health, Aging, and Retirement in Europe (2004-2009). Work-family typologies were similarly distributed in the United States and Europe. Being a lone working mother predicted a higher risk of heart disease, stroke, and smoking among American women, and smoking for European women. Lone working motherhood was more common and had a marginally stronger association with stroke in the United States than in Europe. Simulations indicated that the higher stroke risk among American women would only be marginally reduced if American women had experienced the same work-family trajectories as European women. Combining work and lone motherhood was more common in the United States, but differences in work-family trajectories explained only a small fraction of the higher cardiovascular risk of American relative to European women.

Synthesis and crystal structure of new copper(II) metal complex: Noncovalent interactions and electrical conductance properties

NASA Astrophysics Data System (ADS)

Pathak, Sudipta; Chakraborty, Koushik; Ghosh, Surajit; Roy, Kunal; Jana, Barnali; Konar, Saugata

2018-01-01

[Cu(pydc)(apyz)(H2O)2] (1) (where pydcH2 = pyridine-2,6-dicarboxylic acid; apyz = 2- aminopyrazine) has been synthesized and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction techniques. Crystallographic analysis revealed that complex 1 has distorted octahedral geometry with pydcH2 coordinated as tridentate ligands to metal ion through two oxygen atoms of each carboxylate group, nitrogen atom of the pyridine ring and the auxiliary ligand pyrazine nitrogen atom form basal plane and apical positions are occupied by two oxygen atoms of water molecules. In addition, the coordination compounds are connected by a variety of non covalent interactions like OH … π, lone pair … π, π … π and hydrogen bonds. The evaluation of these noncovalent interactions is useful for rationalizing their influence in the crystal packing. In addition, electrical current measured at room temperature on thin film before and after annealed is in the order of 229 μA and 246 μA respectively with bias voltage 1 V.

Fast detection of toxic industrial compounds by laser ion mobility spectrometry

NASA Astrophysics Data System (ADS)

Oberhuettinger, Carola; Langmeier, Andreas; Oberpriller, Helmut; Kessler, Matthias; Goebel, Johann; Mueller, Gerhard

2009-05-01

Trace detection of toxic industrial compounds has been investigated with the help of a laser ion mobility spectrometer (LIMS). The LIMS was equipped with a tuneable UV laser source for enabling two-photon ionization of the analyte gases and an ion drift tube for the measurement of the ion mobility. Different aromatic and aliphatic hydrocarbons as well as amines were investigated. We find that the first class of molecules can be well ionized due to the delocalization of their valence electron shells and the second due to the presence of non-bonding electrons in lone-pair orbitals. Selectivity of detection is attained on the basis of molecule-specific photo-ionization and drift time spectra. Ion currents were found to scale linearly with the substance concentration over several orders of magnitude down to the detection limits in the ppt range. As besides toxic industrial compounds, similar electron configurations also occur in illicit drugs, toxins and pharmaceutical substances, LIMS can be applied in a variety of fields ranging from environmental analysis, air pollution monitoring, drug detection and chemical process monitoring.

Origin of anomalous giant dielectric performance in novel perovskite: Bi0.5−xLaxNa0.5−xLixTi1−yMyO3 (M = Mg2+, Ga3+)

PubMed Central

Liu, Xiao; Fan, Huiqing; Shi, Jing; Li, Qiang

2015-01-01

Dielectric properties and dielectric relaxation behaviors of A/B sites co-substituted Bi0.5Na0.5TiO3 perovskite-type ferroelectrics are reported. The Bi0.5−xLaxNa0.5−xLixTi1−yMyO3 (M = Mg2+, Ga3+) exhibits anomalous giant dielectric permittivity (ε’) of ~105 under a heterogeneous constitution with easily discernible grain and grain boundary conductivity. The lone pairs substitution theory as well as extrinsic disorders are used to clarify the significant structural evolution and the origin of the dielectric performance. A bigger free volume promotes the anomalous relaxation between oxygen sites, and the polarization direction on the nanoscale deviates from the average polarization direction at its ferroelectric state. Furthermore, no obvious phase transition indicates the considerable static substitutional disorder at the Bi/Na sites, which facilitates delocalized conduction of oxygen ions in the intermediate temperature range. PMID:26239525

Origin of selenium–gold interaction in F{sub 2}CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH{sub 3}): Synergistic effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Xin; Yang, Yu-Ping; Li, Qing-Zhong, E-mail: liqingzhong1990@sina.com, E-mail: lihaibei@sdu.edu.cn

Selenium–gold interaction plays an important role in crystal materials, molecular self-assembly, and pharmacochemistry involving gold. In this paper, we unveiled the mechanism and nature of selenium–gold interaction by studying complexes F{sub 2}CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH{sub 3}). The results showed that the formation of selenium–gold interaction is mainly attributed to the charge transfer from the lone pair of Se atom to the Au—Y anti-bonding orbital. Energy decomposition analysis indicated that the polarization energy is nearly equivalent to or exceeds the electrostatic term in the selenium–gold interaction. Interestingly, the chalcogen–gold interaction becomes stronger with the increasemore » of chalcogen atomic mass in F{sub 2}CX⋯AuCN (X = O, S, Se, and Te). The cyclic ternary complexes are formed with the introduction of NH{sub 3} into F{sub 2}CSe⋯AuY, in which selenium–gold interaction is weakened and selenium–nitrogen interaction is strengthened due to the synergistic effects.« less

Study on conformational stability, molecular structure, vibrational spectra, NBO, TD-DFT, HOMO and LUMO analysis of 3,5-dinitrosalicylic acid by DFT techniques

NASA Astrophysics Data System (ADS)

Sebastian, S.; Sylvestre, S.; Jayabharathi, J.; Ayyapan, S.; Amalanathan, M.; Oudayakumar, K.; Herman, Ignatius A.

2015-02-01

In this work we analyzed the vibrational spectra of 3,5-dinitrosalicylic acid (3,5DNSA) molecule. The total energy of eight possible conformers can be calculated by Density Functional Theory with 6-31G(d,p) as basis set to find the most stable conformer. Computational result identify the most stable conformer of 3,5DNSA is C6. The assignments of the vibrational spectra have been carried out by computing Total Energy Distribution (TED). The molecular geometry, second order perturbation energies and Electron Density (ED) transfer from filled lone pairs of Lewis base to unfilled Lewis acid sites for 3,5-DNSA molecular analyzed on the basis of Natural Bond Orbital (NBO) analysis. The formation of inter and intramolecular hydrogen bonding between sbnd OH and sbnd COOH group gave the evidence for the formation of dimer formation for 3,5-DNSA molecule. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) complements with the experimental findings. The simulated spectra satisfactorily coincides with the experimental spectra.

Halogen Bonding versus Hydrogen Bonding: A Molecular Orbital Perspective

PubMed Central

Wolters, Lando P; Bickelhaupt, F Matthias

2012-01-01

We have carried out extensive computational analyses of the structure and bonding mechanism in trihalides DX⋅⋅⋅A− and the analogous hydrogen-bonded complexes DH⋅⋅⋅A− (D, X, A=F, Cl, Br, I) using relativistic density functional theory (DFT) at zeroth-order regular approximation ZORA-BP86/TZ2P. One purpose was to obtain a set of consistent data from which reliable trends in structure and stability can be inferred over a large range of systems. The main objective was to achieve a detailed understanding of the nature of halogen bonds, how they resemble, and also how they differ from, the better understood hydrogen bonds. Thus, we present an accurate physical model of the halogen bond based on quantitative Kohn–Sham molecular orbital (MO) theory, energy decomposition analyses (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. It appears that the halogen bond in DX⋅⋅⋅A− arises not only from classical electrostatic attraction but also receives substantial stabilization from HOMO–LUMO interactions between the lone pair of A− and the σ* orbital of D–X. PMID:24551497

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whittles, Thomas J.; Veal, Tim D.; Savory, Christopher N.

The earth-abundant material CuSbS 2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuInxGa (1-x)Se 2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from themore » antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.« less

Theoretical investigation of the magnetoelectric properties of Bi2NiTiO6

NASA Astrophysics Data System (ADS)

Patra, Lokanath; Ravindran, P.

2018-04-01

We report the first principle investigations on the structural, electronic, magnetic and ferroelectric properties of a Pb free double perovskite multiferroic Bi2NiTiO6 using density functional theory within the general gradient approximation (GGA) and GGA+U method. Our results show that Bi2NiTiO6 will be an insulator with G-type magnetic ordering in its ground state with Ni2+ in a high spin state and a spin moment of 1.741μB. The paraelectric phase stabilizes in nonmagnetic state with Ni2+ in low spin configuration showing that spin state transition plays an important role in strong magnetoelectric coupling in Bi2NiTiO6. The bonding characteristics of the constituents are analyzed with the help of partial density of states and Born effective charges. The presence of Ti ions at Ni sites suppresses the disproportionation observed in case of BiNiO3 and results in a noncentrosymmetric crystal structure. The coexistence of Bi 6s lone pair and Ti4+ d0 ions which brings covalency produces a polarization of 32 µCcm-2.

Origin of High Electronic Quality in Solar Cell Absorber CH3NH3PbI3

NASA Astrophysics Data System (ADS)

Yin, Wanjian; Shi, Tingting; Wei, Suhua; Yan, Yanfa

Thin-film solar cells based on CH3NH3PbI3 halide perovskites have recently shown remarkable performance. First-principle calculations and molecular dynamic simulations show that the structure of pristine CH3NH3PbI3 is much more disordered than the inorganic archetypal thin-film semiconductor CdTe. However, the structural disorders from thermal fluctuation, point defects and grain boundaries introduce rare deep defect states within the bandgaps; therefore, the material has high electronic quality. We have further shown that this unusually high electronic quality is attributed to the unique electronic structures of halide perovskite: the strong coupling between cation lone-pair Pb s orbitals and anion p orbitals and the large atomic size of constitute cation atoms. We further found that although CH3NH3PbI3 GBs do not introduce a deep gap state, the defect level close to the VBM can still act as a shallow hole trap state. Cl and O can spontaneously segregate into GBs and passivate those defect levels and deactivate the trap state.

Determination of the conformation of 2-hydroxy- and 2-aminobenzoic acid dimers using 13C NMR and density functional theory/natural bond order analysis: the central importance of the carboxylic acid carbon.

PubMed

Burnette, Ronald R; Weinhold, Frank

2006-07-20

The 13C chemical shift for the carboxylic acid carbon provides a powerful diagnostic probe to determine the preferred isomeric dimer structures of benzoic acid derivatives undergoing intra- and intermolecular H-bonding in the gas, solution and crystalline phases. We have employed hybrid density functional calculations and natural bond orbital analysis to elucidate the electronic origins of the observed 13C shieldings and their relationship to isomeric stability. We find that delocalizing interactions from the carbonyl oxygen lone pairs (nO) into vicinal carbon-oxygen and carbon-carbon antibonds (sigmaCO*,sigmaCC*) make critical contributions to the 13C shieldings, and these nO --> sigmaCO*, nO --> sigmaCC* interactions are in turn sensitive to the intramolecular interactions that dictate dimer structure and stability. The carboxyl carbon atom can thus serve as a useful detector of subtle structural and conformational features in this pharmacologically important class of carboxylic acid interactions.

Fun Is More Fun When Others Are Involved.

PubMed

Reis, Harry T; O'Keefe, Stephanie D; Lane, Richard D

2017-01-01

Fun activities are commonly sought and highly desired yet their affective side has received little scrutiny. The present research investigated two features of fun in two daily diary studies and one laboratory experiment. First, we examined the affective state associated with fun experiences. Second, we investigated the social context of fun, considering whether shared fun is more enjoyable than solitary fun. Findings from these studies indicated that fun is associated with both high-activation and low-activation positive affects, and that it is enhanced when experienced with others (especially friends). However, social fun was associated with increases in high-activation but not low-activation positive affect, suggesting that social interaction emphasizes energizing affective experiences. We also found that loneliness moderated the latter effects, such that lonely individuals received a weaker boost from shared compared to solitary fun. These results add to what is known about the impact of social contexts on affective experience.

Fun Is More Fun When Others Are Involved

PubMed Central

Reis, Harry T.; O'Keefe, Stephanie D.; Lane, Richard D.

2016-01-01

Fun activities are commonly sought and highly desired yet their affective side has received little scrutiny. The present research investigated two features of fun in two daily diary studies and one laboratory experiment. First, we examined the affective state associated with fun experiences. Second, we investigated the social context of fun, considering whether shared fun is more enjoyable than solitary fun. Findings from these studies indicated that fun is associated with both high-activation and low-activation positive affects, and that it is enhanced when experienced with others (especially friends). However, social fun was associated with increases in high-activation but not low-activation positive affect, suggesting that social interaction emphasizes energizing affective experiences. We also found that loneliness moderated the latter effects, such that lonely individuals received a weaker boost from shared compared to solitary fun. These results add to what is known about the impact of social contexts on affective experience. PMID:28919919

Spilt milk: an inter-sectoral partnership that failed to advance milk security for low-income lone mothers in Nova Scotia, Canada.

PubMed

McIntyre, Lynn; Glanville, N Theresa; Hilchie-Pye, Andrea

2011-03-01

Canadian agricultural policy supports higher milk prices. Consequently, poor families lack sufficient funds to purchase adequate quantities of milk. Low-income lone mothers in the Canadian province of Nova Scotia suggested their preferred strategies for improved access to milk. We then built inter-sectoral support for a policy intervention to address their recommendations. Our research-to-action process led to a policy dialogue focusing on an electronic smart card that would permit the delivery of lower-priced milk to poor households. While all agreed that milk insecurity was an important issue, the project ultimately failed because of the entrenched positions of influential stakeholder groups.

The Clinical Threat Assessment of the Lone-Actor Terrorist.

PubMed

Meloy, J Reid; Genzman, Jacqueline

2016-12-01

The Terrorist Radicalization Assessment Protocol (TRAP-18) is a structured professional judgment instrument for the assessment of individuals who present a concern for lone-actor terrorism. It consists of eight proximal warning behaviors and 10 distal characteristics. Previous research has demonstrated its interrater reliability and some concurrent and postdictive validity. In this article, TRAP-18 is retrospectively applied to the case of US Army psychiatrist and jihadist Malik Nidal Hasan, who committed a mass murder at Fort Hood, Texas in 2009. The strengths and limitations of TRAP-18 as a structured professional judgment instrument for mental health clinicians are discussed, and clinical risk management suggestions are made. Copyright © 2016 Elsevier Inc. All rights reserved.

The high pressure crystal structures of tin sulphate: a case study for maximal information recovery from 2D powder diffraction data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hinrichsen, Bernd; Dinnebier, Robert E.; Liu, Haozhe

2008-12-09

Our recently proposed method for automatic detection, calibration and evaluation of Debye-Scherrer ellipses using pattern recognition techniques and advanced signal filtering was applied to 2D powder diffraction data of tin sulphate in dependence on pressure. Three phase transitions towards higher pressure could be identified, and their respective crystal structures have been determined. The high pressure behaviour of the stereoactive lone pair of Sn{sup 2+} was investigated. At ambient conditions, SnSO{sub 4} crystallizes in a strongly distorted Barite structure type in space group Pnma (phase I). In the pressure range between P = 0.15 and P = 0.2 GPa, it exhibitsmore » a displacive second order phase transition into a structure with space group P112{sub 1}/a (phase II at P = 0.2 GPa: a = 8.7022(9) {angstrom}, b = 5.3393(5) {angstrom}, c = 7.0511(6) A, y = 89.90(1){sup o}). A second displacive phase transition occurs between P = 4.40 and P = 5.07 GPa into another structure with space group PI (phase III at P = 13.5 GPa: a = 8.067(3) {angstrom}, b = 5.141(2) {angstrom}, c = 6.609(2) {angstrom}, a = 90.56(3){sup o}, {beta} = 90.65(2){sup o}, y = 89.46(2){sup o}). A third displacive phase transition towards another crystal structure in space group P1 occurs between P = 13.6 and P = 15.3 GPa (phase IV at P = 20.5 GPa: a = 7.889(5) {angstrom}, b = 5.028(3) {angstrom}, c = 6.462(3) {angstrom}, a = 90.99(3){sup o}, {beta}=91.01(3){sup o}, y = 89.89(4){sup o}). A non-linear compression behaviour over the entire pressure range is observed, which can be described by three Vinet relations in the ranges from P = 0.21 to 4.4 GPa, from P = 5.07 to 13.55 GPa and from P = 15.26 to 20.5 GPa. The extrapolated bulk moduli of the high-pressure phases were determined to K{sub 0} = 48(1) GPa for phase II, K{sub 0} = 56(2) GPa for phase III, and K{sub 0} = 51(13) GPa for phase IV. The crystal structures of all phases are refined against X-ray powder diffraction data measured at several pressures between 0.15 and 20.5 GPa. The structural phase transitions of SnSO{sub 4} are mainly characterized by a reorientation of the SO{sub 4} tetrahedra, in order to optimize crystal packing. With increasing pressure, the lone pair which is localized at Sn{sup 2+} increasingly adopts pure s-character.« less

Insights on the interaction of Zn2 + cation with triazoles: Structures, bonding, electronic excitation and applications

NASA Astrophysics Data System (ADS)

Dahmani, R.; Ben Yaghlane, S.; Boughdiri, S.; Mogren Al-Mogren, M.; Prakash, M.; Hochlaf, M.

2018-03-01

At present, we investigate the structures, the stability, the bonding and the spectroscopy of the Zn2 +-triazole complexes (Zn2 +-Tz), which are subunits of triazolate based porous materials and Zn-enzymes. This theoretical work is performed using ab initio methods and density functional theory (DFT) where dispersion correction is included. Through these benchmarks, we establish the ability and reliability of M05-2X + D3 and PBE0 + D3 functionals for the correct description of Zn2 +-Tz bond since these DFTs lead to close agreement with post Hartree-Fock methods. Therefore, M05-2X + D3 and PBE0 + D3 functionals are recommended for the characterization of larger organometallic complexes formed by Zn and N-rich linkers. For Zn2 +-Tz, we found two stable σ-type complexes: (i) a planar structure where Zn2 + links to unprotonated nitrogen and (ii) an out-of-plane cluster where carbon interacts with Zn2 +. The most stable isomers consist on a coordinated covalent bond between the lone pair of unprotonated nitrogen and the vacant 4 s orbital of Zn2 +. The roles of covalent interactions within these complexes are discussed after vibrational, NBO, NPA charges and orbital analyses. The bonding is dominated by charge transfer from Zn2 + to Tz and intramolecular charge transfer, which plays a vital role for the catalytic activity of these complexes. These findings are important to understand, at the microscopic level, the structure and the bonding within triazolate based macromolecular porous materials and Zn-enzymes.

Features of electronic structure of hypovalent lithides ALi/sub k/ and ALi/sub k+1//sup +/

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klimenko, N.M.; Mebel', A.M.; Charkin, O.P.

The features of the chemical bonding and the behavior of the original energies of the lithides ALi/sub k/ and ALi/sub K+1//sup +/ have been analyzed on the basis of nonempirical calculations in the MP3/(DZHD + P/sub A/) approximation. It has been found that the new A-Li bond appearing upon the addition of Li/sup +/ to Ali/sub k/ is formed with the participation of only the p/sub A/ AO's from the atom A. In contrast to the case of the hydrides AK/sub k/ and the fluorides AF/sub k/, in the case of the lithides ALi/sub k/ and ALi/sub k+1//sup +/, themore » lone pair of the atom A consists of its almost pure s/sub A/ AO, which maintains its spherical shape, is not active stereochemically, and practically does not participate in the bonding. The lithides ALi/sub k/ and Ali/sub k+1//sup +/ (such as CLi/sub 2/, Cli/sub 3//sup +/, NLi/sub 3/, NLi/sub 4//sup +/, OLi/sub 2/, OLi/sub 3//sup +/, Fli, Fli/sub 2//sup +/, etc.) may be classified as hypovalent compounds, in which the number of valence AO's of the atom A participating in the bonding is smaller than the number of atoms of Li directly bonded to the atom A. The bonding in them is delocalized over all the atoms comparing the molecule, and the two-center approach and Gillespie's rules are, in principle, not suitable.« less

How adolescents construct their future: the effect of loneliness on future orientation.

PubMed

Seginer, Rachel; Lilach, Efrat

2004-12-01

This study examined the effect of loneliness, gender, and two dimensions of prospective life domains on adolescent future orientation. Future orientation was studied in four prospective domains: social relations, marriage and family, higher education and work and career. These domains are described in terms of two dimensions: theme (relational vs. instrumental) and distance (near vs. distant future). Data collected from Israeli Jewish adolescents (11th graders) were analysed by repeated measures ANOVAs and ANCOVAs (covariate: depressive experiences) for seven future orientation variables: value, expectance, control (motivational variables), hopes, fears (cognitive representation variables), exploration, commitment (behavioural variables). As predicted, lonely adolescents scored lower than socially embedded adolescents on future orientation variables applied to the relational and near future domains and lonely boys scored lower than lonely girls. However, effects were found only on the three future orientation motivational variables and not on the cognitive representation and behavioural variables. Contrary to prediction controlling for the effect of depressive experiences did not reduce the effect of loneliness on the future orientation variables, but reduced the tendency of adolescents to score higher on all future orientation variables in the instrumental than in the relational prospective domains. The contribution of these findings to the understanding of adolescent loneliness and future orientation was discussed and directions for future research were suggested.

Sedimentary facies of the upper Cambrian (Furongian; Jiangshanian and Sunwaptan) Tunnel City Group, Upper Mississippi Valley: new insight on the old stormy debate

USGS Publications Warehouse

Eoff, Jennifer D.

2014-01-01

New data from detailed measured sections permit a comprehensive revision of the sedimentary facies of the Furongian (upper Cambrian; Jiangshanian and Sunwaptan stages) Tunnel City Group (Lone Rock Formation and Mazomanie Formation) of Wisconsin and Minnesota. Heterogeneous sandstones, comprising seven lithofacies along a depositional transect from shoreface to transitional-offshore environments, record sedimentation in a storm-dominated, shallow-marine epicontinental sea. The origin of glauconite in the Birkmose Member and Reno Member of the Lone Rock Formation was unclear, but its formation and preserved distribution are linked to inferred depositional energy rather than just net sedimentation rate. Flat-pebble conglomerate, abundant in lower Paleozoic strata, was associated with the formation of a condensed section during cratonic flooding. Hummocky cross-stratification was a valuable tool used to infer depositional settings and relative paleobathymetry, and the model describing formation of this bedform is expanded to address flow types dominant during its genesis, in particular the importance of an early unidirectional component of combined flow. The depositional model developed here for the Lone Rock Formation and Mazomanie Formation is broadly applicable to other strata common to the early Paleozoic that document sedimentation along flooded cratonic interiors or shallow shelves.

Atrial Fibrillation in Eight New World Camelids.

PubMed

Bozorgmanesh, R; Magdesian, K G; Estell, K E; Stern, J A; Swain, E A; Griffiths, L G

2016-01-01

There is limited information on the incidence of clinical signs, concurrent illness and treatment options for atrial fibrillation (AF) in New World Camelids (NWC). Describe clinical signs and outcome of AF in NWC. Eight New World Camelids admitted with AF. A retrospective observational study of camelids diagnosed with AF based on characteristic findings on electrocardiogram (ECG). All animals had an irregularly irregular heart rhythm detected on physical examination and 4 cases had obtunded mentation on admission. Three camelids were diagnosed with AF secondary to oleander intoxication, 3 animals had underlying cardiovascular disease, 1 was diagnosed with lone AF and 1 had AF diagnosed on examination for a urethral obstruction. Five of eight animals survived to discharge and nonsurvivors consisted of animals which died or were euthanized as a result of cardiovascular disease (2/8) or extra-cardiac disease unrelated to the AF (1/8). Atrial fibrillation occurs in NWC in association with cardiovascular disease, extra-cardiac disease or as lone AF. Amiodarone and transthoracic cardioversion were attempted in one llama with lone AF, but were unsuccessful. Atrial fibrillation was recorded in 0.1% of admissions. Copyright © 2015 The Authors. Journal of Veterinary Internal Medicine published by Wiley Periodicals, Inc. on behalf of the American College of Veterinary Internal Medicine.

The Detrimental Effects of Adolescents' Chronic Loneliness on Motivation and Emotion Regulation in Social Situations.

PubMed

Vanhalst, Janne; Luyckx, Koen; Van Petegem, Stijn; Soenens, Bart

2018-01-01

In adolescence, when establishing and maintaining satisfying social relationships is a key developmental task, chronic loneliness is related to a host of negative outcomes. This study aimed at examining motivational and regulatory factors related to chronic loneliness. Specifically, this study investigated chronically lonely adolescents' responses to hypothetical vignettes of social inclusion and exclusion, thereby focusing on (a) adolescents' willingness and motivation to approach social inclusion and (b) emotion regulation strategies to deal with social exclusion. A total of 730 adolescents (Mage = 15.43 years, 72% female) participated in this four-wave study with annual loneliness assessments and hypothetical vignettes of social inclusion and exclusion at the final wave. After each social inclusion vignette, participants rated their willingness to accept the invitation for social inclusion and five types of motivation to approach the situation. After each social exclusion vignette, participants rated nine cognitive emotion regulation strategies. Compared to individuals following other trajectories, chronically lonely adolescents were less likely to accept invitations for social inclusion and the quality of their motivation for accepting such invitations was lower. Further, they were more likely to employ maladaptive emotion regulation strategies. In sum, this study adds significantly to understanding the motivational and regulatory processes that differentiate chronically lonely adolescents from adolescents following other trajectories.

Boxer crabs induce asexual reproduction of their associated sea anemones by splitting and intraspecific theft

PubMed Central

Karplus, Ilan; Achituv, Yair

2017-01-01

Crabs of the genus Lybia have the remarkable habit of holding a sea anemone in each of their claws. This partnership appears to be obligate, at least on the part of the crab. The present study focuses on Lybia leptochelis from the Red Sea holding anemones of the genus Alicia (family Aliciidae). These anemones have not been found free living, only in association with L. leptochelis. In an attempt to understand how the crabs acquire them, we conducted a series of behavioral experiments and molecular analyses. Laboratory observations showed that the removal of one anemone from a crab induces a “splitting” behavior, whereby the crab tears the remaining anemone into two similar parts, resulting in a complete anemone in each claw after regeneration. Furthermore, when two crabs, one holding anemones and one lacking them, are confronted, the crabs fight, almost always leading to the “theft” of a complete anemone or anemone fragment by the crab without them. Following this, crabs “split” their lone anemone into two. Individuals of Alicia sp. removed from freshly collected L. leptochelis were used for DNA analysis. By employing AFLP (Fluorescence Amplified Fragments Length Polymorphism) it was shown that each pair of anemones from a given crab is genetically identical. Furthermore, there is genetic identity between most pairs of anemone held by different crabs, with the others showing slight genetic differences. This is a unique case in which one animal induces asexual reproduction of another, consequently also affecting its genetic diversity. PMID:28168117

Sleeping with one eye open: loneliness and sleep quality in young adults.

PubMed

Matthews, T; Danese, A; Gregory, A M; Caspi, A; Moffitt, T E; Arseneault, L

2017-09-01

Feelings of loneliness are common among young adults, and are hypothesized to impair the quality of sleep. In the present study, we tested associations between loneliness and sleep quality in a nationally representative sample of young adults. Further, based on the hypothesis that sleep problems in lonely individuals are driven by increased vigilance for threat, we tested whether past exposure to violence exacerbated this association. Data were drawn from the Environmental Risk (E-Risk) Longitudinal Twin Study, a birth cohort of 2232 twins born in England and Wales in 1994 and 1995. We measured loneliness using items from the UCLA Loneliness Scale, and sleep quality using the Pittsburgh Sleep Quality Index. We controlled for covariates including social isolation, psychopathology, employment status and being a parent of an infant. We examined twin differences to control for unmeasured genetic and family environment factors. Feelings of loneliness were associated with worse overall sleep quality. Loneliness was associated specifically with subjective sleep quality and daytime dysfunction. These associations were robust to controls for covariates. Among monozygotic twins, within-twin pair differences in loneliness were significantly associated with within-pair differences in sleep quality, indicating an association independent of unmeasured familial influences. The association between loneliness and sleep quality was exacerbated among individuals exposed to violence victimization in adolescence or maltreatment in childhood. Loneliness is robustly associated with poorer sleep quality in young people, underscoring the importance of early interventions to mitigate the long-term outcomes of loneliness. Special care should be directed towards individuals who have experienced victimization.

Atrioesophageal Fistula after Minimally Invasive Video-Assisted Epicardial Ablation for Lone Atrial Fibrillation.

PubMed

Kik, Charles; van Valen, Richard; Mokhles, Mostafa M; Bekkers, Jos A; Bogers, Ad J J C

2017-09-01

Minimally invasive video-assisted epicardial beating heart ablation for lone atrial fibrillation claims to be safe and effective. We, however, report on three patients with an atrioesophageal fistula after this procedure. The exact pathogenesis of this complication is unknown. All patients presented around 6 weeks after surgery with either fever or neurological deficits. Diagnosis can be made by computed tomography scan. We advocate an aggressive surgical approach with closure of the atrial defect on cardiopulmonary bypass and closure and reinforcement of the esophagus with an intercostal muscle flap in a single-stage surgery. Some caution as to the low-risk character of this procedure seems to be realistic. Georg Thieme Verlag KG Stuttgart · New York.

Loneliness and sleep quality: dyadic effects and stress effects.

PubMed

Segrin, Chris; Burke, Tricia J

2015-01-01

The aims of this investigation are to determine whether loneliness is associated with a person's own sleep quality and sleep quality of their partner, and to test stress as a potential mediator. Participants were 255 couples in married (75%) or cohabiting relationships who completed self-report measures of loneliness, sleep quality, stress, and depression. Results of Actor-Partner Interdependence analyses replicated findings in the literature showing an association between loneliness and poor sleep quality. The more lonely a male participant was, the lower his partner's sleep quality. In addition, the more lonely participants were, the higher they rated their partner's sleep disturbance. There were significant indirect effects of loneliness on poor sleep quality through increased stress, even after controlling for depression.

The Windowed Removable Partial Denture: A Treatment Option for Patients with Lone-Standing Teeth.

PubMed

Jum'ah, Ahmad A; Haite, Terence; Nattress, Brian

2015-03-01

The decision as to whether to retain or extract a single remaining natural tooth prior to the provision of dentures can be a difficult one. If the tooth is left in situ, the development of an adequate peripheral seal around the denture is not possible thereby compromising the appliance' retention. If the tooth is extracted the possibility of gaining direct retention with the use of clasps or attachments is lost. This paper aims to illustrate the use of windowed removable partial denture design and review the literature relevant to this area. The use of such a design can enhance the retention of the appliance by encircling the lone standing tooth/teeth utilising an elastomeric permanent soft lining material.

Correlates of social and emotional loneliness in older people: evidence from an English community study

PubMed Central

Dahlberg, Lena; McKee, Kevin J.

2013-01-01

Objectives Loneliness is an important influence on quality of life in old age and has been conceptualised as consisting of two dimensions, social and emotional. This article describes analyses that sought to produce models of social and emotional loneliness in older people, using demographic, psychological and health, and social variables. Method Older people (aged 65+, n = 1255) from the Barnsley metropolitan area of the United Kingdom were recruited randomly from within a stratified sampling frame and received a questionnaire-based interview (response rate: 68.1%). The questionnaire contained items and scales on demographic, psychological and health, and social characteristics, and a validated measure of loneliness that assesses both social and emotional loneliness. Results Of the respondents, 7.7% were found to be severely or very severely lonely, while another 38.3% were moderately lonely. Social and emotional loneliness shared 19.36% variance. Being male, being widowed, low well-being, low self-esteem, low-income comfort, low contact with family, low contact with friends, low activity, low perceived community integration, and receipt of community care were significant predictors of social loneliness (R = 0.50, R2 = 0.25, F(18, 979) = 18.17, p < 0.001). Being widowed, low well-being, low self-esteem, high activity restriction, low-income comfort, and non-receipt of informal care were significant predictors of emotional loneliness (R = 0.55, R2 = 0.30, F(18, 973) = 23.00, p < 0.001). Conclusion This study provides further empirical support for the conceptual separation of emotional and social loneliness. Consequently, policy on loneliness in older people should be directed to developing a range of divergent intervention strategies if both emotional and social loneliness are to be reduced. PMID:24251626

Correlates of social and emotional loneliness in older people: evidence from an English community study.

PubMed

Dahlberg, Lena; McKee, Kevin J

2014-05-01

Loneliness is an important influence on quality of life in old age and has been conceptualised as consisting of two dimensions, social and emotional. This article describes analyses that sought to produce models of social and emotional loneliness in older people, using demographic, psychological and health, and social variables. Older people (aged 65+, n=1255) from the Barnsley metropolitan area of the United Kingdom were recruited randomly from within a stratified sampling frame and received a questionnaire-based interview (response rate: 68.1%). The questionnaire contained items and scales on demographic, psychological and health, and social characteristics, and a validated measure of loneliness that assesses both social and emotional loneliness. Of the respondents, 7.7% were found to be severely or very severely lonely, while another 38.3% were moderately lonely. Social and emotional loneliness shared 19.36% variance. Being male, being widowed, low well-being, low self-esteem, low-income comfort, low contact with family, low contact with friends, low activity, low perceived community integration, and receipt of community care were significant predictors of social loneliness (R=0.50, R2=0.25, F(18, 979)=18.17, p<0.001). Being widowed, low well-being, low self-esteem, high activity restriction, low-income comfort, and non-receipt of informal care were significant predictors of emotional loneliness (R=0.55, R2=0.30, F (18, 973)=23.00, p<0.001). This study provides further empirical support for the conceptual separation of emotional and social loneliness. Consequently, policy on loneliness in older people should be directed to developing a range of divergent intervention strategies if both emotional and social loneliness are to be reduced.

Antifungal agents. 10. New derivatives of 1-[(aryl)[4-aryl-1H-pyrrol-3-yl]methyl]-1H-imidazole, synthesis, anti-candida activity, and quantitative structure-analysis relationship studies.

PubMed

Tafi, Andrea; Costi, Roberta; Botta, Maurizio; Di Santo, Roberto; Corelli, Federico; Massa, Silvio; Ciacci, Andrea; Manetti, Fabrizio; Artico, Marino

2002-06-20

The synthesis, anti-Candida activity, and quantitative structure-activity relationship (QSAR) studies of a series of 2,4-dichlorobenzylimidazole derivatives having a phenylpyrrole moiety (related to the antibiotic pyrrolnitrin) in the alpha-position are reported. A number of substituents on the phenyl ring, ranging from hydrophobic (tert-butyl, phenyl, or 1-pyrrolyl moiety) to basic (NH(2)), polar (CF(3), CN, SCH(3), NO(2)), or hydrogen bond donors and acceptor (OH) groups, were chosen to better understand the interaction of these compounds with cytochrome P450 14-alpha-lanosterol demethylase (P450(14DM)). Finally, the triazole counterpart of one of the imidazole compounds was synthesized and tested to investigate influence of the heterocyclic ring on biological activity. The in vitro antifungal activities of the newly synthesized azoles 10p-v,x-c' were tested against Candida albicans and Candida spp. at pH 7.2 and pH 5.6. A CoMFA model, previously derived for a series of antifungal agents belonging to chemically diverse families related to bifonazole, was applied to the new products. Because the results produced by this approach were not encouraging, Catalyst software was chosen to perform a new 3D-QSAR study. Catalyst was preferred this time because of the possibility of considering each compound as a collection of energetically reasonable conformations and of considering alternative stereoisomers. The pharmacophore model developed by Catalyst, named HYPO1, showed good performances in predicting the biological activity data, although it did not exhibit an unequivocal preference for one enantiomeric series of inhibitors relative to the other. One aromatic nitrogen with a lone pair in the ring plane (mapped by all of the considered compounds) and three aromatic ring features were recognized to have pharmacophoric relevance, whereas neither hydrogen bond acceptor nor hydrophobic features were found. These findings confirmed that the key interaction of azole antifungals with the demethylase enzyme is the coordination bond to the iron ion of the porphyrin system, while interactions with amino acids localized in proximity of heme could modulate the biological activity of diverse antifungal agents. In conclusion, HYPO1 conveys important information in an intuitive manner and can provide predictive capability for evaluating new compounds.

Is social isolation/alienation confounded with, and non-independent of, emotional distress in its association with early onset of coronary artery disease?

PubMed

Ketterer, Mark; Rose, Benjamin; Knysz, Walter; Farha, Amjad; Deveshwar, Sangita; Schairer, John; Keteyian, Steven J

2011-03-01

Both emotional distress (ED) and social isolation/alienation (SI/A) have been found to prospectively predict adverse cardiac events, but few studies have tested the confounding/redundancy of these measures as correlates/predictors of outcomes. In this study, 163 patients with documented coronary artery disease (CAD) were interviewed for multiple indices of SI/A and administered the Symptom Checklist 90 - Revised (SCL90R). A spouse or friend provided an independent rating of ED using the spouse/friend version of the Ketterer Stress Symptom Frequency Checklist (KSSFC). The measures of ED and SI/A covaried. All three scales from the KSSFC (depression, anxiety, and "AIAI" - aggravation, irritation, anger, and impatience), and three scales from the SCL90R (anxiety, depression, and psychoticism), were associated with early Age at Initial Diagnosis (AAID) of CAD. Neither three scales derived from the SCL90R (shyness, feeling abused, and feeling lonely) nor the interview indices of SI/A (married, living alone, having a confidant, self description as a lone wolf, and self-description as lonely) were associated with early AAID. Thus, it is concluded that the present results indicate that ED and SI/A are confounded and that, even when tested head-to-head in a multivariate analysis, only ED is associated with AAID.

Understanding how education/support groups help lone mothers.

PubMed

Lipman, Ellen L; Kenny, Meghan; Jack, Susan; Cameron, Ruth; Secord, Margaret; Byrne, Carolyn

2010-01-04

Lone-mother led families are at increased risk of psychosocial disadvantage, social isolation and mental health morbidity. Community-based programs are more accessible for families seeking assistance. We examine the experiences of eight lone mothers participating in a larger randomized controlled trial (RCT) of a community-based education/support group program using mixed methods. A purposeful sample of eight mothers participating in the intervention arm of an RCT of community-based support/education groups was selected for the qualitative study. Individual interviews asked mothers about themselves and their relationships with their children before and after the group. Interviews were taped, transcribed and content analysis was used to code and interpret the data. Quantitative data collected in the RCT were used to describe these mothers. Mothers participating in the RCT and qualitative study experienced multiple difficulties, including financial and mood problems. These mothers reported that before participating in the group, they had shared experiences of social isolation, stigma, a sense of failure, poor relationships with their children and difficulties with financial management. After the group, mothers identified improved self-esteem, support from other mothers, improved parenting skills and improved communication with their children as outcomes of group participation. The qualitative data revealed mothers' perceptions of specific areas that improved by participating in the group. The utility of complementary information provided by qualitative and quantitative methods in understanding program impact, as well as the need for broader assistance is noted.

An investigation on capability of hybrid Nd:YAG laser-TIG welding technology for AA2198 Al-Li alloy

NASA Astrophysics Data System (ADS)

Faraji, Amir Hosein; Moradi, Mahmoud; Goodarzi, Massoud; Colucci, Pietro; Maletta, Carmine

2017-09-01

This paper surveys the capability of the hybrid laser-arc welding in comparison with lone laser welding for AA2198 aluminum alloy experimentally. In the present research, a continuous Nd:YAG laser with a maximum power of 2000 W and a 350 A electric arc were used as two combined welding heat sources. In addition to the lone laser welding experiments, two strategies were examined for hybrid welding; the first one was low laser power (100 W) accompanied by high arc energy, and the second one was high laser power (2000 W) with low arc energy. Welding speed and arc current varied in the experiments. The influence of heat input on weld pool geometry was surveyed. The macrosection, microhardness profile and microstructure of the welded joints were studied and compared. The results indicated that in lone laser welding, conduction mode occurred and keyhole was not formed even in low welding speeds and thus the penetration depth was so low. It was also found that the second approach (high laser power accompanied with low arc energy) is superior to the first one (low laser power accompanied with high arc energy) in hybrid laser-arc welding of Al2198, since lower heat input was needed for full penetration weld and as a result a smaller HAZ was created.

Loneliness, Depression, and Inflammation: Evidence from the Multi-Ethnic Study of Atherosclerosis.

PubMed

Mezuk, Briana; Choi, Moon; DeSantis, Amy S; Rapp, Stephen R; Diez Roux, Ana V; Seeman, Teresa

2016-01-01

Both objective and subjective aspects of social isolation have been associated with alterations in immune markers relevant to multiple chronic diseases among older adults. However, these associations may be confounded by health status, and it is unclear whether these social factors are associated with immune functioning among relatively healthy adults. The goal of this study was to examine the associations between perceived loneliness and circulating levels of inflammatory markers among a diverse sample of adults. Data come from a subset of the Multi-Ethnic Study of Atherosclerosis (n = 441). Loneliness was measured by three items derived from the UCLA Loneliness Scale. The association between loneliness and C-reactive protein (CRP) and fibrinogen was assessed using multivariable linear regression analyses. Models were adjusted for demographic and health characteristics. Approximately 50% of participants reported that they hardly ever felt lonely and 17.2% felt highly lonely. Individuals who were unmarried/unpartnered or with higher depressive symptoms were more likely to report being highly lonely. There was no relationship between perceived loneliness and ln(CRP) (β = -0.051, p = 0.239) adjusting for demographic and health characteristics. Loneliness was inversely associated with ln(fibrinogen) (β = -0.091, p = 0.040), although the absolute magnitude of this relationship was small. These results indicate that loneliness is not positively associated with fibrinogen or CRP among relatively healthy middle-aged adults.

Loneliness, Depression, and Inflammation: Evidence from the Multi-Ethnic Study of Atherosclerosis

PubMed Central

Mezuk, Briana; Choi, Moon; DeSantis, Amy S.; Rapp, Stephen R.; Diez Roux, Ana V.; Seeman, Teresa

2016-01-01

Objective Both objective and subjective aspects of social isolation have been associated with alterations in immune markers relevant to multiple chronic diseases among older adults. However, these associations may be confounded by health status, and it is unclear whether these social factors are associated with immune functioning among relatively healthy adults. The goal of this study was to examine the associations between perceived loneliness and circulating levels of inflammatory markers among a diverse sample of adults. Methods Data come from a subset of the Multi-Ethnic Study of Atherosclerosis (n = 441). Loneliness was measured by three items derived from the UCLA Loneliness Scale. The association between loneliness and C-reactive protein (CRP) and fibrinogen was assessed using multivariable linear regression analyses. Models were adjusted for demographic and health characteristics. Results Approximately 50% of participants reported that they hardly ever felt lonely and 17.2% felt highly lonely. Individuals who were unmarried/unpartnered or with higher depressive symptoms were more likely to report being highly lonely. There was no relationship between perceived loneliness and ln(CRP) (β = -0.051, p = 0.239) adjusting for demographic and health characteristics. Loneliness was inversely associated with ln(fibrinogen) (β = -0.091, p = 0.040), although the absolute magnitude of this relationship was small. Conclusion These results indicate that loneliness is not positively associated with fibrinogen or CRP among relatively healthy middle-aged adults. PMID:27367428

Implementing a sustainable clinical supervision model for Isles nurses in Orkney.

PubMed

Hall, Ian

2018-03-02

The Isles Network of Care (INOC) community nurses work at the extreme of the remote and rural continuum, working mostly as lone practitioners. Following the development of sustainable clinical supervision model for Isles nurses in Orkney, clinical supervision was found to improve both peer support and governance for this group of isolated staff. A literature overview identified the transition of clinical supervision in general nursing over 24 years from 'carrot' to 'stick'. The study included a questionnaire survey that was sent to the 2017 Queen's Nursing Institute Scotland cohort to elicit information about the nurses' experience of clinical supervision. The survey found that 55% provide supervision and 40% receive it. Health board encouragement of its use was found to be disappointingly low at 40%. The INOC nurses were surveyed about the new peer-support (restorative) model, which relies on video-conference contact to allow face to face interaction between isolated isles nurses. Feedback prompted a review of clinical supervision pairings, and the frequency and methods of meeting. The need for supervisor training led to agreement with the Remote and Rural Health Education Alliance to provide relevant support. The perceived benefits of supervision included increased support and reflection, and improved relationships with isolated colleagues.

Charge transfer and charge localization in extended radical cations: Investigation of model molecules for peptides

NASA Astrophysics Data System (ADS)

Weinkauf, Rainer; Lehrer, Florian

1998-12-01

Molecules consisting of a flexible tail and an aromatic chromophore are used as model systems to understand the situation of a single chromophore in a small peptide. Their S0-S1 resonant multiphoton ionization (REMPI) spectra show, that in neutral molecules the tail-chromophore interaction is weak and electronic excitation is localized at the chromophore. For molecules, where the ionization energy of the tail is considerable higher than that of the chromophore, by high resolution REMPI photoelectron spectroscopy we find the charge to be localized on the aromatic chromophore. This scheme also in suitable peptides allows local ionization at the aromatic chromophore. An estimate for various charge positions in peptide chains, however, shows, that for most of the amino acids electron hole positions in the nitrogen and oxygen "lone pair" orbitals of the peptide bond are nearly degenerate. REMPI photoelectron spectra of phenylethylamine, which as a model system contains such two degenerate charge positions, show small energetic shift of the ionization energy but strong geometry changes upon electron removal. This result is interpreted as direct ionization into a mixed charge delocalized state. Consequences for the charge transfer mechanism in peptides are discussed.

First-principles investigation of graphitic carbon nitride monolayer with embedded Fe atom

NASA Astrophysics Data System (ADS)

Abdullahi, Yusuf Zuntu; Yoon, Tiem Leong; Halim, Mohd Mahadi; Hashim, Md. Roslan; Lim, Thong Leng

2018-01-01

Density-functional theory (DFT) calculations with spin-polarized generalized gradient approximation and Hubbard U correction are carried out to investigate the mechanical, structural, electronic and magnetic properties of graphitic heptazine with embedded Fe atom under bi-axial tensile strain and applied perpendicular electric field. It was found that the binding energy of heptazine with embedded Fe atom system decreases as larger tensile strain is applied, while it increases as larger electric field strength is applied. Our calculations also predict a band gap at a peak value of 5% tensile strain but at expense of the structural stability of the system. The band gap open up at 5% tensile strain is due to distortion in the structure caused by the repulsive effect in the cavity between the lone pairs of the edge nitrogen atoms and dxy /dx2 -y2 orbital of Fe atom, forcing the unoccupied pz- orbital is forced to shift toward higher energy. The electronic and magnetic properties of the heptazine with embedded Fe system under perpendicular electric field up to a peak value of 8 V/nm is also well preserved despite an obvious buckled structure. Such properties are desirable for diluted magnetic semiconductors, spintronics, and sensing devices.

Vocalizations produced by humpback whale (Megaptera novaeangliae) calves recorded in Hawaii.

PubMed

Zoidis, Ann M; Smultea, Mari A; Frankel, Adam S; Hopkins, Julia L; Day, Andy; McFarland, A Sasha; Whitt, Amy D; Fertl, Dagmar

2008-03-01

Although humpback whale (Megaptera novaeangliae) calves are reported to vocalize, this has not been measurably verified. During March 2006, an underwater video camera and two-element hydrophone array were used to record nonsong vocalizations from a mother-calf escort off Hawaii. Acoustic data were analyzed; measured time delays between hydrophones provided bearings to 21 distinct vocalizations produced by the male calf. Signals were pulsed (71%), frequency modulated (19%), or amplitude modulated (10%). They were of simple structure, low frequency (mean=220 Hz), brief duration (mean=170 ms), and relatively narrow bandwidth (mean=2 kHz). The calf produced three series of "grunts" when approaching the diver. During winters of the years 2001-2005 in Hawaii, nonsong vocalizations were recorded in 109 (65%) of 169 groups with a calf using an underwater video and single (omnidirectional) hydrophone. Nonsong vocalizations were most common (34 of 39) in lone mother-calf pairs. A subsample from this dataset of 60 signals assessed to be vocalizations provided strong evidence that 10 male and 18 female calves vocalized based on statistical similarity to the 21 verified calf signals, proximity to an isolated calf (27 of 28 calves), strong signal-to-noise ratio, and/or bubble emissions coincident to sound.

The Different Sensitive Behaviors of a Hydrogen-Bond Acidic Polymer-Coated SAW Sensor for Chemical Warfare Agents and Their Simulants

PubMed Central

Long, Yin; Wang, Yang; Du, Xiaosong; Cheng, Luhua; Wu, Penglin; Jiang, Yadong

2015-01-01

A linear hydrogen-bond acidic (HBA) linear functionalized polymer (PLF), was deposited onto a bare surface acoustic wave (SAW) device to fabricate a chemical sensor. Real-time responses of the sensor to a series of compounds including sarin (GB), dimethyl methylphosphonate (DMMP), mustard gas (HD), chloroethyl ethyl sulphide (2-CEES), 1,5-dichloropentane (DCP) and some organic solvents were studied. The results show that the sensor is highly sensitive to GB and DMMP, and has low sensitivity to HD and DCP, as expected. However, the sensor possesses an unexpected high sensitivity toward 2-CEES. This good sensing performance can’t be solely or mainly attributed to the dipole-dipole interaction since the sensor is not sensitive to some high polarity solvents. We believe the lone pair electrons around the sulphur atom of 2-CEES provide an electron-rich site, which facilitates the formation of hydrogen bonding between PLF and 2-CEES. On the contrary, the electron cloud on the sulphur atom of the HD molecule is offset or depleted by its two neighbouring strong electron-withdrawing groups, hence, hydrogen bonding can hardly be formed. PMID:26225975

Twisted intramolecular charge transfer investigation of semi organic L-Glutamic acid hydrochloride single crystal for organic light-emitting and optical limiting applications

NASA Astrophysics Data System (ADS)

Joy, Lija K.; George, Merin; Alex, Javeesh; Aravind, Arun; Sajan, D.; Vinitha, G.

2018-03-01

Single crystals of L-Glutamic acid hydrochloride (LGHCl) were grown by slow evaporation solution technique and good crystalline perfection was confirmed by Powder X-ray diffraction studies. The complete vibrational studies of the compound were analyzed by FT-IR, FT-Raman and UV-visible spectra combined with Normal Coordinate Analysis (NCA) following the scaled quantum mechanical force field methodology and density functional theory (DFT). Twisted Intramolecular Charge Transfer (ICT) occurs due to the presence of strong ionic intra-molecular Nsbnd H⋯O hydrogen bonding was confirmed by Hirshfeld Surface analysis. The existence of intermolecular Nsbnd H⋯Cl hydrogen bonds due to the interaction between the lone pair of oxygen with the antibonding orbital was established by NBO analysis. The Z-scan result indicated that the title molecule exhibits saturable absorption behavior. The attractive third-order nonlinear properties suggest that LGHCl can be a promising candidate for the design and development devices for optical limiting applications. LGHCL exhibits distinct emission in the blue region of the fluorescence lifetime which proves to be a potential candidate for blue- Organic light-emitting diodes (OLEDs) fabrication.

The Nature of Bonding in Bulk Tellurium Composed of One-Dimensional Helical Chains.

PubMed

Yi, Seho; Zhu, Zhili; Cai, Xiaolin; Jia, Yu; Cho, Jun-Hyung

2018-05-07

Bulk tellurium (Te) is composed of one-dimensional (1D) helical chains which have been considered to be coupled by van der Waals (vdW) interactions. However, on the basis of first-principles density functional theory calculations, we here propose a different bonding nature between neighboring chains: i.e., helical chains made of normal covalent bonds are connected together by coordinate covalent bonds. It is revealed that the lone pairs of electrons of Te atoms participate in forming coordinate covalent bonds between neighboring chains, where each Te atom behaves as both an electron donor to neighboring chains and an electron acceptor from neighboring chains. This ligand-metal-like bonding nature in bulk Te results in the same order of bulk moduli along the directions parallel and perpendicular to the chains, contrasting with the large anisotropy of bulk moduli in vdW crystals. We further find that the electron effective masses parallel and perpendicular to the chains are almost the same as each other, consistent with the observed nearly isotropic electrical resistivity. It is thus demonstrated that the normal/coordinate covalent bonds parallel/perpendicular to the chains in bulk Te lead to a minor anisotropy in structural and transport properties.

Core Levels, Band Alignments, and Valence-Band States in CuSbS 2 for Solar Cell Applications

DOE PAGES

Whittles, Thomas J.; Veal, Tim D.; Savory, Christopher N.; ...

2017-11-10

The earth-abundant material CuSbS 2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuInxGa (1-x)Se 2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from themore » antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.« less

Multipolar electrostatics.

PubMed

Cardamone, Salvatore; Hughes, Timothy J; Popelier, Paul L A

2014-06-14

Atomistic simulation of chemical systems is currently limited by the elementary description of electrostatics that atomic point-charges offer. Unfortunately, a model of one point-charge for each atom fails to capture the anisotropic nature of electronic features such as lone pairs or π-systems. Higher order electrostatic terms, such as those offered by a multipole moment expansion, naturally recover these important electronic features. The question remains as to why such a description has not yet been widely adopted by popular molecular mechanics force fields. There are two widely-held misconceptions about the more rigorous formalism of multipolar electrostatics: (1) Accuracy: the implementation of multipole moments, compared to point-charges, offers little to no advantage in terms of an accurate representation of a system's energetics, structure and dynamics. (2) Efficiency: atomistic simulation using multipole moments is computationally prohibitive compared to simulation using point-charges. Whilst the second of these may have found some basis when computational power was a limiting factor, the first has no theoretical grounding. In the current work, we disprove the two statements above and systematically demonstrate that multipole moments are not discredited by either. We hope that this perspective will help in catalysing the transition to more realistic electrostatic modelling, to be adopted by popular molecular simulation software.

Observation of paramorphic phenomenon and non-tilted orthogonal smectic phases in hydrogen bonded ferroelectric liquid crystals for photonic applications

NASA Astrophysics Data System (ADS)

Subhasri, P.; Venugopal, D.; Jayaprakasam, R.; Chitravel, T.; Vijayakumar, V. N.

2018-06-01

A new class of hydrogen bonded ferroelectric liquid crystals (HBFLC) have been designed and synthesized by intermolecular hydrogen bonds between mesogenic 4-decyloxybenzoic acid (10OBA) and non-mesogenic (R)-(+)-Methylsuccinic acid (MSA) which have been confirmed through experimental and theoretical studies. Further, Mulliken population analysis clearly reveals that the existence of hydrogen bonds, strength and dynamic properties. Textural observation and its corresponding enthalpy values are analyzed by polarizing optical microscope (POM) and differential scanning calorimetry (DSC) respectively. Paramorphic changes in Sm C* phase due to the change of refractive index, which clearly reveal that the complex could be used for filtering action in photonic devices. The transition from lone pair to π* with large stabilization energy evidently exposes the chiral phases in the present HBFLC complex. Intermolecular interaction is analyzed by using natural bond orbital (NBO) studies. The highest energy in the HOMO-LUMO shows the stable phase in the HBFLC complex. Molecular structure of the HBFLC complex possesses the monoclinic which has been evinced through x-ray analysis. The randomly oriented bunch of homogeneous molecules in Sm A* phase of the HBFLC complex is reported.

Synthesis of inorganic fullerene-like molecules.

PubMed

Bai, Junfeng; Virovets, Alexander V; Scheer, Manfred

2003-05-02

The reaction of [Cp*Fe(eta5-P5)] with Cu(I)Cl in solvent mixtures of CH2Cl2/CH3CN leads to the formation of entirely inorganic fullerene-like molecules of the formula [[Cp*Fe(eta5:eta1:eta1:eta1:eta1:eta1-P5)]12[CuCl]10[Cu2Cl3]5[Cu(CH3CN)2]5] (1) possessing 90 inorganic core atoms. This compound represents a structural motif similar to that of C60: cyclo-P5 rings of [Cp*Fe(eta5-P5)] molecules are surrounded by six-membered P4Cu2 rings that result from the coordination of each of the phosphorus lone pairs to CuCl metal centers, which are further coordinated by P atoms of other cyclo-P5 rings. Thus, five- and six-membered rings alternate in a manner comparable to that observed in the fullerene molecules. The so-formed half shells are joined by [Cu2Cl3]- as well as by [Cu(CH3CN)2]+ units. The spherical body has an inside diameter of 1.25 nanometers and an outside diameter of 2.13 nanometers, which is about three times as large as that of C60.

Influence of La doping on structural and dielectric properties of SrBi2Nb2O9 ceramics

NASA Astrophysics Data System (ADS)

Verma, Maya; Sreenivas, K.; Gupta, Vinay

2009-01-01

Lanthanum doped SrBi2Nb2O9 ceramics with the chemical formula SrBi2-xLaxNb2O9 (SBLN) (x =0-0.5) have been prepared through conventional solid state route. X-ray diffraction reveals the shrinkage of unit cell of strontium bismuth niobate with incorporation of La3+ dopant, having no lone pair electrons. Shifting of Raman phonon modes indicates the reduced rattling space of NbO6 octahedra with increase in La doping concentration. Further, the softening of lowest frequency phonon mode with increasing x in SBLN shows the transition from ferroelectric to paraelectric at room temperature. The dielectric properties for all the compositions are studied as a function of temperature (25 to 500 °C) over the frequency range of 10 kHz-1 MHz. With increase in lanthanum doping concentration the phase transition becomes diffused and transition temperature gets shifted toward lower temperature. A phase transition from normal ferroelectric to paraelectric has been observed via relaxor-type ferroelectrics with increase in x. The frequency dependence of transition temperature was studied in terms of Vogel-Fulcher relation for SBLN (x =0.4).

One-pot synthesis, quantum chemical calculations and X-ray diffraction studies of thiazolyl-coumarin hybrid compounds

NASA Astrophysics Data System (ADS)

Saeed, Aamer; Arif, Mubeen; Erben, Mauricio F.; Flörke, Ulrich; Simpson, Jim

2018-06-01

Two closely related hybrid species containing both, thiazolyl and coumarin groups, were synthesized by using two different one-pot procedures from a common precursor. The reaction of α-bromoacetylcoumarin with thioacetamide in methanol furnished 3‑(2‑methylthiazol‑4‑yl)‑2H‑chromen‑2‑one (2), whereas refluxing α‑bromoacetylcoumarin with potassium thiocyanate in ethanol afforded 3‑(2‑ethoxythiazol‑4‑yl)‑2H‑chromen‑2‑one (3). Both derivatives were fully characterized by spectroscopic methods, elemental analysis and X-ray diffraction studies. Intramolecular C4sbnd H⋯N and C5‧sbnd H⋯Odbnd C hydrogen bonds between the heterocycles determine the conformational behavior. The co-planarity of the coumarin and thiazolyl rings favors the occurrence of two remote orbital interactions involving the oxygen and nitrogen lone pairs and the corresponding σ*Csbnd H electron acceptor, as demonstrated by Natural Bond Orbital population analysis. The 2-substitution of the thiazol‑4‑yl group has little effect on the molecular structures but causes significant differences in the crystal packing of the two compounds.

Substitution and protonation effects on spin-spin coupling constants in prototypical aromatic rings: C6H6, C5H5N and C5H5P.

PubMed

Del Bene, Janet E; Elguero, José

2006-08-01

Ab initio equation-of-motion coupled cluster calculations have been carried out to evaluate one-, two-, and three-bond 13C-13C, 15N-13C, 31P-13C coupling constants in benzene, pyridine, pyridinium, phosphinine, and phosphininium. The introduction of N or P heteroatoms into the aromatic ring not only changes the magnitudes of the corresponding X-C coupling constants (J, for X = C, N, or P) but also the signs and magnitudes of corresponding reduced coupling constants (K). Protonation of the heteroatoms also produces dramatic changes in coupling constants and, by removing the lone pair of electrons from the sigma-electron framework, leads to the same signs for corresponding reduced coupling constants for benzene, pyridinium, and phosphininium. C-C coupling constants are rather insensitive to the presence of the heteroatoms and protonation. All terms that contribute to the total coupling constant (except for the diamagnetic spin-orbit (DSO) term) must be computed if good agreement with experimental data is to be obtained. Copyright 2006 John Wiley & Sons, Ltd.

A theoretical-electron-density databank using a model of real and virtual spherical atoms.

PubMed

Nassour, Ayoub; Domagala, Slawomir; Guillot, Benoit; Leduc, Theo; Lecomte, Claude; Jelsch, Christian

2017-08-01

A database describing the electron density of common chemical groups using combinations of real and virtual spherical atoms is proposed, as an alternative to the multipolar atom modelling of the molecular charge density. Theoretical structure factors were computed from periodic density functional theory calculations on 38 crystal structures of small molecules and the charge density was subsequently refined using a density model based on real spherical atoms and additional dummy charges on the covalent bonds and on electron lone-pair sites. The electron-density parameters of real and dummy atoms present in a similar chemical environment were averaged on all the molecules studied to build a database of transferable spherical atoms. Compared with the now-popular databases of transferable multipolar parameters, the spherical charge modelling needs fewer parameters to describe the molecular electron density and can be more easily incorporated in molecular modelling software for the computation of electrostatic properties. The construction method of the database is described. In order to analyse to what extent this modelling method can be used to derive meaningful molecular properties, it has been applied to the urea molecule and to biotin/streptavidin, a protein/ligand complex.

Structure of hydrophobic hydration of benzene and hexafluorobenzene from first principles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allesch, M; Schwegler, E; Galli, G

We report on the aqueous hydration of benzene and hexafluorobenzene, as obtained by carrying out extensive (>100 ps) first principles molecular dynamics simulations. Our results show that benzene and hexafluorobenzene do not behave as ordinary hydrophobic solutes, but rather present two distinct regions, one equatorial and the other axial, that exhibit different solvation properties. While in both cases the equatorial regions behave as typical hydrophobic solutes, the solvation properties of the axial regions depend strongly on the nature of the {pi}-water interaction. In particular, {pi}-hydrogen and {pi}-lone pair interactions are found to dominate in benzene and hexafluorobenzene, respectively, which leadsmore » to substantially different orientations of water near the two solutes. We present atomic and electronic structure results (in terms of Maximally Localized Wannier Functions) providing a microscopic description of benzene- and hexafluorobenzene-water interfaces, as well as a comparative study of the two solutes. Our results point at the importance of an accurate description of interfacial water in order to characterize hydration properties of apolar molecules, as these are strongly influenced by subtle charge rearrangements and dipole moment redistributions in interfacial regions.« less

Core Levels, Band Alignments, and Valence-Band States in CuSbS2 for Solar Cell Applications.

PubMed

Whittles, Thomas J; Veal, Tim D; Savory, Christopher N; Welch, Adam W; de Souza Lucas, Francisco Willian; Gibbon, James T; Birkett, Max; Potter, Richard J; Scanlon, David O; Zakutayev, Andriy; Dhanak, Vinod R

2017-12-06

The earth-abundant material CuSbS 2 (CAS) has shown good optical properties as a photovoltaic solar absorber material, but has seen relatively poor solar cell performance. To investigate the reason for this anomaly, the core levels of the constituent elements, surface contaminants, ionization potential, and valence-band spectra are studied by X-ray photoemission spectroscopy. The ionization potential and electron affinity for this material (4.98 and 3.43 eV) are lower than those for other common absorbers, including CuIn x Ga (1-x) Se 2 (CIGS). Experimentally corroborated density functional theory (DFT) calculations show that the valence band maximum is raised by the lone pair electrons from the antimony cations contributing additional states when compared with indium or gallium cations in CIGS. The resulting conduction band misalignment with CdS is a reason for the poor performance of cells incorporating a CAS/CdS heterojunction, supporting the idea that using a cell design analogous to CIGS is unhelpful. These findings underline the critical importance of considering the electronic structure when selecting cell architectures that optimize open-circuit voltages and cell efficiencies.

Chlorine-Incorporation-Induced Formation of the Layered Phase for Antimony-Based Lead-Free Perovskite Solar Cells.

PubMed

Jiang, Fangyuan; Yang, Dongwen; Jiang, Youyu; Liu, Tiefeng; Zhao, Xingang; Ming, Yue; Luo, Bangwu; Qin, Fei; Fan, Jiacheng; Han, Hongwei; Zhang, Lijun; Zhou, Yinhua

2018-01-24

The environmental toxicity of Pb in organic-inorganic hybrid perovskite solar cells remains an issue, which has triggered intense research on seeking alternative Pb-free perovskites for solar applications. Halide perovskites based on group-VA cations of Bi 3+ and Sb 3+ with the same lone-pair ns 2 state as Pb 2+ are promising candidates. Herein, through a joint experimental and theoretical study, we demonstrate that Cl-incorporated methylammonium Sb halide perovskites (CH 3 NH 3 ) 3 Sb 2 Cl X I 9-X show promise as efficient solar absorbers for Pb-free perovskite solar cells. Inclusion of methylammonium chloride into the precursor solutions suppresses the formation of the undesired zero-dimensional dimer phase and leads to the successful synthesis of high-quality perovskite films composed of the two-dimensional layered phase favored for photovoltaics. Solar cells based on the as-obtained (CH 3 NH 3 ) 3 Sb 2 Cl X I 9-X films reach a record-high power conversion efficiency over 2%. This finding offers a new perspective for the development of nontoxic and low-cost Sb-based perovskite solar cells.

NBO, conformational, NLO, HOMO-LUMO, NMR and electronic spectral study on 1-phenyl-1-propanol by quantum computational methods

NASA Astrophysics Data System (ADS)

Xavier, S.; Periandy, S.; Ramalingam, S.

2015-02-01

In this study, FT-IR, FT-Raman, NMR and UV spectra of 1-phenyl-1-propanol, an intermediate of anti-depressant drug fluoxetine, has been investigated. The theoretical vibrational frequencies and optimized geometric parameters have been calculated by using HF and density functional theory with the hybrid methods B3LYP, B3PW91 and 6-311+G(d,p)/6-311++G(d,p) basis sets. The theoretical vibrational frequencies have been found in good agreement with the corresponding experimental data. 1H and 13C NMR spectra were recorded and chemical shifts of the molecule were compared to TMS by using the Gauge-Independent Atomic Orbital (GIAO) method. A study on the electronic and optical properties, absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies are performed using HF and DFT methods. The thermodynamic properties (heat capacity, entropy and enthalpy) at different temperatures are also calculated. NBO analysis is carried out to picture the charge transfer between the localized bonds and lone pairs. The local reactivity of the molecule has been studied using the Fukui function. NLO properties related to polarizability and hyperpolarizability are also discussed.

A new perspective on loneliness in later life.

PubMed

Rane-Szostak, D; Herth, K A

1995-01-01

Loneliness in later life remains a serious problem despite extensive research across the life span. Unfortunately, most studies of loneliness that include older adults focus on individuals who are already lonely; findings suggest interventions dependent upon external factors such as socialization and functional status. Such interventions are not always feasible for older adults, who may have experienced social and functional losses. Nurses must adopt a new perspective in examining loneliness in later life. This new perspective should include a more positive approach that focuses on older adults who are not lonely even though they may have experienced decreased socialization or physical function. Identification of strategies employed by these older individuals may be used to help many elders avoid loneliness and help others cope with the related losses so frequent in later life.

Multiple-stage integrating accelerometer

DOEpatents

Devaney, H.F.

1984-06-27

An accelerometer assembly is provided for use in activating a switch in response to multiple acceleration pulses in series. The accelerometer includes a housing forming a chamber. An inertial mass or piston is slidably disposed in the chamber and spring biased toward a first or reset position. A damping system is also provided to damp piston movement in response to first and subsequent acceleration pulses. Additionally, a cam, including a Z-shaped slot, and cooperating follower pin slidably received therein are mounted to the piston and the housing. The middle or cross-over leg of the Z-shaped slot cooperates with the follower pin to block or limit piston movement and prevent switch activation in response to a lone acceleration pulse. The switch of the assembly is only activated after two or more separate acceleration pulses are sensed and the piston reaches the end of the chamber opposite the reset position.

A curfew on women.

PubMed

McDonald, Elsie

1991-04-24

Shortly after I read Christopher Goodall's excellent piece on pornography (A Social Disease? Nursing Standard, March 20), the British Safety Council launched a code to protect lone women drivers whose cars break down.

Combined Effects of Pesticides and Trematode Infections on Hourglass Tree Frog Polypedates cruciger

PubMed Central

Jayawardena, Uthpala A.; Rohr, Jason R.; Navaratne, Ayanthi N.; Amerasinghe, Priyanie H.; Rajakaruna, Rupika S.

2016-01-01

The impact of widespread and common environmental factors, such as chemical contaminants, on infectious disease risk in amphibians is particularly important because both chemical contaminants and infectious disease have been implicated in worldwide amphibian declines. Here we report on the lone and combined effects of exposure to parasitic cercariae (larval stage) of the digenetic trematode, Acanthostomum burminis, and four commonly used pesticides (insecticides: chlorpyrifos, dimethoate; herbicides: glyphosate, propanil) at ecologically relevant concentrations on the survival, growth, and development of the common hourglass tree frog, Polypedates cruciger Blyth 1852. There was no evidence of any pesticide-induced mortality on cercariae because all the cercariae successfully penetrated each tadpole host regardless of pesticide treatment. In isolation, both cercarial and pesticide exposure significantly decreased frog survival, development, and growth, and increased developmental malformations, such as scoliosis, kyphosis, and also edema and skin ulcers. The combination of cercariae and pesticides generally posed greater risk to frogs than either factor alone by decreasing survival or growth or increasing time to metamorphosis or malformations. The exception was that lone exposure to chlorpyrifos had higher mortality without than with cercariae. Consistent with mathematical models that suggest that stress should increase the impact of generalist parasites, the weight of the evidence from the field and laboratory suggests that ecologically relevant concentrations of agrochemicals generally increase the threat that trematodes pose to amphibians, highlighting the importance of elucidating interactions between anthropogenic activities and infectious disease in taxa of conservation concern. PMID:26911919

Combined Effects of Pesticides and Trematode Infections on Hourglass Tree Frog Polypedates cruciger.

PubMed

Jayawardena, Uthpala A; Rohr, Jason R; Navaratne, Ayanthi N; Amerasinghe, Priyanie H; Rajakaruna, Rupika S

2016-03-01

The impact of widespread and common environmental factors, such as chemical contaminants, on infectious disease risk in amphibians is particularly important because both chemical contaminants and infectious disease have been implicated in worldwide amphibian declines. Here we report on the lone and combined effects of exposure to parasitic cercariae (larval stage) of the digenetic trematode, Acanthostomum burminis, and four commonly used pesticides (insecticides: chlorpyrifos, dimethoate; herbicides: glyphosate, propanil) at ecologically relevant concentrations on the survival, growth, and development of the common hourglass tree frog, Polypedates cruciger Blyth 1852. There was no evidence of any pesticide-induced mortality on cercariae because all the cercariae successfully penetrated each tadpole host regardless of pesticide treatment. In isolation, both cercarial and pesticide exposure significantly decreased frog survival, development, and growth, and increased developmental malformations, such as scoliosis, kyphosis, and also edema and skin ulcers. The combination of cercariae and pesticides generally posed greater risk to frogs than either factor alone by decreasing survival or growth or increasing time to metamorphosis or malformations. The exception was that lone exposure to chlorpyrifos had higher mortality without than with cercariae. Consistent with mathematical models that suggest that stress should increase the impact of generalist parasites, the weight of the evidence from the field and laboratory suggests that ecologically relevant concentrations of agrochemicals generally increase the threat that trematodes pose to amphibians, highlighting the importance of elucidating interactions between anthropogenic activities and infectious disease in taxa of conservation concern.

Synthesis, crystal structure, spectroscopic characterization, docking simulation and density functional studies of 1-(3,4-dimethoxyphenyl) -3-(4-flurophenyl)-propan-1-one

NASA Astrophysics Data System (ADS)

Khamees, Hussien Ahmed; Jyothi, Mahima; Khanum, Shaukath Ara; Madegowda, Mahendra

2018-06-01

The compound 1-(3,4-dimethoxyphenyl)-3-(4-flurophenyl)-propan-1-one (DFPO) was synthesized by Claisen-Schmidt condensation reaction and the single crystals were obtained by slow evaporation method. Three-dimensional structure was confirmed by single crystal X-ray diffraction method and exhibiting the triclinic crystal system with space group P-1. The crystal structure is stabilized by Csbnd H⋯O intermolecular and weak interactions. Computed molecular geometry has been obtained by density functional theory (DFT) and compared with experimental results. The spectra of both FT-IR in the range (4000-400 cm-1) and FT- Raman (3500-50 cm-1) of DFPO were recorded experimentally and computed by (DFT) using B3LYP/6-311G (d,p) as basis sets. Intramolecular charge transfer has been scanned using natural bond orbital (NBO) analysis and revealed the various contribution of bonding and lone pair to the stabilization of molecule. Nonlinear optical activity (NLO) of the title compound has been determined by second harmonic generation (SHG) and computed using DFT method. Hyperpolarizability, HOMO-LUMO energy gap, hardness, softness electronegativity and others Global reactivity descriptors of DFPO has been calculated and revealed complete picture of chemical reactivity of DFPO. Hirshfeld surface analyses were applied to investigate the intermolecular interactions and revealed that more than two-thirds of the inter contacts are associated with O⋯H, C⋯H and H⋯H interactions. Docking studies of DFPO showed inhibition of Vascular endothelial growth Factor human receptor (VEGFR-2) signalling pathway, which indicates DFPO as anti-angiogenesis, that play pivotal role in cancer, so we suggest it for clinical studies to evaluate its potential to treat human cancers.

Applying Molecular Bonding Concepts to the Solid State

NASA Astrophysics Data System (ADS)

Dunnington, Benjamin D.

In this thesis, we describe the extension and application of Natural Bond Orbital (NBO) analysis to periodic systems. This enables the translation of rigorous, quantum mechanical calculation results of solid systems into the localized lone pairs and two-center bonds of Lewis structures. Such localized bonding descriptions form the basic language of chemistry, and application of these ideas to solids allows for the understanding of complex phenomena in bulk systems using readily accessible concepts from molecular science. In addition to the algorithmic adjustments needed for to account for periodic boundary conditions in the NBO process, we also discuss methodology to interface the ubiquitous plane wave basis sets of the solid state with the atom-centered basis functions needed as input for NBO analysis. We will describe one method using projection of the plane wave eigenstates, and a second projection-free method that involves the direct calculation of matrix elements of the plane wave Hamiltonian in an atom-centered basis. The reliance of many localized, post-computational analysis techniques on an atom-centered description of the orbitals, means these interfaces will have applicability beyond our NBO development. An ideal area for application of such molecular descriptions of periodic systems is heterogeneous catalysis, where reactants from a gas/liquid phase react on a solid catalyst surface. Previous studies of these systems have originated from the delocalized perspective of the bulk catalyst. NBO provides an explicit description of the perturbative effect of the catalyst on the covalent bonds of the reactant, which is correlated with the catalytic activity of the material. Such a shift to an adsorbate focused description of surface reactivity will enable understanding of catalysis across a variety of materials.

Isothermal Fourier transform infrared microspectrosopic studies on the stability kinetics of solid-state intramolecular cyclization of aspartame sweetener.

PubMed

Cheng, Y D; Lin, S Y

2000-03-01

A novel Fourier transform infrared (FT-IR) microspectrophotometer equipped with differential scanning calorimetry (DSC) was used to investigate the kinetics of intramolecular cyclization of aspartame (APM) sweetener in the solid state under isothermal conditions. The thermal-dependent changes in the peak intensity of IR spectra at 1543, 1283, and 1259 cm(-1) were examined to explore the reaction. The results support that the intramolecular cyclization process in APM proceeded in three steps: the methoxyl group of ester was first thermolyzed to release methanol, then an acyl cation was attacked by the lone pair of electrons available on nitrogen by an S(N)1 pathway, and finally ring-closure occurred. The intramolecular cyclization of APM determined by this microscopic FT-IR/DSC system was found to follow zero-order kinetics after a brief induction period. The bond cleavage energy (259.38 kJ/mol) of thermolysis for the leaving group of -OCH(3), the bond conversion energy (328.88 kJ/mol) for the amide II NH band to DKP NH band, and the CN bond formation energy (326.93 kJ/mol) of cyclization for the DKP in the APM molecule were also calculated from the Arrhenius equation. The total activation energy of the DKP formation via intramolecular cyclization was 261.33 kJ/mol, calculated by the above summation of the bond energy of cleavage, conversion, and formation, which was near to the value determined by the DSC or TGA method. This indicates that the microscopic FT-IR/DSC system is useful as a potential tool not only to investigate the degradation mechanism of drugs in the solid state but also to directly predict the bond energy of the reaction.

A computational assessment of the electronic, thermoelectric, and defect properties of bournonite (CuPbSbS 3) and related substitutions

DOE PAGES

Faghaninia, Alireza; Yu, Guodong; Aydemir, Umut; ...

2017-02-08

Bournonite (CuPbSbS 3) is an earth-abundant mineral with potential thermoelectric applications. This material has a complex crystal structure (space group Pmn2 1 #31) and has previously been measured to exhibit a very low thermal conductivity (κ < 1 W m -1 K -1 at T ≥ 300 K). In this study, we employ high-throughput density functional theory calculations to investigate how the properties of the bournonite crystal structure change with elemental substitutions. Specifically, we compute the stability and electronic properties of 320 structures generated via substitutions {Na-K-Cu-Ag}{Si-Ge-Sn-Pb}{N-P-As-Sb-Bi}{O-S-Se-Te} in the ABCD 3 formula. We perform two types of transport calculations: themore » BoltzTraP model, which has been extensively tested, and a newer AMSET model that we have developed and which incorporates scattering effects. We discuss the differences in the model results, finding qualitative agreement except in the case of degenerate bands. Based on our calculations, we identify p-type CuPbSbSe 3 , CuSnSbSe 3 and CuPbAsSe 3 as potentially promising materials for further investigation. We additionally calculate the defect properties, finding that n-type behavior in bournonite and the selected materials is highly unlikely, and p-type behavior might be enhanced by employing Sb-poor synthesis conditions to prevent the formation of Sb Pb defects. Finally, we discuss the origins of various trends with chemical substitution, including the possible role of stereochemically active lone pair effects in stabilizing the bournonite structure and the effect of cation and anion selection on the calculated band gap.« less

Direct Growth of CuO Nanorods on Graphitic Carbon Nitride with Synergistic Effect on Thermal Decomposition of Ammonium Perchlorate

PubMed Central

Tan, Linghua; Xu, Jianhua; Li, Shiying; Li, Dongnan; Dai, Yuming; Kou, Bo; Chen, Yu

2017-01-01

Novel graphitic carbon nitride/CuO (g-C3N4/CuO) nanocomposite was synthesized through a facile precipitation method. Due to the strong ion-dipole interaction between copper ions and nitrogen atoms of g-C3N4, CuO nanorods (length 200–300 nm, diameter 5–10 nm) were directly grown on g-C3N4, forming a g-C3N4/CuO nanocomposite, which was confirmed via X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS). Finally, thermal decomposition of ammonium perchlorate (AP) in the absence and presence of the prepared g-C3N4/CuO nanocomposite was examined by differential thermal analysis (DTA), and thermal gravimetric analysis (TGA). The g-C3N4/CuO nanocomposite showed promising catalytic effects for the thermal decomposition of AP. Upon addition of 2 wt % nanocomposite with the best catalytic performance (g-C3N4/20 wt % CuO), the decomposition temperature of AP was decreased by up to 105.5 °C and only one decomposition step was found instead of the two steps commonly reported in other examples, demonstrating the synergistic catalytic activity of the as-synthesized nanocomposite. This study demonstrated a successful example regarding the direct growth of metal oxide on g-C3N4 by ion-dipole interaction between metallic ions, and the lone pair electrons on nitrogen atoms, which could provide a novel strategy for the preparation of g-C3N4-based nanocomposite. PMID:28772844

Idiopathic Interstitial Pneumonia Associated With Autoantibodies: A Large Case Series Followed Over 1 Year.

PubMed

Collins, Bridget F; Spiekerman, Charles F; Shaw, Megan A; Ho, Lawrence A; Hayes, Jennifer; Spada, Carolyn A; Stamato, Caroline M; Raghu, Ganesh

2017-07-01

Some patients with autoimmune characteristics and idiopathic interstitial pneumonia, particularly usual interstitial pneumonia (UIP), do not fit neatly into the category of connective tissue disease-associated interstitial lung disease (CTD-ILD), idiopathic pulmonary fibrosis (IPF), or recently proposed yet to be validated criteria for interstitial pneumonia with autoimmune features (IPAF). Outcomes of these patients are unknown. This was a retrospective single-center study. Analyses of variance compared differences in mean change in FVC and diffusion capacity (Dlco) over 1 year among 124 well-defined patients (20 patients with positive autoantibodies with or without symptoms of connective tissue disease [AI-ILD], 15 patients with IPAF, 36 patients with CTD-ILD, and 53 patients with IPF with negative CTD serologies [Lone-IPF]). Of the patients, 75% with AI-ILD, 33% with IPAF, and 33% with CTD-ILD had UIP. Initial FVC and Dlco were similarly moderately reduced across groups. Mean change in FVC over 12 months was as follows: -60 mL (IPAF), -110 mL (AI-ILD), -10 mL (CTD-ILD), and -90 mL (Lone-IPF) (P = .52). Mean change in Dlco was as follows: 2.39 mL/mm Hg/min (IPAF), -1.15 mL/mm Hg/min (AI-ILD), -0.27 mL/mm Hg/min (CTD-ILD), and -1.05 mL/mm Hg/min (Lone-IPF) (P < .001). By pattern of disease, the mean change in FVC was as follows: -140 mL (UIP), 10 mL (nonspecific interstitial pneumonia), and 12 mL (unclassifiable/other) (P = .001). No clinically significant differences in pulmonary function to distinguish between patients with AI-ILD, IPAF, CTD-ILD, and Lone-IPF were observed after 1 year. Longer periods of follow-up are needed to understand the outcomes of these patients. It is not yet clear whether AI-ILD is a distinct phenotype or a variant of the newly proposed entity IPAF. Copyright © 2017 American College of Chest Physicians. Published by Elsevier Inc. All rights reserved.

Raptor responses to low-level jet aircraft and sonic booms

USGS Publications Warehouse

Ellis, David H.; Ellis, Catherine H.; Mindell, David P.

1991-01-01

We estimated effects of low-level military jet aircraft and mid- to high-altitude sonic booms (actual and simulated) on nesting peregrine falcons (Falco peregrinus) and seven other raptors by observing their responses to test stimuli, determining nesting success for the test year, and evaluating site reoccupancy rates for the year following the tests. Frequent and nearby jet aircraft passes: (1) sometimes noticeably alarmed birds, (2) occasionally caused birds to fly from perches or eyries, (3) most often evoked only minimal responses, and (4) were never associated with reproductive failure. Similarly, responses to real and simulated mid- to high-altitude sonic booms were often minimal and never appeared productivity limiting. Eighteen (95%) of 19 nest sites subjected to low-level jet flights and/or simulated sonic booms in 1980 fledged young during that year. Eighteen (95%) of 19 sites disturbed in 1980 were reoccupied by pairs or lone birds of the same species in 1981.We subjected four pairs of prairie falcons (Falco mexicanus) to low-level aircraft at ad libitum levels during the courtship and incubation phases when adults were most likely to abandon: all four eyries fledged young. From heart rate (HR) data taken via a telemetering egg at another prairie falcon eyrie, we determined that stimulus-induced HR alterations were comparable to rate changes for birds settling to incubate following flight.While encouraging, our findings cannot be taken as conclusive evidence that jet flights and/or sonic booms will have no long-term negative effects for other raptor species or for other areas. In addition, we did not experiment with totally naive wild adults, rotary-winged aircraft, or low-level sonic booms.

Solution structure of a modified 2′,5′-linked RNA hairpin involved in an equilibrium with duplex

PubMed Central

Plevnik, Miha; Gdaniec, Zofia; Plavec, Janez

2005-01-01

The isomerization of phosphodiester functionality of nucleic acids from 3′,5′- to a less common 2′,5′-linkage influences the complex interplay of stereoelectronic effects that drive pseudorotational equilibrium of sugar rings and thus affect the conformational propensities for compact or more extended structures. The present study highlights the subtle balance of non-covalent forces at play in structural equilibrium of 2′,5′-linked RNA analogue, 3′-O-(2-methoxyethyl) substituted dodecamer *CG*CGAA*U*U*CG*CG, 3′-MOE-2′,5′-RNA, where all cytosines and uracils are methylated at C5. The NMR and UV spectroscopic studies have shown that 3′-MOE-2′,5′-RNA adopts both hairpin and duplex secondary structures, which are involved in a dynamic exchange that is slow on the NMR timescale and exhibits strand and salt concentration as well as pH dependence. Unusual effect of pH over a narrow physiological range is observed for imino proton resonances with exchange broadening observed at lower pH and relatively sharp lines observed at higher pH. The solution structure of 3′-MOE-2′,5′-RNA hairpin displays a unique and well-defined loop, which is stabilized by Watson–Crick A5·*U8 base pair and by n → π* stacking interactions of O4′ lone-pair electrons of A6 and *U8 with aromatic rings of A5 and *U7, respectively. In contrast, the stem region of 3′-MOE-2′,5′-RNA hairpin is more flexible. Our data highlight the important feature of backbone modifications that can have pronounced effects on interstrand association of nucleic acids. PMID:15788747

Putting an End to Lonely Street.

ERIC Educational Resources Information Center

Katz, Claudia Anne

1994-01-01

Discusses how portfolios can assist middle-school teachers in placing graduating students in English class at the high school level. Illustrates issues involved by using the example of Elvis Presley completing his portfolio. (RS)

Severe loneliness in community-dwelling aging adults with mental illness.

PubMed

Loboprabhu, Sheila; Molinari, Victor

2012-01-01

Successful aging involves adapting to changing needs. The 2009 U.S. Census noted that 43% of adult Americans are single and that the oldest-old population is the most rapidly growing aging segment. Geriatric, lonely, hopeless individuals are at high risk for depression and suicide. Lonely individuals fail to adapt to their circumstances; and physical and mental illness place them at risk for neglect, morbidity, and mortality. The authors discuss the role of attachment in the individual's subjective experience of loneliness and suggest how attachment theory can be used to guide interventions to improve the individual's self-esteem, coping, and problem-solving abilities. This article also discusses the use of multimodal therapy, including psychodynamic, interpersonal, and cognitive-behavior therapy and coping skills training, to improve the individual's ability to adapt to the surrounding environment and to reintegrate into the community.

Social Relationships and Health: The Toxic Effects of Perceived Social Isolation.

PubMed

Cacioppo, John T; Cacioppo, Stephanie

2014-02-01

Research in social epidemiology suggests that the absence of positive social relationships is a significant risk factor for broad-based morbidity and mortality. The nature of these social relationships and the mechanisms underlying this association are of increasing interest as the population gets older and the health care costs associated with chronic disease escalate in industrialized countries. We review selected evidence on the nature of social relationships and focus on one particular facet of the connection continuum - the extent to which an individual feels isolated (i.e., feels lonely) in a social world. Evidence indicates that loneliness heightens sensitivity to social threats and motivates the renewal of social connections, but it can also impair executive functioning, sleep, and mental and physical well-being. Together, these effects contribute to higher rates of morbidity and mortality in lonely older adults.

Validation of the DeLone and McLean Information Systems Success Model.

PubMed

Ojo, Adebowale I

2017-01-01

This study is an adaptation of the widely used DeLone and McLean information system success model in the context of hospital information systems in a developing country. A survey research design was adopted in the study. A structured questionnaire was used to collect data from 442 health information management personnel in five Nigerian teaching hospitals. A structural equation modeling technique was used to validate the model's constructs. It was revealed that system quality significantly influenced use (β = 0.53, p < 0.001) and user satisfaction (β = 0.17, p < 0.001). Information quality significantly influenced use (β = 0.24, p < 0.001) and user satisfaction (β = 0.17, p < 0.001). Also, service quality significantly influenced use (β = 0.22, p < 0.001) and user satisfaction (β = 0.51, p < 0.001). However, use did not significantly influence user satisfaction (β = 0.00, p > 0.05), but it significantly influenced perceived net benefits (β = 0.21, p < 0.001). Furthermore, user satisfaction did not significantly influence perceived net benefits (β = 0.00, p > 0.05). The study validates the DeLone and McLean information system success model in the context of a hospital information system in a developing country. Importantly, system quality and use were found to be important measures of hospital information system success. It is, therefore, imperative that hospital information systems are designed in such ways that are easy to use, flexible, and functional to serve their purpose.

Validation of the DeLone and McLean Information Systems Success Model

PubMed Central

2017-01-01

Objectives This study is an adaptation of the widely used DeLone and McLean information system success model in the context of hospital information systems in a developing country. Methods A survey research design was adopted in the study. A structured questionnaire was used to collect data from 442 health information management personnel in five Nigerian teaching hospitals. A structural equation modeling technique was used to validate the model's constructs. Results It was revealed that system quality significantly influenced use (β = 0.53, p < 0.001) and user satisfaction (β = 0.17, p < 0.001). Information quality significantly influenced use (β = 0.24, p < 0.001) and user satisfaction (β = 0.17, p < 0.001). Also, service quality significantly influenced use (β = 0.22, p < 0.001) and user satisfaction (β = 0.51, p < 0.001). However, use did not significantly influence user satisfaction (β = 0.00, p > 0.05), but it significantly influenced perceived net benefits (β = 0.21, p < 0.001). Furthermore, user satisfaction did not significantly influence perceived net benefits (β = 0.00, p > 0.05). Conclusions The study validates the DeLone and McLean information system success model in the context of a hospital information system in a developing country. Importantly, system quality and use were found to be important measures of hospital information system success. It is, therefore, imperative that hospital information systems are designed in such ways that are easy to use, flexible, and functional to serve their purpose. PMID:28261532

The relationship of loneliness and social anxiety with children's and adolescents' online communication.

PubMed

Bonetti, Luigi; Campbell, Marilyn Anne; Gilmore, Linda

2010-06-01

Children and adolescents now communicate online to form and/or maintain relationships with friends, family, and strangers. Relationships in "real life" are important for children's and adolescents' psychosocial development; however, they can be difficult for those who experience feelings of loneliness and/or social anxiety. The aim of this study was to investigate differences in usage of online communication patterns between children and adolescents with and without self-reported loneliness and social anxiety. Six hundred twenty-six students ages 10 to 16 years completed a survey on the amount of time they spent communicating online, the topics they discussed, the partners they engaged with, and their purposes for communicating over the Internet. Participants were administered a shortened version of the UCLA Loneliness Scale and an abbreviated subscale of the Social Anxiety Scale for Adolescents (SAS-A). Additionally, age and gender differences in usage of the online communication patterns were examined across the entire sample. Findings revealed that children and adolescents who self-reported being lonely communicated online significantly more frequently about personal and intimate topics than did those who did not self-report being lonely. The former were motivated to use online communication significantly more frequently to compensate for their weaker social skills to meet new people. Results suggest that Internet usage allows them to fulfill critical needs of social interactions, self-disclosure, and identity exploration. Future research, however, should explore whether or not the benefits derived from online communication may also facilitate lonely children's and adolescents' offline social relationships.

Acetonitrile covalent adduct chemical ionization mass spectrometry for double bond localization in non-methylene-interrupted polyene fatty acid methyl esters.

PubMed

Lawrence, Peter; Brenna, J Thomas

2006-02-15

Covalent adduct chemical ionization (CACI) using a product of acetonitrile self-reaction, (1-methyleneimino)-1-ethenylium (MIE; CH2=C=N+=CH2), has been investigated as a method for localizing double bonds in a series of 16 non-methylene-interrupted fatty acid methyl esters (NMI-FAME) of polyenes with three and more double bonds. As with polyunsaturated homoallylic (methylene-interrupted) FAME and conjugated dienes, MIE (m/z 54) reacts across double bonds to yield molecular ions 54 mass units above the parent analyte. [M + 54]+ ions of several 20- and 22-carbon FAME that include one double bond in the C2-C3 position separated by two to five methylene units from a three, four, or five C homoallylic system dissociated according to rules for the homoallylic system, with an additional fragment corresponding to cleavage between the lone double bond and the carboxyl group and defining the position of the lone double bond. Triene FAME with both methylene and ethylene interruption yielded characteristic fragments distinguishable from homoallylic trienes. Fragmentation of fully conjugated trienes in the MS-1 spectra yields ratios of [M + 54]+/[M + 54 - 32]+ (loss of methanol) near unity, which distinguishes them from homoallylic FAME having a ratio of 8 or more; collisionally activated dissociation of [M + 54]+ yields a series of ions, including some rearrangement products, indicative of double bond position. Unlike conjugated dienes, fully conjugated triene diagnostic ion signal ratios did not follow any pattern based on double bond geometry. Partially conjugated trienes behave similarly to monoenes and conjugated dienes, yielding [M + 54]+/[M + 54 - 32]+ of 2-3 and, permitting them to be assigned as partially conjugated FAME using the MS-1 spectrum. They yield unique MS/MS spectra with weaker but assignable fragment ions, along with a diagnostic fragment that locates the lone double bond and permits 6,10,12-octatrienoate to be distinguished from 6,8,12-octatrienoate. The presence of a triple bond did not affect fragment formation in a methylene-interrupted yne-ene but did change fragments in a conjugated yne-ene. These data extend the principle of double bond localization by acetonitrile CACI-MS/MS to double bond structure in complex FAME found in nature.

Welfare-to-work interventions and their effects on the mental and physical health of lone parents and their children.

PubMed

Gibson, Marcia; Thomson, Hilary; Banas, Kasia; Lutje, Vittoria; McKee, Martin J; Martin, Susan P; Fenton, Candida; Bambra, Clare; Bond, Lyndal

2018-02-26

Lone parents in high-income countries have high rates of poverty (including in-work poverty) and poor health. Employment requirements for these parents are increasingly common. 'Welfare-to-work' (WtW) interventions involving financial sanctions and incentives, training, childcare subsidies and lifetime limits on benefit receipt have been used to support or mandate employment among lone parents. These and other interventions that affect employment and income may also affect people's health, and it is important to understand the available evidence on these effects in lone parents. To assess the effects of WtW interventions on mental and physical health in lone parents and their children living in high-income countries. The secondary objective is to assess the effects of welfare-to-work interventions on employment and income. We searched the Cochrane Central Register of Controlled Trials (CENTRAL), MEDLINE Ovid, Embase Ovid, PsycINFO EBSCO, ERIC EBSCO, SocINDEX EBSCO, CINAHL EBSCO, Econlit EBSCO, Web of Science ISI, Applied Social Sciences Index and Abstracts (ASSIA) via Proquest, International Bibliography of the Social Sciences (IBSS) via ProQuest, Social Services Abstracts via Proquest, Sociological Abstracts via Proquest, Campbell Library, NHS Economic Evaluation Database (NHS EED) (CRD York), Turning Research into Practice (TRIP), OpenGrey and Planex. We also searched bibliographies of included publications and relevant reviews, in addition to many relevant websites. We identified many included publications by handsearching. We performed the searches in 2011, 2013 and April 2016. Randomised controlled trials (RCTs) of mandatory or voluntary WtW interventions for lone parents in high-income countries, reporting impacts on parental mental health, parental physical health, child mental health or child physical health. One review author extracted data using a standardised extraction form, and another checked them. Two authors independently assessed risk of bias and the quality of the evidence. We contacted study authors to obtain measures of variance and conducted meta-analyses where possible. We synthesised data at three time points: 18 to 24 months (T1), 25 to 48 months (T2) and 49 to 72 months (T3). Twelve studies involving 27,482 participants met the inclusion criteria. Interventions were either mandatory or voluntary and included up to 10 discrete components in varying combinations. All but one study took place in North America. Although we searched for parental health outcomes, the vast majority of the sample in all included studies were female. Therefore, we describe adult health outcomes as 'maternal' throughout the results section. We downgraded the quality of all evidence at least one level because outcome assessors were not blinded. Follow-up ranged from 18 months to six years. The effects of welfare-to-work interventions on health were generally positive but of a magnitude unlikely to have any tangible effects.At T1 there was moderate-quality evidence of a very small negative impact on maternal mental health (standardised mean difference (SMD) 0.07, 95% Confidence Interval (CI) 0.00 to 0.14; N = 3352; studies = 2)); at T2, moderate-quality evidence of no effect (SMD 0.00, 95% CI 0.05 to 0.05; N = 7091; studies = 3); and at T3, low-quality evidence of a very small positive effect (SMD -0.07, 95% CI -0.15 to 0.00; N = 8873; studies = 4). There was evidence of very small positive effects on maternal physical health at T1 (risk ratio (RR) 0.85, 95% CI 0.54 to 1.36; N = 311; 1 study, low quality) and T2 (RR 1.06, 95% CI 0.95 to 1.18; N = 2551; 2 studies, moderate quality), and of a very small negative effect at T3 (RR 0.97, 95% CI 0.91 to 1.04; N = 1854; 1 study, low quality).At T1, there was moderate-quality evidence of a very small negative impact on child mental health (SMD 0.01, 95% CI -0.06 to 0.09; N = 2762; studies = 1); at T2, of a very small positive effect (SMD -0.04, 95% CI -0.08 to 0.01; N = 7560; studies = 5), and at T3, there was low-quality evidence of a very small positive effect (SMD -0.05, 95% CI -0.16 to 0.05; N = 3643; studies = 3). Moderate-quality evidence for effects on child physical health showed a very small negative effect at T1 (SMD -0.05, 95% CI -0.12 to 0.03; N = 2762; studies = 1), a very small positive effect at T2 (SMD 0.07, 95% CI 0.01 to 0.12; N = 7195; studies = 3), and a very small positive effect at T3 (SMD 0.01, 95% CI -0.04 to 0.06; N = 8083; studies = 5). There was some evidence of larger negative effects on health, but this was of low or very low quality.There were small positive effects on employment and income at 18 to 48 months (moderate-quality evidence), but these were largely absent at 49 to 72 months (very low to moderate-quality evidence), often due to control group members moving into work independently. Since the majority of the studies were conducted in North America before the year 2000, generalisabilty may be limited. However, all study sites were similar in that they were high-income countries with developed social welfare systems. The effects of WtW on health are largely of a magnitude that is unlikely to have tangible impacts. Since income and employment are hypothesised to mediate effects on health, it is possible that these negligible health impacts result from the small effects on economic outcomes. Even where employment and income were higher for the lone parents in WtW, poverty was still high for the majority of the lone parents in many of the studies. Perhaps because of this, depression also remained very high for lone parents whether they were in WtW or not. There is a lack of robust evidence on the health effects of WtW for lone parents outside North America.

Welfare-to-work interventions and their effects on the mental and physical health of lone parents and their children.

PubMed

Gibson, Marcia; Thomson, Hilary; Banas, Kasia; Lutje, Vittoria; McKee, Martin J; Martin, Susan P; Fenton, Candida; Bambra, Clare; Bond, Lyndal

2017-08-20

Lone parents in high-income countries have high rates of poverty (including in-work poverty) and poor health. Employment requirements for these parents are increasingly common. 'Welfare-to-work' (WtW) interventions involving financial sanctions and incentives, training, childcare subsidies and lifetime limits on benefit receipt have been used to support or mandate employment among lone parents. These and other interventions that affect employment and income may also affect people's health, and it is important to understand the available evidence on these effects in lone parents. To assess the effects of WtW interventions on mental and physical health in lone parents and their children living in high-income countries. The secondary objective is to assess the effects of welfare-to-work interventions on employment and income. We searched the Cochrane Central Register of Controlled Trials (CENTRAL), MEDLINE Ovid, Embase Ovid, PsycINFO EBSCO, ERIC EBSCO, SocINDEX EBSCO, CINAHL EBSCO, Econlit EBSCO, Web of Science ISI, Applied Social Sciences Index and Abstracts (ASSIA) via Proquest, International Bibliography of the Social Sciences (IBSS) via ProQuest, Social Services Abstracts via Proquest, Sociological Abstracts via Proquest, Campbell Library, NHS Economic Evaluation Database (NHS EED) (CRD York), Turning Research into Practice (TRIP), OpenGrey and Planex. We also searched bibliographies of included publications and relevant reviews, in addition to many relevant websites. We identified many included publications by handsearching. We performed the searches in 2011, 2013 and April 2016. Randomised controlled trials (RCTs) of mandatory or voluntary WtW interventions for lone parents in high-income countries, reporting impacts on parental mental health, parental physical health, child mental health or child physical health. One review author extracted data using a standardised extraction form, and another checked them. Two authors independently assessed risk of bias and the quality of the evidence. We contacted study authors to obtain measures of variance and conducted meta-analyses where possible. We synthesised data at three time points: 18 to 24 months (T1), 25 to 48 months (T2) and 49 to 72 months (T3). Twelve studies involving 27,482 participants met the inclusion criteria. Interventions were either mandatory or voluntary and included up to 10 discrete components in varying combinations. All but one study took place in North America. Although we searched for parental health outcomes, the vast majority of the sample in all included studies were female. Therefore, we describe adult health outcomes as 'maternal' throughout the results section. We downgraded the quality of all evidence at least one level because outcome assessors were not blinded. Follow-up ranged from 18 months to six years. The effects of welfare-to-work interventions on health were generally positive but of a magnitude unlikely to have any tangible effects.At T1 there was moderate-quality evidence of a very small negative impact on maternal mental health (standardised mean difference (SMD) 0.07, 95% Confidence Interval (CI) 0.00 to 0.14; N = 3352; studies = 2)); at T2, moderate-quality evidence of no effect (SMD 0.00, 95% CI 0.05 to 0.05; N = 7091; studies = 3); and at T3, low-quality evidence of a very small positive effect (SMD -0.07, 95% CI -0.15 to 0.00; N = 8873; studies = 4). There was evidence of very small positive effects on maternal physical health at T1 (risk ratio (RR) 0.85, 95% CI 0.54 to 1.36; N = 311; 1 study, low quality) and T2 (RR 1.06, 95% CI 0.95 to 1.18; N = 2551; 2 studies, moderate quality), and of a very small negative effect at T3 (RR 0.97, 95% CI 0.91 to 1.04; N = 1854; 1 study, low quality).At T1, there was moderate-quality evidence of a very small negative impact on child mental health (SMD 0.01, 95% CI -0.06 to 0.09; N = 2762; studies = 1); at T2, of a very small positive effect (SMD -0.04, 95% CI -0.08 to 0.01; N = 7560; studies = 5), and at T3, there was low-quality evidence of a very small positive effect (SMD -0.05, 95% CI -0.16 to 0.05; N = 3643; studies = 3). Moderate-quality evidence for effects on child physical health showed a very small negative effect at T1 (SMD -0.05, 95% CI -0.12 to 0.03; N = 2762; studies = 1), a very small positive effect at T2 (SMD 0.07, 95% CI 0.01 to 0.12; N = 7195; studies = 3), and a very small positive effect at T3 (SMD 0.01, 95% CI -0.04 to 0.06; N = 8083; studies = 5). There was some evidence of larger negative effects on health, but this was of low or very low quality.There were small positive effects on employment and income at 18 to 48 months (moderate-quality evidence), but these were largely absent at 49 to 72 months (very low to moderate-quality evidence), often due to control group members moving into work independently. Since the majority of the studies were conducted in North America before the year 2000, generalisabilty may be limited. However, all study sites were similar in that they were high-income countries with developed social welfare systems. The effects of WtW on health are largely of a magnitude that is unlikely to have tangible impacts. Since income and employment are hypothesised to mediate effects on health, it is possible that these negligible health impacts result from the small effects on economic outcomes. Even where employment and income were higher for the lone parents in WtW, poverty was still high for the majority of the lone parents in many of the studies. Perhaps because of this, depression also remained very high for lone parents whether they were in WtW or not. There is a lack of robust evidence on the health effects of WtW for lone parents outside North America.

North America Mosaic

Atmospheric Science Data Center

2014-05-15

... models from the Shuttle Radar Topography Mission (SRTM) and other sources. An astonishing diversity of geological features, ecological ... to the lonely Bermuda Islands and southward to the Bahamas, Cuba and Mexico. Draped in green, the eastern and central United States and ...

Loneliness and Media Gratifications.

ERIC Educational Resources Information Center

Canary, Daniel J.; Spitzberg, Brian H.

1993-01-01

Assesses the nature of the relationship between experienced loneliness and media gratifications. Finds that chronically lonely college students rely less on media for escape than do others and that they reported the least motivation for watching their favorite soap opera. (SR)

Chemical tuning of dynamic cation off-centering in the cubic phases of hybrid tin and lead halide perovskites† †Electronic supplementary information (ESI) available: Details of the sample synthesis. LeBail fits of the X-ray diffraction data at 360 K. Fourier transform optimization of the X-ray total scattering data. Cubic fits of the XPDF data over 10 Å to 20 Å. Fits of the XPDF data over 2 Å to 5 Å against all models. Cubic and rhombohedral fits of APbBr3 at 300 K and 360 K. See DOI: 10.1039/c7sc01429e Click here for additional data file.

PubMed Central

Laurita, Geneva; Fabini, Douglas H.; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.

2017-01-01

Hybrid halide perovskites combine ease of preparation and relatively abundant constituent elements with fascinating photophysical properties. Descriptions of the chemical and structural drivers of the remarkable properties have often focused on the potential role of the dynamic order/disorder of the molecular A-site cations. We reveal here a key aspect of the inorganic framework that potentially impacts the electronic, thermal, and dielectric properties. The temperature evolution of the X-ray pair distribution functions of hybrid perovskites ABX3 [A+ = CH3NH3 (MA) or CH(NH2)2 (FA); B2+ = Sn or Pb; X– = Br, or I] in their cubic phases above 300 K reveals temperature-activated displacement (off-centering) of the divalent group 14 cations from their nominal, centered sites. This symmetry-lowering distortion phenomenon, previously dubbed emphanisis in the context of compounds such as PbTe, is attributed to Sn2+ and Pb2+ lone pair stereochemistry. Of the materials studied here, the largest displacements from the center of the octahedral sites are found in tin iodides, a more moderate effect is found in lead bromides, and the weakest effect is seen in lead iodides. The A-site cation appears to play a role as well, with the larger FA resulting in greater off-centering for both Sn2+ and Pb2+. Dynamic off-centering, which is concealed within the framework of traditional Bragg crystallography, is proposed to play a key role in the remarkable defect-tolerant nature of transport in these semiconductors via its effect on the polarizability of the lattice. The results suggest a novel chemical design principle for future materials discovery. PMID:28989600

The Sibsize Revolution and Social Disparities in Children's Family Contexts in the United States, 1940-2012.

PubMed

Fahey, Tony

2017-06-01

This article points to a sharp decline in children's sibling numbers (sibsize) that occurred in the United States since the 1970s and was large enough among children with lower socioeconomic status (SES) (particularly black children) to amount to a revolution in their family circumstances. It interprets sibsize decline as a source of social convergence in children's family contexts that ran counter to trends toward social divergence caused by the rise of lone parenthood. The article is based on new estimates of differences in children's sibsize and lone parenthood by race and maternal education generated from public-use samples from the Census of Population and Current Population Survey (CPS), focusing especially on the period 1940-2012. I discuss some methodological and substantive challenges for existing scholarship arising from the findings and point to questions for future research.

Social stress in early adolescents' daily lives: Associations with affect and loneliness.

PubMed

van Roekel, Eeske; Ha, Thao; Verhagen, Maaike; Kuntsche, Emmanuel; Scholte, Ron H J; Engels, Rutger C M E

2015-12-01

Adolescence is characterized by increased social stress due to changes in interpersonal relationships, but little is known about daily experiences of social stress. The aim of the present study was to examine daily life predictors of increases in social stress, how these increases affected adolescents' mood, and whether loneliness moderated these relations. The Experience Sampling Method was used to measure positive and negative affect and increases in social stress in 278 early adolescents from the Netherlands. Results showed that adolescents were most likely to experience increases in social stress when they were with classmates, during week days, and in the morning. Lonely adolescents showed higher increases in social stress and responded more negatively to increases in social stress, compared to non-lonely adolescents. Copyright © 2015 The Foundation for Professionals in Services for Adolescents. Published by Elsevier Ltd. All rights reserved.

Why is terrorism a man's business?

PubMed

Möller-Leimkühler, Anne Maria

2018-04-01

Terrorism, whether it is group-related or performed as lone actor terrorism, is a predominantly male phenomenon. Generally and throughout history, young males have been the main protagonists of criminal and political violence.This article aims to contribute, from different perspecives, to the question of what makes young men violent. These include neurobiological aspects, such as sex differences in the brain that predispose males to physical aggression and violence; gender role aspects, with regard to aggression and violence being basic components for demonstrating and reconstructing masculinity; demographic aspects of male youth bulges as potential breeding grounds for terrorism; aspects of group dynamics and identity fusion in the process of radicalization; and psychosocial characteristics of lone actor terrorists, which differ from group-related terrorists.It is concluded that in addition to ideological, political, economic, regional, demographic, or psychosocial causes, experiences of threatened masculinity may be an underlying factor and driving force for terrorism.

Social Relationships and Health: The Toxic Effects of Perceived Social Isolation

PubMed Central

Cacioppo, John T.; Cacioppo, Stephanie

2014-01-01

Research in social epidemiology suggests that the absence of positive social relationships is a significant risk factor for broad-based morbidity and mortality. The nature of these social relationships and the mechanisms underlying this association are of increasing interest as the population gets older and the health care costs associated with chronic disease escalate in industrialized countries. We review selected evidence on the nature of social relationships and focus on one particular facet of the connection continuum – the extent to which an individual feels isolated (i.e., feels lonely) in a social world. Evidence indicates that loneliness heightens sensitivity to social threats and motivates the renewal of social connections, but it can also impair executive functioning, sleep, and mental and physical well-being. Together, these effects contribute to higher rates of morbidity and mortality in lonely older adults. PMID:24839458

Spatial displacement among pedestrians: a cross-cultural replication.

PubMed

Rawdon, V A; Willis, F N

1993-10-01

An observational study of pedestrians in a shopping mall in a mid-western U.S. city was replicated in shopping malls in London. The avoidance movements of 2692 shoppers were recorded as they approached other shoppers. The relationships between these movements and the shoppers' gender, age, race, group size, and other characteristics were examined. Results of both studies indicated that men were likely to be displaced by women, smaller groups by larger ones, and nonhandicapped persons by handicapped ones. The results differed, however, with respect to race, with black persons tending to displace white individuals in the Midwest regardless of group size, while lone white pedestrians tended to displace lone black pedestrians in London. In London larger groups tended to displace smaller ones regardless of race. Hypotheses regarding spatial displacement were discussed. The need for more cross-situational and cross-cultural research in social psychology was clear.

Atrial fibrillation in the elderly: physicians' attitudes to anticoagulation.

PubMed

King, D; Davies, K N; Slee, A; Silas, J H

1995-01-01

The use of warfarin and aspirin for the primary prevention of stroke in elderly patients with atrial fibrillation (AF) is controversial. To establish current practice we circulated a questionnaire to 300 geriatricians (G) and 300 cardiologists (C). The response rates were 47% G and 51% C. Most physicians prescribed warfarin in AF associated with mitral stenosis (G vs C, 86% vs 89%, NS). Cardiologists were more likely to prescribe warfarin in AF associated with dilated cardiomyopathy (G vs C, 52% vs 86%, P < 0.01). A minority would prescribe warfarin in aortic valve disease and AF (G vs C, 37% vs 24%, P < 0.05) and lone AF (G vs C, 10% vs 26%, P < 0.01). Aspirin was favoured in aortic valve disease and lone AF. The cardiologists were less reluctant to use warfarin in the young and more likely to electrically cardiovert the young with chronic AF.

Utility of the Lone Star Retractor System in Microsurgical Carotid Endarterectomy.

PubMed

Toyota, Shingo; Kumagai, Tetsuya; Goto, Tetsu; Mori, Kanji; Taki, Takuyu

2017-05-01

The retractor system is an important device in carotid endarterectomy (CEA). We applied the Lone Star (LS) Retractor System, which is a self-retaining retractor originally designed for improved visualization in many other surgical fields, in microsurgical CEA. The LS disposal retractor (14.1 cm × 14.1 cm) and LS elastic stays (5-mm sharp hook) were used as a retractor system in 38 consecutive CEAs. Using the LS retractor system, a shallow operative field could be obtained by lifting up the connective tissue surrounding the deep structures hooked by the LS elastic stays. The LS elastic stays were quick and easy to handle in the microsurgical operative field. There were no complications using the LS retractor system. The application of the LS retractor system in microsurgical CEA is feasible. An additional merit is that it is single use. Copyright © 2017 Elsevier Inc. All rights reserved.

The evaluation of a virtual education system based on the DeLone and McLean model:  A path analysis.

PubMed

Mahmoodi, Zohreh; Esmaelzadeh-Saeieh, Sara; Lotfi, Razieh; Baradaran Eftekhari, Monir; Akbari Kamrani, Mahnaz; Mehdizadeh Tourzani, Zahra; Salehi, Katayoun

2017-01-01

Background : The Internet has dramatically influenced the introduction of virtual education. Virtual education is a term that involves online education and e-learning. This study was conducted to evaluate a virtual education system based on the DeLone and McLean model. Methods : This descriptive analytical study was conducted using the census method on all the students of the Nursing and Midwifery Department of Alborz University of Medical Sciences who had taken at least one online course in 2016-2017. Data were collected using a researcher-made questionnaire based on the DeLone and McLean model in six domains and then analyzed in SPSS-16 and LISREL-8.8 using the path analysis. Results : The goodness of fit indices (GFI) of the model represent the desirability and good fit of the model, and the rational nature of the adjusted relationships between the variables based on a conceptual model (GFI = 0.98; RMSEA = 0.014).The results showed that system quality has the greatest impact on the net benefits of the system through both direct and indirect paths (β=0.52), service quality through the indirect path (β=0.03) and user satisfaction through the direct path (β=0.73). Conclusions : According to the results, system quality has the greatest overall impact on the net benefits of the system, both directly and indirectly by affecting user satisfaction and the intention to use. System quality should therefore be further emphasized, to use these systems more efficiently.

Loneliness and social isolation among young and late middle-age adults: Associations with personal networks and social participation.

PubMed

Child, Stephanie T; Lawton, Leora

2017-11-24

Associations between social networks and loneliness or social isolation are well established among older adults. Yet, limited research examines personal networks and participation on perceived loneliness and social isolation as distinct experiences among younger adults. Accordingly, we explore relationships among objective and subjective measures of personal networks with loneliness and isolation, comparing a younger and older cohort. The UC Berkeley Social Networks Study offers unique cohort data on young (21-30 years old, n = 472) and late middle-age adults' (50-70 years old, n = 637) personal network characteristics, social participation, network satisfaction, relationship status, and days lonely and isolated via online survey or in-person interview. Negative binomial regression models were used to examine associations between social network characteristics, loneliness, and isolation by age group. Young adults reported twice as many days lonely and isolated than late middle-age adults, despite, paradoxically, having larger networks. For young adults, informal social participation and weekly religious attendance were associated with fewer days isolated. Among late middle-age adults, number of close kin and relationship status were associated with loneliness. Network satisfaction was associated with fewer days lonely or isolated among both age groups. Distinct network characteristics were associated with either loneliness or isolation for each cohort, suggesting network factors are independently associated with each outcome, and may fluctuate over time. Network satisfaction was associated with either loneliness or isolation among both cohorts, suggesting perceptions of social networks may be equally important as objective measures, and remain salient for loneliness and isolation throughout the life course.

Is the minimum enough? Affordability of a nutritious diet for minimum wage earners in Nova Scotia (2002-2012).

PubMed

Newell, Felicia D; Williams, Patricia L; Watt, Cynthia G

2014-05-09

This paper aims to assess the affordability of a nutritious diet for households earning minimum wage in Nova Scotia (NS) from 2002 to 2012 using an economic simulation that includes food costing and secondary data. The cost of the National Nutritious Food Basket (NNFB) was assessed with a stratified, random sample of grocery stores in NS during six time periods: 2002, 2004/2005, 2007, 2008, 2010 and 2012. The NNFB's cost was factored into affordability scenarios for three different household types relying on minimum wage earnings: a household of four; a lone mother with three children; and a lone man. Essential monthly living expenses were deducted from monthly net incomes using methods that were standardized from 2002 to 2012 to determine whether adequate funds remained to purchase a basic nutritious diet across the six time periods. A 79% increase to the minimum wage in NS has resulted in a decrease in the potential deficit faced by each household scenario in the period examined. However, the household of four and the lone mother with three children would still face monthly deficits ($44.89 and $496.77, respectively, in 2012) if they were to purchase a nutritiously sufficient diet. As a social determinant of health, risk of food insecurity is a critical public health issue for low wage earners. While it is essential to increase the minimum wage in the short term, adequately addressing income adequacy in NS and elsewhere requires a shift in thinking from a focus on minimum wage towards more comprehensive policies ensuring an adequate livable income for everyone.

Loneliness, common mental disorders and suicidal behavior: Findings from a general population survey.

PubMed

Stickley, Andrew; Koyanagi, Ai

2016-06-01

Loneliness has been linked to an increased risk of engaging in suicidal behavior. To date, however, there has been comparatively little research on this in the general adult population, or on the role of common mental disorders (CMDs) in this association. The current study examined these associations using nationally representative data from England. Data came from the Adult Psychiatric Morbidity Survey 2007. Information was obtained from 7403 household residents aged ≥16 years on perceived loneliness and lifetime and past 12-month suicide ideation and attempts. The Clinical Interview Schedule Revised (CIS-R) was used to assess six forms of CMD. Logistic regression analysis was used to examine these associations. Loneliness was associated with suicidal behavior. Although adjusting for CMDs attenuated associations, higher levels of loneliness were still significantly associated with suicidal ideation and suicide attempts with odds ratios (OR) for those in the most severe loneliness category ranging from 3.45 (lifetime suicide attempt) to 17.37 (past 12-month suicide attempt). Further analyses showed that ORs for suicidal behavior were similar for individuals who were lonely without CMDs, and for those respondents with CMDs who were not lonely. Lonely individuals with CMDs had especially elevated odds for suicidal ideation. This study used cross-sectional data and a single-item measure to obtain information on loneliness. Loneliness is associated with suicidal behavior in the general adult population. This highlights the importance of efforts to reduce loneliness in order to mitigate its harmful effects on health and well-being. Copyright © 2016 Elsevier B.V. All rights reserved.

Internet Gamblers Differ on Social Variables: A Latent Class Analysis.

PubMed

Khazaal, Yasser; Chatton, Anne; Achab, Sophia; Monney, Gregoire; Thorens, Gabriel; Dufour, Magali; Zullino, Daniele; Rothen, Stephane

2017-09-01

Online gambling has gained popularity in the last decade, leading to an important shift in how consumers engage in gambling and in the factors related to problem gambling and prevention. Indebtedness and loneliness have previously been associated with problem gambling. The current study aimed to characterize online gamblers in relation to indebtedness, loneliness, and several in-game social behaviors. The data set was obtained from 584 Internet gamblers recruited online through gambling websites and forums. Of these gamblers, 372 participants completed all study assessments and were included in the analyses. Questionnaires included those on sociodemographics and social variables (indebtedness, loneliness, in-game social behaviors), as well as the Gambling Motives Questionnaire, Gambling Related Cognitions Scale, Internet Addiction Test, Problem Gambling Severity Index, Short Depression-Happiness Scale, and UPPS-P Impulsive Behavior Scale. Social variables were explored with a latent class model. The clusters obtained were compared for psychological measures and three clusters were found: lonely indebted gamblers (cluster 1: 6.5%), not lonely not indebted gamblers (cluster 2: 75.4%), and not lonely indebted gamblers (cluster 3: 18%). Participants in clusters 1 and 3 (particularly in cluster 1) were at higher risk of problem gambling than were those in cluster 2. The three groups differed on most assessed variables, including the Problem Gambling Severity Index, the Short Depression-Happiness Scale, and the UPPS-P subscales (except the sensation seeking subscore). Results highlight significant between-group differences, suggesting that Internet gamblers are not a homogeneous group. Specific intervention strategies could be implemented for groups at risk.

Lone Star Industries, Inc. (Buzzi), Clean Air Act Settlement

EPA Pesticide Factsheets

Buzzi agreed to invest approximately $1 million in pollution control technology that will protect public health and resolve violations of the CAA. The settlement requires that Buzzi spend approximately $1.7 million on an environmental mitigation project

78 FR 65701 - Notice of Availability of the Nevada and Northeastern California Greater Sage-Grouse Draft Land...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-01

.../White Pine, Clan Alpine, Cortez; Desatoya, Desert, East Valley, Fish Creek, Gollaher, Islands, Lincoln, Lone Willow, Massacre, Monitor, North Fork, O'Neil Basin, Pine Forest, Reese River, Ruby Valley, Santa...

New product evaluation : Aucem cement blend, Lone Star Industries, Inc. : technical assistance report.

DOT National Transportation Integrated Search

2003-01-01

The Louisiana Department of Transportation and Development (DOTD) receives many requests to use new products for soil treatment, soil stabilization, or reinforcements on construction projects. The product information provided by the manufacturer gene...

Impaired endothelial function in lone atrial fibrillation.

PubMed

Polovina, Marija; Potpara, Tatjana; Giga, Vojislav; Stepanović, Jelena; Ostojić, Miodrag

2013-10-01

Impaired endothelial function has been previously documented in patients with atrial fibrillation (AF) and underlying comorbidities or older patients with idiopathic AF. The aim of this study was to evaluate systemic endothelial function in younger AF patients (less than < 60 years old) with lone AF (that is, without associated cardiopulmonary comorbidities, including arterial hypertension), by comparing brachial artery flow-mediated dilation (FMD) in lone AF patients with FMD of healthy subjects in sinus rhythm. Two groups of participants were prospectively enrolled. The first group comprised of 38 AF patients (the mean age 45 +/- 11 years, 68% male) with persistent (> 7 days) lone AF. The second group comprised of 28 healthy controls in sinus rhythm (the mean age 43 +/- 13, 53% male), matched by age, gender and atherosclerotic risk factors. All the participants underwent physical examination, laboratory analysis [including determination of C-reactive protein (CRP)], standard echocardiography and exercise-stress testing. Brachial artery FMD and endothelium independent dilation (NMD) were assessed with a high-resolution ultrasound probe and arterial diameters taken from 5 consecutive cardiac cycles were averaged for each measurement to accommodate to beat-to-beat flow variations in AF. There were no differences between the 2 groups regarding age, gender and most clinical, laboratory and echocardiographic characteristics (all p > 0.05), apart from the increased heart rate (p = 0.018), body mass index (p = 0.027), CRP levels (p = 0.007) and left atrial anteroposterior dimension (p < 0.001) in AF patients. FMD of AF patients [median value 5.0%, interquartile range (IQR) 2.87%-7.50%] was significantly lower (p < 0.001) than FMD of healthy controls (median value 8.85%, IQR 5.80%-12.50%), whereas there were no differences in median NMD values (p > 0.05). In the multivariate analysis, the independent FMD determinants in our study population were the presence of AF, smoking and total cholesterol levels (all p < 0.001). In patients with AF, the strongest independent FMD determinant was arrhythmia duration (p < 0.001), followed by smoking (p = 0.013) and total cholesterol levels (p = 0.045). Our findings confirm that sustained AF is associated with systemic endothelial dysfunction even in relatively young patients with no cardiovascular disorders or risk factors. AF is an independent contributor to lower FMD and a prolonged arrhythmia duration may confer the risk for more profound endothelial damage.

Loneliness as the cause and the effect of problematic Internet use: the relationship between Internet use and psychological well-being.

PubMed

Kim, Junghyun; LaRose, Robert; Peng, Wei

2009-08-01

The current research started from the assumption that one of the major motives driving individuals' Internet use is to relieve psychosocial problems (e.g., loneliness, depression). This study showed that individuals who were lonely or did not have good social skills could develop strong compulsive Internet use behaviors resulting in negative life outcomes (e.g., harming other significant activities such as work, school, or significant relationships) instead of relieving their original problems. Such augmented negative outcomes were expected to isolate individuals from healthy social activities and lead them into more loneliness. Even though previous research suggests that social use of the Internet (e.g., social networking sites, instant messaging) could be more problematic than entertainment use (e.g., downloading files), the current study showed that the former did not show stronger associations than the latter in the key paths leading to compulsive Internet use.

Synthesis, structure, computational and in-silico anticancer studies of N,N-diethyl-N‧-palmitoylthiourea

NASA Astrophysics Data System (ADS)

Asegbeloyin, Jonnie Niyi; Oyeka, Ebube Evaristus; Okpareke, Obinna; Ibezim, Akachukwu

2018-02-01

A new potential ONS donor ligand N,N-diethyl-N‧-palmitoylthiourea (PACDEA) with the molecular formular C21H42N2OS has been synthesized and characterized by ESI-MS, UV, FTIR 1H and 13C NMR spectroscopy and single X-ray crystallography. The asymmetric molecules crystallized in the centrosymmetric structure of monoclinic crystal system with space group P21/c. In the crystal structure of the compound, molecules are linked in a continuous chain by intermolecular Nsbnd H⋯Odbnd C hydrogen bonds, which stabilized the crystal structure. The palmitoyl moiety and N (2)-ethyl group lie on a plane, while the thiocarbonyl moiety is twisted and lying othorgonal to the plane. Non-covalent interaction (NCI) analysis on the hydrogen bonded solid state structure of the molecule revealed the presence of a significant number of non-covalent interactions including intermolecular hydrogen bonding interactions, Csbnd Hsbnd -lone pair interactions, weak Van der Waals interactions, and steric/ring closure interactions. The NCI analysis also showed the presence of intramolecular stabilizing Csbnd H⋯Odbnd C and Csbnd H⋯Sdbnd C interactions. Docking simulation revealed that the compound interacted favourably with ten selected validated anticancer drug targets, which is an indication that the compound could possess some anticancer properties.

Molecular orbital analysis of the inverse halogen dependence of nuclear magnetic shielding in LaX₃, X = F, Cl, Br, I.

PubMed

Moncho, Salvador; Autschbach, Jochen

2010-12-01

The NMR nuclear shielding tensors for the series LaX(3), with X = F, Cl, Br and I, have been computed using two-component relativistic density functional theory based on the zeroth-order regular approximation (ZORA). A detailed analysis of the inverse halogen dependence (IHD) of the La shielding was performed via decomposition of the shielding tensor elements into contributions from localized and delocalized molecular orbitals. Both spin-orbit and paramagnetic shielding terms are important, with the paramagnetic terms being dominant. Major contributions to the IHD can be attributed to the La-X bonding orbitals, as well as to trends associated with the La core and halogen lone pair orbitals, the latter being related to X-La π donation. An 'orbital rotation' model for the in-plane π acceptor f orbital of La helps to rationalize the significant magnitude of deshielding associated with the in-plane π donation. The IHD goes along with a large increase in the shielding tensor anisotropy as X becomes heavier, which can be associated with trends for the covalency of the La-X bonds, with a particularly effective transfer of spin-orbit coupling induced spin density from iodine to La in LaI(3). Copyright © 2010 John Wiley & Sons, Ltd.

Mild and Selective Hydrozirconation of Amides to Aldehydes Using Cp2Zr(H)Cl

PubMed Central

Spletstoser, Jared T.; White, Jonathan M.; Tunoori, Ashok Rao; Georg, Gunda I.

2008-01-01

An investigation of the use of Cp2Zr(H)Cl (Schwartz’s reagent) to reduce a variety of amides to the corresponding aldehydes under very mild reaction conditions and in high yields is reported. A range of tertiary amides, including Weinreb’s amide, can be converted directly to the corresponding aldehydes with remarkable chemoselectivity. Primary and secondary amides proved to be viable substrates for reduction as well, although the yields were somewhat diminished compared to the corresponding tertiary amides. Results from NMR experiments suggested the presence of a stable, 18-electron zirconacycle intermediate that presumably affords the aldehyde upon water or silica gel workup. A series of competition experiments revealed a preference of the reagent for substrates in which the lone pair of the nitrogen is electron releasing and thus more delocalized across the amide bond by resonance. This trend accounts for the observed excellent selectivity for tertiary amides versus esters. Experiments regarding the solvent dependence of the reaction suggested a kinetic profile similar to that postulated for the hydrozirconation of alkenes and alkynes. Addition of p-anisidine to the reaction intermediate resulted in the formation of the corresponding imine mimicking the addition of water that forms the aldehyde. PMID:17315870

Durable polydopamine-coated porous sulfur core-shell cathode for high performance lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Deng, Yuanfu; Xu, Hui; Bai, Zhaowen; Huang, Baoling; Su, Jingyang; Chen, Guohua

2015-12-01

Lithium-sulfur batteries show fascinating potential for advanced energy system due to their high specific capacity, low-cost, and environmental benignity. However, their wide applications have been plagued by low coulombic efficiency, fast capacity fading and poor rate performance. Herein, a facile method for preparation of S@PDA (PDA = polydopamine) composites with core-shell structure and good electrochemical performance as well as the First-Principles calculations on the interactions of PDA and polysulfides are reported. Taking the advantages of the core-shell structure with porous sulfur core, the high mechanical flexibility of PDA for accommodating the volumetric variation during the discharge/charge processes, the good lithium ion conductivity and the strong chemical interactions between the nitrogen/oxygen atoms with lone electron pair and lithium polysulfides for alleviating their dissolution, the S@PDA composites exhibit high discharge capacities at different current densities (1048 and 869 mAh g-1 at 0.2 and 0.8 A g-1, respectively) and excellent capacity retention capability. A capacity decay as low as 0.021% per cycle and an average coulombic efficiency of 98.5% is observed over a long-term cycling of 890 cycles at 0.8 A g-1. The S@PDA electrode has great potential as a low-cost cathode in high energy Li-S batteries.

Non-adiabatic behavior in the homolytic and heterolytic bond dissociation of protonated hydrazine: A guided ion beam and theoretical investigation

NASA Astrophysics Data System (ADS)

McNary, Christopher P.; Armentrout, P. B.

2017-09-01

Threshold collision-induced dissociation using a guided ion beam tandem mass spectrometer was performed on protonated hydrazine and its perdeuterated variant. The dominant dissociation pathways observed were endothermic homolytic and heterolytic cleavages of the N-N bond. The data were analyzed using a statistical model after accounting for internal and kinetic energy distributions, multiple collisions, and kinetic shifts to obtain 0 K bond dissociation energies. Comparison with literature thermochemistry demonstrates that both channels behave non-adiabatically. Heterolytic bond cleavage yields NH2+ + NH3 products, but the NH2+ fragment is in the spin-restricted excited 1A1 state and not in the spin-forbidden ground 3B1 state, whereas homolytic bond cleavage leads to dissociation to the NH3+ + NH2 product asymptote with NH2 in its excited 2A1 state rather than the energetically favored 2B1 state. The rationale for the non-adiabatic behavior observed in the homolytic bond cleavage is revealed by detailed theoretical calculations of the relevant potential energy surfaces and the relevant occupied valence molecular orbitals. These calculations suggest that the non-adiabatic behavior results from conservation of the σ and π character of the binding and lone pair electrons on the nitrogen atoms.

Effect of polarizable lone pair cations on the second-harmonic generation (SHG) properties of noncentrosymmetric (NCS) Bi(2-x)Y(x)TeO₅ (x = 0-0.2).

PubMed

Jo, Hongil; Kim, Yeong Hun; Lee, Dong Woo; Ok, Kang Min

2014-08-14

Y(3+)-doped noncentrosymmetric (NCS) bismuth tellurite materials, Bi(2-x)Y(x)TeO5 (x = 0, 0.1, and 0.2), have been synthesized through standard solid-state reactions and structurally characterized by powder neutron diffraction. The reported NCS materials crystallize in the orthorhombic space group Abm2 (no. 39), and exhibit pseudo-three-dimensional frameworks that are composed of BiO3, BiO5, and TeO3 polyhedra. Detailed diffraction studies show that the cell volume of Bi(2-x)Y(x)TeO5 decreases with an increasing amount of Y(3+)on the Bi(3+) sites. However, no ordering between Bi(3+) and Y(3+) was observed in the Bi(2-x)Y(x)TeO5. Powder second-harmonic generation (SHG) measurements, using 1064 nm radiation, reveal that Bi2TeO5, Bi(1.9)Y(0.1)TeO5, and Bi(1.8)Y(0.2)TeO5 exhibit SHG efficiencies of approximately 300, 200, and 60 times that of α-SiO2, respectively. The reduction in SHG for Y(3+)-doped materials is consistent with the lack of net moment originating from polyhedra with a polarizable Bi(3+) cation.

PNacPNacE: (E = Ga, In, Tl) - monomeric group 13 metal(i) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide.

PubMed

Sindlinger, Christian P; Lawrence, Samuel R; Acharya, Shravan; Ohlin, C André; Stasch, Andreas

2017-12-12

The salt metathesis reaction of the sterically demanding bis(iminophosphoranyl)methanide alkali metal complexes LM (L - = HC(Ph 2 P[double bond, length as m-dash]NDip) 2 - , Dip = 2,6- i Pr 2 C 6 H 3 ; M = Li, Na, K) with "GaI", InBr or TlBr afforded the monomeric group 13 metal(i) complexes LE:, E = Ga (1), In (2) and Tl (3) in moderate yields, and small quantities of LGaI 2 4 in the case of Ga, respectively. The molecular structures of LE: 1-3 from X-ray single crystal diffraction show them to contain puckered six-membered rings with N,N'-chelating methanide ligands and two-coordinated metal(i) centres. Reduction reactions of LAlI 2 5, prepared by iodination of LAlMe 2 , were not successful and no aluminium(i) congener could be prepared so far. DFT studies on LE:, E = Al-Tl, were carried out and support the formulation as an anionic, N,N'-chelating methanide ligand coordinating to group 13 metal(i) cations. The HOMOs of the molecules for E = Al-In show a dominant contribution from a metal-based lone pair that is high in s-character.

First example of a high-level correlated calculation of the indirect spin-spin coupling constants involving tellurium: tellurophene and divinyl telluride.

PubMed

Rusakov, Yury Yu; Krivdin, Leonid B; Østerstrøm, Freja F; Sauer, Stephan P A; Potapov, Vladimir A; Amosova, Svetlana V

2013-08-21

This paper documents the very first example of a high-level correlated calculation of spin-spin coupling constants involving tellurium taking into account relativistic effects, vibrational corrections and solvent effects for medium sized organotellurium molecules. The (125)Te-(1)H spin-spin coupling constants of tellurophene and divinyl telluride were calculated at the SOPPA and DFT levels, in good agreement with experimental data. A new full-electron basis set, av3z-J, for tellurium derived from the "relativistic" Dyall's basis set, dyall.av3z, and specifically optimized for the correlated calculations of spin-spin coupling constants involving tellurium was developed. The SOPPA method shows a much better performance compared to DFT, if relativistic effects calculated within the ZORA scheme are taken into account. Vibrational and solvent corrections are next to negligible, while conformational averaging is of prime importance in the calculation of (125)Te-(1)H spin-spin couplings. Based on the performed calculations at the SOPPA(CCSD) level, a marked stereospecificity of geminal and vicinal (125)Te-(1)H spin-spin coupling constants originating in the orientational lone pair effect of tellurium has been established, which opens a new guideline in organotellurium stereochemistry.

Study of lithium cation in water clusters: based on atom-bond electronegativity equalization method fused into molecular mechanics.

PubMed

Li, Xin; Yang, Zhong-Zhi

2005-05-12

We present a potential model for Li(+)-water clusters based on a combination of the atom-bond electronegativity equalization and molecular mechanics (ABEEM/MM) that is to take ABEEM charges of the cation and all atoms, bonds, and lone pairs of water molecules into the intermolecular electrostatic interaction term in molecular mechanics. The model allows point charges on cationic site and seven sites of an ABEEM-7P water molecule to fluctuate responding to the cluster geometry. The water molecules in the first sphere of Li(+) are strongly structured and there is obvious charge transfer between the cation and the water molecules; therefore, the charge constraint on the ionic cluster includes the charged constraint on the Li(+) and the first-shell water molecules and the charge neutrality constraint on each water molecule in the external hydration shells. The newly constructed potential model based on ABEEM/MM is first applied to ionic clusters and reproduces gas-phase state properties of Li(+)(H(2)O)(n) (n = 1-6 and 8) including optimized geometries, ABEEM charges, binding energies, frequencies, and so on, which are in fair agreement with those measured by available experiments and calculated by ab initio methods. Prospects and benefits introduced by this potential model are pointed out.

Reaction of (carbonylimido)sulfur(IV) derivatives with TAS-fluoride, (Me2N)3S+Me3SiF2-.

PubMed

Lork, E; Viets, D; Mews, R; Oberhammer, H

2000-10-16

In the reaction of TAS-fluoride, (Me2N)3S+Me3SiF2-, with carbonyl sulfur difluoride imides RC(O)NSF2 (R = F, CF3), C-N bond, cleavage is observed, and TAS+RC(O)F2- and NSF are the final products. From TASF and RC(O)NS(CF3)F, the salts TAS+RC(O)NS(CF3)F2- (R = F (14), CF3 (15)), with psi-pentacoordinate sulfur centers in the anions, are formed. An X-ray structure investigation of 14 shows that the fluorine atoms occupy axial positions and CF3, NC(O)F, and the sulfur lone pair occupy equatorial positions of the trigonal bipyramid. The -C(O)F group lies in the equatorial plane with the CO bond synperiplanar to the SN bond. According to B3LYP calculations, this structure corresponds to a global minimum and the expected axial orientation of the -C(O)F group represents a transition state. Calculations for the unstable FC(O)NSF3- anion show a different geometry. The -C(O)F group deviates 40 degrees from axial orientation, and the equatorially bonded fluorine is, in contrast to the -CF3 group in 14, syn positioned.

Intrinsic Conformational Preferences of Cα,α-Dibenzylglycine

PubMed Central

Casanovas, Jordi; Nussinov, Ruth; Alemán, Carlos

2009-01-01

The intrinsic conformational preferences of Cα,α-dibenzylglycine, a symmetric α,α-dialkylated amino acid bearing two benzyl substituents on the α-carbon atom, have been determined using quantum chemical calculations at the B3LYP/6-31+G(d,p) level. A total of 46 minimum energy conformations were found for the N-acetyl-N'-methylamide derivative, even though only 9 of them showed a relative energy lower than 5.0 kcal/mol. The latter involves C7, C5 and α' backbone conformations stabilized by intramolecular hydrogen bonds and/or N-H…π interactions. Calculation of the conformational free energies in different environments (gas-phase, carbon tetrachloride, chloroform, methanol and water solutions) indicates that four different minima (two C5 and two C7) are energetically accessible at room temperature in the gas-phase, while in methanol and aqueous solutions one such minimum (C5) becomes the only significant conformation. Comparison with results recently reported for Cα,α-diphenylglycine indicates that substitution of phenyl side groups by benzyl enhances the conformational flexibility leading to (i) a reduction of the strain of the peptide backbone; and (ii) alleviating the repulsive interactions between the π electron density of the phenyl groups and the lone pairs of the carbonyl oxygen atoms. PMID:18465898

Organic Molecules On the Surfaces of Iapetus and Phoebe

NASA Technical Reports Server (NTRS)

Pendleton, Yvonne J.; Dalle Ore, Cristina M.; Clark, Roger N.; Cruikshank, Dale P.

2017-01-01

Absorption bands of both aliphatic and aromatic organic molecules are found in the reflectance spectra of Saturn satellites Iapetus, Phoebe, and Hyperion obtained with the Cassini Visible-Infrared Mapping Spectrometer (VIMS). The VIMS data do not fully resolve the individual bands of C-H functional groups specific to particular molecules, but instead show absorption envelopes representing blended clusters of the bands of aromatic (approximately 3.28 microns) and aliphatic (approximately 3.4 microns) hydrocarbons known in spectra of interstellar dust. In Cruikshank et al. (2014), we matched components of the unresolved hydrocarbon band envelopes with clusters of bands of a range of functional groups in specific types of organic compounds (e.g., normal and N-substituted polycyclic aromatic hydrocarbons, olefins, cycloalkanes, and molecules with lone-pair interactions of N and O with CH3+). In the work reported here, we revisit the spectra of Iapetus and Phoebe using VIMS data processed with improved radiometric and wavelength calibration (denoted RC19). The band envelopes of both aromatic and aliphatic hydrocarbons are now more clearly defined, corroborating the provisional assignment of specific classes of molecules in Cruikshank et al. 2014, but permitting a more reliable quantitative assessment of the relative contributions of those classes, and a revision to the earlier estimate of the ratio of the abundances of aromatic to aliphatic molecules.

Intrinsic Folding Proclivities in Cyclic β-Peptide Building Blocks: Configuration and Heteroatom Effects Analyzed by Conformer-Selective Spectroscopy and Quantum Chemistry.

PubMed

Alauddin, Mohammad; Gloaguen, Eric; Brenner, Valérie; Tardivel, Benjamin; Mons, Michel; Zehnacker-Rentien, Anne; Declerck, Valérie; Aitken, David J

2015-11-09

This work describes the use of conformer-selective laser spectroscopy following supersonic expansion to probe the local folding proclivities of four-membered ring cyclic β-amino acid building blocks. Emphasis is placed on stereochemical effects as well as on the structural changes induced by the replacement of a carbon atom of the cycle by a nitrogen atom. The amide A IR spectra are obtained and interpreted with the help of quantum chemistry structure calculations. Results provide evidence that the building block with a trans-substituted cyclobutane ring has a predilection to form strong C8 hydrogen bonds. Nitrogen-atom substitution in the ring induces the formation of the hydrazino turn, with a related but distinct hydrogen-bonding network: the structure is best viewed as a bifurcated C8/C5 bond with the N heteroatom lone electron pair playing a significant acceptor role, which supports recent observations on the hydrazino turn structure in solution. Surprisingly, this study shows that the cis-substituted cyclobutane ring derivative also gives rise predominantly to a C8 hydrogen bond, although weaker than in the two former cases, a feature that is not often encountered for this building block. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the temperature dependence of H-U{sub iso} in the riding hydrogen model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lübben, Jens; Volkmann, Christian; Grabowsky, Simon

The temperature dependence of hydrogen U{sub iso} and parent U{sub eq} in the riding hydrogen model is investigated by neutron diffraction, aspherical-atom refinements and QM/MM and MO/MO cluster calculations. Fixed values of 1.2 or 1.5 appear to be underestimated, especially at temperatures below 100 K. The temperature dependence of H-U{sub iso} in N-acetyl-l-4-hydroxyproline monohydrate is investigated. Imposing a constant temperature-independent multiplier of 1.2 or 1.5 for the riding hydrogen model is found to be inaccurate, and severely underestimates H-U{sub iso} below 100 K. Neutron diffraction data at temperatures of 9, 150, 200 and 250 K provide benchmark results for thismore » study. X-ray diffraction data to high resolution, collected at temperatures of 9, 30, 50, 75, 100, 150, 200 and 250 K (synchrotron and home source), reproduce neutron results only when evaluated by aspherical-atom refinement models, since these take into account bonding and lone-pair electron density; both invariom and Hirshfeld-atom refinement models enable a more precise determination of the magnitude of H-atom displacements than independent-atom model refinements. Experimental efforts are complemented by computing displacement parameters following the TLS+ONIOM approach. A satisfactory agreement between all approaches is found.« less

Spectroscopic investigations on the interaction of thioacetamide with ZnO quantum dots and application for its fluorescence sensing

NASA Astrophysics Data System (ADS)

Saha, Dipika; Negi, Devendra P. S.

2018-01-01

The purpose of the present work was to develop a method for the sensing of thioacetamide by using spectroscopic techniques. Thioacetamide is a carcinogen and it is important to detect its presence in food-stuffs. Semiconductor quantum dots are frequently employed as sensing probes since their absorption and fluorescence properties are highly sensitive to the interaction with substrates present in the solution. In the present work, the interaction between thioacetamide and ZnO quantum dots has been investigated by using UV-visible, fluorescence and infrared spectroscopy. Besides, dynamic light scattering (DLS) has also been utilized for the interaction studies. UV-visible absorption studies indicated the bonding of the lone pair of sulphur atom of thioacetamide with the surface of the semiconductor. The fluorescence band of the ZnO quantum dots was found to be quenched in the presence of micromolar concentrations of thioacetamide. The quenching was found to follow the Stern-Volmer relationship. The Stern-Volmer constant was evaluated to be 1.20 × 105 M- 1. Infrared spectroscopic measurements indicated the participation of the sbnd NH2 group and the sulphur atom of thioacetamide in bonding with the surface of the ZnO quantum dots. DLS measurements indicated that the surface charge of the semiconductor was shielded by the thioacetamide molecules.

Remediation of Nitrobenzene Contaminated Soil by Combining Surfactant Enhanced Soil Washing and Effluent Oxidation with Persulfate

PubMed Central

Yan, Jingchun; Gao, Weiguo; Qian, Linbo; Han, Lu; Chen, Yun; Chen, Mengfang

2015-01-01

The combination of surfactant enhanced soil washing and degradation of nitrobenzene (NB) in effluent with persulfate was investigated to remediate NB contaminated soil. Aqueous solution of sodium dodecylbenzenesulfonate (SDBS, 24.0 mmol L-1) was used at a given mass ratio of solution to soil (20:1) to extract NB contaminated soil (47.3 mg kg-1), resulting in NB desorption removal efficient of 76.8%. The washing effluent was treated in Fe2+/persulfate and Fe2+/H2O2 systems successively. The degradation removal of NB was 97.9%, being much higher than that of SDBS (51.6%) with addition of 40.0 mmol L-1 Fe2+ and 40.0 mmol L-1 persulfate after 15 min reaction. The preferential degradation was related to the lone pair electron of generated SO4•−, which preferably removes electrons from aromatic parts of NB over long alkyl chains of SDBS through hydrogen abstraction reactions. No preferential degradation was observed in •OH based oxidation because of its hydrogen abstraction or addition mechanism. The sustained SDBS could be reused for washing the contaminated soil. The combination of the effective surfactant-enhanced washing and the preferential degradation of NB with Fe2+/persulfate provide a useful option to remediate NB contaminated soil. PMID:26266532

Hydrazino-methoxy-1,3,5-triazine Derivatives' Excellent Corrosion Organic Inhibitors of Steel in Acidic Chloride Solution.

PubMed

El-Faham, Ayman; Osman, Sameh M; Al-Lohedan, Hamad A; El-Mahdy, Gamal A

2016-06-01

The corrosion inhibition performance of 2-hydrazino-4,6-dimethoxy-1,3,5-tirazine (DMeHT), 2,4-dihydrazino-6-methoxy-1,3,5-triaizine (DHMeT), and 2,4,6-tridydrazino-1,3,5-triaizne (TH₃) on steel corrosion in acidic media was examined using electrochemical techniques. The results showed 2,4-Ddihydrazino-6-methoxy-1,3,5-triaizine (DHMeT) gave the best corrosion protection performance among the other hydrazino derivatives even at a low concentration of 25 ppm (95%). The number of hydrazino groups play an important role in the corrosion inhibition, where the two hydrazine groups increased the electrostatic interactions between the protonated tested compounds, the negatively charged steel surface resulted from the adsorption of the chloride anions, and the presence of the methoxy group made the compound more reliable for formation of film protection on the surface of steel through the lone pair of oxygen atoms. Electrochemical Impedance Spectroscopy (EIS) measurements suggested that the corrosion process of steel in presence of the hydrazino-s-triazine derivatives (TH₃, DMeHT and DHMeT) were being controlled by the charge transfer reaction. Polarization curves indicated that the examined TH₃, DMeHT and DHMeT behaved as mixed type inhibitors.

Synthesis and characterization of an anticoagulant 4-hydroxy-1-thiocoumarin by FTIR, FT-Raman, NMR, DFT, NBO and HOMO-LUMO analysis

NASA Astrophysics Data System (ADS)

Arjunan, V.; Santhanam, R.; Sakiladevi, S.; Marchewka, M. K.; Mohan, S.

2013-04-01

Experimental and theoretical investigations on the molecular structural, electronic and the vibrational characteristics of 4-hydroxy-1-thiocoumarin are presented. Conformational analysis was carried out to obtain the more stable configuration of the compound. The vibrational frequencies were obtained by DFT/B3LYP calculations employing 6-311++G(d,p), 6-31G(d,p), cc-pVTZ basic sets and B3PW91 method with 6-311++G(d,p) basis set and are compared with FTIR and FT-Raman spectral data recorded in the region of 4000-400 and 4000-100 cm-1, respectively. The total electron density and molecular electrostatic potential surfaces of the molecule were constructed to display electrostatic potential (electron + nuclei) distribution. The electronic properties HOMO and LUMO energies were measured. 1H and 13C NMR spectra were recorded and 1H and 13C nuclear magnetic resonance chemical shifts of the molecule were calculated by using the Gauge-Independent Atomic Orbital (GIAO) method and analyzed. The picture of localized bonds and lone pairs, stabilization energy of the delocalization of electrons, the charge and hybridisation of the atoms of 4-hydroxy-1-thiocoumarin were clearly explained by NBO analysis.

Increasing Social Integration for College Students with Autism Spectrum Disorder

PubMed Central

Ashbaugh, Kristen; Koegel, Robert; Koegel, Lynn

2016-01-01

Increasing numbers of individuals with Autism Spectrum Disorder (ASD) are entering postsecondary education; however, many report feeling lonely and isolated. These difficulties with socialization have been found to impact students’ academic success, involvement within the university, and overall well being. Therefore, the purpose of this study was to assess, within the context of a multiple-baseline across participants design, whether a structured social planning intervention would increase social integration for college students with ASD. The intervention consisted of weekly meetings to plan social activities around the student with ASD's interests, improve organizational skills, and target specific social skills. Additionally, each participant had a peer mentor for support during the social activities. The results showed that following intervention all participants increased their number of community-based social events, extracurricular activities, and peer interactions. Furthermore, participants improved in their academic performance and satisfaction with their college experience. Results are discussed in regards to developing specialized programs to assist college students with ASD. PMID:28642808

Ingenuity and National Security

DTIC Science & Technology

2013-06-01

is in an unfamiliar situation as the lone super power without a significant existential threat. China is a rising power and Russia aspires to...independence to the most powerful nation on the planet . The time period surrounding World War II demonstrated that governmental processes and

Are they out there?

NASA Astrophysics Data System (ADS)

Wesson, John; Seberkuhn

2015-01-01

In reply to the book review "A lucky, but lonely, planet" (November 2014 p50, http://ow.ly/EWb5J) and the comment "Not so unlikely" by Peter Morgan (Feedback, December 2014 p22), which discussed the likelihood of life existing on other planets.

77 FR 28880 - Ocean Transportation Intermediary License Applicants

Federal Register 2010, 2011, 2012, 2013, 2014

2012-05-16

... (NVO & OFF), 332 Hindry Avenue, Inglewood, CA 90301, Officers: Edison Chen, Manager (Qualifying Individual), Wei-Nung (Janus) Lin, Member/Manager/CEO, Application Type: QI Change/Trade Name Change. Lone... 77032, Officer: Albert E. Garcia, President/Manager/Member (Qualifying Individual), Application Type...

Chapter 9 : getting ready for NextGen.

DOT National Transportation Integrated Search

2008-01-01

George W. Bush became the forty-third president on January 20, : 2001. Five days later, former Member of Congress Norman Mineta : (D-CA) took the oath of office as the nations fourteenth Secretary : of Transportation. The lone Democrat in George W...

Manage Emotions Without Cigarettes

Cancer.gov

Maybe you used to reach for a cigarette after a tough day at the office. Or found comfort in the companionship of a cigarette on a lonely night. Maybe you used to have cigarettes available as one way to help you deal with uncomfortable emotions.

Teleworking in connection with technical aids for disabled persons.

PubMed

Alimandi, L; Andrich, R; Porqueddu, B

1995-01-01

An experimental teleworking arrangement was established between Milan and Rome in order to evaluate the use of multimedia technology and remote working for improving the service provided by an information and advice centre for the disabled. This activity requires a highly interdisciplinary approach and both clinical and technical expertise. The hypothesis was that offering the lone expert in Rome the possibility of teleconsulting with colleagues in Milan (where the whole range of expertise was available) would provide a comprehensive service for disabled clients asking for advice on technical aids in Rome. The results of an experiment demonstrated the feasibility of such teleworking and allowed a teleconsulting method to be defined that fits the specific needs of the technical-aid information service and improves quality.

A new termite (Isoptera, Termitidae, Syntermitinae, Macuxitermes) from Colombia

PubMed Central

Postle, Anthony C.; Scheffrahn, Rudolf H.

2016-01-01

Abstract A new species of termite, Macuxitermes colombicus Postle & Scheffrahn is described from soldiers and workers collected from Departamento Magdalena, Colombia. The soldier of Macuxitermes colombicus differs from its lone congener in having no protuberances on the head capsule. PMID:27408525

78 FR 61352 - Change in Bank Control Notices; Acquisitions of Shares of a Bank or Bank Holding Company

Federal Register 2010, 2011, 2012, 2013, 2014

2013-10-03

... shares of FirstSecure Bank and Trust Company, Palos Hill, IL. B. Federal Reserve Bank of Minneapolis..., Julie Jennings, Lone Tree, Colorado, and R. Will Isham, Gordon, Nebraska, in their individual capacities...

NDCEE Annual Technologies Publication

DTIC Science & Technology

2004-07-01

LCAAP), Independence, Missouri Lone Star Army Ammunition Plant (LSAAP), Texarkana , Texas Marine Corps Logistics Base, Yermo Annex, Barstow...100-101, 117, 123, 186, 210, 251, 258, 285, 291; 200-312, 337, 339, 852; 800-801; 900- 909, 1956, 1989, 2016, 2017 , 2018, 2019, 2021, 2089, 2097, 2106

Common Atrial Fibrillation Risk Alleles at 4q25 Predict Recurrence after Catheter-based Atrial Fibrillation Ablation

PubMed Central

Shoemaker, M. Benjamin; Muhammad, Raafia; Parvez, Babar; White, Brenda W.; Streur, Megan; Song, Yanna; Stubblefield, Tanya; Kucera, Gayle; Blair, Marcia; Rytlewski, Jason; Parvathaneni, Sunthosh; Nagarakanti, Rangadham; Saavedra, Pablo; Ellis, Christopher; Whalen, S. Patrick; Roden, Dan M; Darbar, Dawood

2012-01-01

Background Common single nucleotide polymorphisms (SNPs) at chromosome 4q25 (rs2200733, rs10033464) are associated with both lone and typical AF. Risk alleles at 4q25 have recently been shown to predict recurrence of AF after ablation in a population of predominately lone AF, but lone AF represents only 5–30% of AF cases. Objective To test the hypothesis that 4q25 AF risk alleles can predict response to AF ablation in the majority of AF cases. Methods Patients enrolled in the Vanderbilt AF Registry underwent 378 catheter-based AF ablations (median age 60 years, 71% male, 89% typical AF) between 2004 and 2011. The primary endpoint was time to recurrence of any non-sinus atrial tachyarrhythmia (atrial tachycardia, atrial flutter, or AF; [AT/AF]). Results Two-hundred AT/AF recurrences (53%) were observed. In multivariable analysis, the rs2200733 risk allele predicted a 24% shorter recurrence-free time (survival time ratio 0.76 95% confidence interval [CI] 0.6–0.95, P=0.016) compared with wild-type. The heterozygous haplotype demonstrated a 21% shorter recurrence-free time (survival time ratio = 0.79, 95% CI 0.62–0.99) and the homozygous risk allele carriers a 39% shorter recurrence-free time (survival time ratio = 0.61, 95% CI 0.37–1.0) (P=0.037). Conclusion Risk alleles at the 4q25 loci predict impaired clinical response to AF ablation in a population of predominately typical AF patients. Our findings suggest the rs2200733 polymorphism may hold promise as an as an objectively measured patient characteristic that can used as a clinical tool for selection of patients for AF ablation. PMID:23178686