Novel thioarsenates {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]}: introducing an anionic second ligand to modify MnII complex cations of 2,2'-bipyridine.

PubMed

Liu, Guang-Ning; Guo, Guo-Cong; Wang, Ming-Sheng; Huang, Jin-Shun

2014-03-14

Two novel manganese thioarsenates, {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 (1, 2,2'-bipy = 2,2'-bipyridine) and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]} (2), containing thiocyanate-modified Mn-2,2'-bipy complex cations were synthesized. They feature two terminal [Mn(2,2'-bipy)2(SCN)](+) complex cations bridged by a polyanion {[Mn(2,2'-bipy)]2(As(V)S4)2}(2-) for 1 and a cyclic thioarsenate anion (As(III)2S6)(2-) for 2. In 2, the [As(III)2(S2)2S2](2-) anion can be described as two (As(III)S3)(3-) trigonal-pyramids interlinked through S-S bonds. The method to obtain new metal complex cations shown here, introducing an anionic second ligand to modify the number of coordination sites and the charges of the metal complex cations simultaneously, is different from the traditional methods, varying either the TM center or the organic ligand or employing mixed neutral organic ligands, and may open up a new route for preparing novel chalcogenidometalates. Compounds 1 and 2 exhibit wide optical gaps of 2.20 and 2.67 eV, respectively, and photoluminescence with the emission maxima occurring around 440 nm. Magnetic measurements show the presence of antiferromagnetic interactions between Mn(II) centers in the two compounds.

Injuries to the Collateral Ligaments of the Metacarpophalangeal Joint of the Thumb, Including Simultaneous Combined Thumb Ulnar and Radial Collateral Ligament Injuries, in National Football League Athletes.

PubMed

Werner, Brian C; Belkin, Nicole S; Kennelly, Steve; Weiss, Leigh; Barnes, Ronnie P; Rodeo, Scott A; Warren, Russell F; Hotchkiss, Robert N

2017-01-01

Thumb collateral ligament injuries occur frequently in the National Football League (NFL). In the general population or in recreational athletes, pure metacarpophalangeal (MCP) abduction or adduction mechanisms yield isolated ulnar collateral ligament (UCL) and radial collateral ligament (RCL) tears, respectively, while NFL athletes may sustain combined mechanism injury patterns. To evaluate the incidence of simultaneous combined thumb UCL and RCL tears among all thumb MCP collateral ligament injuries in NFL athletes on a single team. Case series; Level of evidence, 4. A retrospective review of all thumb injuries on a single NFL team from 1991 to 2014 was performed. All players with a thumb MCP collateral ligament injury were included. Collateral ligament injuries were confirmed by review of both physical examination findings and magnetic resonance imaging. Player demographics, surgical details, and return-to-play data were obtained from the team electronic medical record and surgeons' records. A total of 36 thumbs in 32 NFL players were included in the study, yielding an incidence of 1.6 thumb MCP collateral ligament injuries per year on a single NFL team. Of these, 9 thumbs (25%) had a simultaneous combined UCL and RCL tear injury pattern confirmed on both physical examination and MRI. The remaining 27 thumbs (75%) were isolated UCL injuries. All combined UCL/RCL injuries required surgery due to dysfunction from instability; 63.0% of isolated UCL injuries required surgical repair ( P = .032) due to continued pain and dysfunction from instability. Repair, when required, was delayed until the end of the season. All players with combined UCL/RCL injuries and isolated UCL injuries returned to play professional football the following season. Simultaneous combined thumb UCL and RCL tear is a previously undescribed injury pattern that occurred in 25% of thumb MCP collateral ligament injuries on a single NFL team over a 23-year period. All players with combined thumb UCL/RCL injuries required surgical repair, which was significantly higher compared with players with isolated UCL injuries. Team physicians and hand surgeons treating elite football players with suspected thumb collateral ligament injuries should examine for RCL and UCL instability and consider MRI if any concern exists for a combined ligament injury pattern, as this injury is likely frequently missed.

Bis(2,3,5,6-tetra-2-pyridylpyrazine-κ3 N 2,N 1,N 6)iron(II) bis­(dicyanamidate) 4.5-hydrate

PubMed Central

Callejo, L.; De la Pinta, N.; Madariaga, G.; Fidalgo, M.L.; Cortés, R.

2010-01-01

In the title compound, [Fe(C24H16N6)2][N(CN)2]2·4.5H2O, the central iron(II) ion is hexa­coordinated by six N atoms of two tridentate 2,3,5,6-tetra-2-pyridylpyrazine (tppz) ligands. Two dicyanamide anions [dca or N(CN)2 −] act as counter-ions, and 4.5 water mol­ecules act as solvation agents. The structure contains isolated cationic iron(II)–tppz complexes and the final neutrality is obtained with the two dicyanamide anions. One of the dicyanamide anions and a water mol­ecule are disordered with an occupancy ratio of 0.614 (8):0.386 (8). O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds involving dca, water and tppz mol­ecules are observed. PMID:21580205

Prevalence of Ulnar Collateral Ligament Surgery in Professional Baseball Players.

PubMed

Conte, Stan A; Fleisig, Glenn S; Dines, Joshua S; Wilk, Kevin E; Aune, Kyle T; Patterson-Flynn, Nancy; ElAttrache, Neal

2015-07-01

While the high rate of ulnar collateral ligament (UCL) injuries in professional baseball is widely discussed in the media and medical literature, the actual prevalence of UCL reconstruction has not been documented. The prevalence of UCL reconstruction will be higher among pitchers than nonpitchers, and Major League Baseball (MLB) pitchers will have a higher prevalence than will minor league pitchers. Descriptive epidemiology study. An online questionnaire was distributed to all 30 MLB organizations. Certified athletic trainers from each team administered the questionnaire to all players in the organization, including major league players and 6 levels of minor league players. Demographic data were compared between major and minor league players. Continuous variables (age, years of professional baseball, country of origin, etc) were compared with Student t tests (P < .05). Categorical variables (level, position, etc) were compared using chi-square analysis (P < .05). A total of 5088 professional baseball players (722 major league and 4366 minor league) participated in the survey. Pitchers represented 53% of all players, and 497 players reported at least 1 UCL reconstruction, demonstrating a prevalence rate of 10% (497 of 5088). Pitchers reported a significantly higher prevalence of UCL reconstruction (16%; 437 of 2706) than nonpitchers (3%; 60 of 2382; P < .001). Among major league pitchers, 25% (96 of 382) had a history of UCL reconstruction, while minor league pitchers showed a 15% (341 of 2324) prevalence (P < .001). Major league pitchers were also significantly older (28.8 ± 3.9 years) than minor league pitchers (22.8 ± 3.0; P < .001). The majority of major leaguers (86%) had their UCL reconstruction as professional pitchers, whereas the majority of minor league pitchers (61%) underwent their UCL reconstruction during high school and college (P < .001). The rates of UCL revision, prior elbow surgery, prior shoulder surgery, and types of UCL graft were similar between the major league and minor league pitchers. No difference in prevalence was shown between pitchers born in the United States versus Latin American countries. Pitchers have a high prevalence of UCL reconstruction in professional baseball, with 25% of major league pitchers and 15% of minor league pitchers having a history of the surgery. © 2015 The Author(s).

Analysis of pitching velocity in major league baseball players before and after ulnar collateral ligament reconstruction.

PubMed

Jiang, Jimmy J; Leland, J Martin

2014-04-01

Ulnar collateral ligament (UCL) reconstructions are relatively common among professional pitchers in Major League Baseball (MLB). To the authors' knowledge, there has not been a study specifically analyzing pitching velocity after UCL surgery. These measurements were examined in a cohort of MLB pitchers before and after UCL reconstruction. There is no significant loss in pitch velocity after UCL reconstruction in MLB pitchers. Cohort study; Level of evidence, 3. Between the years 2008 to 2010, a total of 41 MLB pitchers were identified as players who underwent UCL reconstruction. Inclusion criteria for this study consisted of a minimum of 1 year of preinjury and 2 years of postinjury pitch velocity data. After implementing exclusion criteria, performance data were analyzed from 28 of the 41 pitchers over a minimum of 4 MLB seasons for each player. A pair-matched control group of pitchers who did not have a known UCL injury were analyzed for comparison. Of the initial 41 players, 3 were excluded for revision UCL reconstruction. Eight of the 38 players who underwent primary UCL reconstruction did not return to pitching at the major league level, and 2 players who met the exclusion criteria were omitted, leaving data on 28 players available for final velocity analysis. The mean percentage change in the velocity of pitches thrown by players who underwent UCL reconstruction was not significantly different compared with that of players in the control group. The mean innings pitched was statistically different only for the year of injury and the first postinjury year. There were also no statistically significant differences between the 2 groups with regard to commonly used statistical performance measurements, including earned run average, batting average against, walks per 9 innings, strikeouts per 9 innings, and walks plus hits per inning pitched. There were no significant differences in pitch velocity and common performance measurements between players who returned to MLB after UCL reconstruction and pair-matched controls.

Absorption spectra analysis of hydrated uranium(III) complex chlorides

NASA Astrophysics Data System (ADS)

Karbowiak, M.; Gajek, Z.; Drożdżyński, J.

2000-11-01

Absorption spectra of powdered samples of hydrated uranium(III) complex chlorides of the formulas NH 4UCl 4 · 4H 2O and CsUCl 4 · 3H 2O have been recorded at 4.2 K in the 4000-26 000 cm -1 range. The analysis of the spectra enabled the determination of crystal-field parameters and assignment of 83 and 77 crystal-field levels for the tetrahydrate and trihydrate, respectively. The energies of the levels were computed by applying a simplified angular overlap model as well as a semiempirical Hamiltonian representing the combined atomic and crystal-field interactions. Ab initio calculations have enabled the application of a simplified parameterization and the determination of the starting values of the AOM parameters. The received results have proved that the AOM approach can quite well predict both the structure of the ground multiplet and the positions of the crystal-field levels in the 17 000-25 000 cm -1 range, usually obscured by strong f-d bands.

Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C 5Me 4R) 2UBr 2, (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br), and [K(THF)][(C 5Me 4R) 2UBr 2] (R = Me, Et)

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

Lichtscheidl, Alejandro Gaston; Pagano, Justin K.; Scott, Brian Lindley

The organometallic uranium species (C 5Me 4R) 2UBr 2 (R = Me, Et) were obtained by treating their chloride analogues (C 5Me 4R) 2UCl 2 (R = Me, Et) with Me 3SiBr. Treatment of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with K(O-2,6- iPr 2C 6H 3) afforded the halide aryloxide mixed-ligand complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(X) (R = Me, Et; X = Cl, Br). Complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br) (R = Me, Et) can also be synthesized by treating (C 5Me 4R) 2U(O-2,6-more » iPr 2C 6H 3)(Cl) (R = Me, Et) with Me 3SiBr, respectively. Reduction of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with KC 8 led to isolation of uranium(III) “ate” species [K(THF)][(C 5Me 5) 2UX 2] (X = Cl, Br) and [K(THF) 0.5][(C 5Me 4Et) 2UX 2] (X = Cl, Br), which can be converted to the neutral complexes (C 5Me 4R) 2U[N(SiMe 3) 2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.« less

Expanding the Chemistry of Actinide Metallocene Bromides. Synthesis, Properties and Molecular Structures of the Tetravalent and Trivalent Uranium Bromide Complexes: (C 5Me 4R) 2UBr 2, (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br), and [K(THF)][(C 5Me 4R) 2UBr 2] (R = Me, Et)

DOE PAGES

Lichtscheidl, Alejandro Gaston; Pagano, Justin K.; Scott, Brian Lindley; ...

2016-01-06

The organometallic uranium species (C 5Me 4R) 2UBr 2 (R = Me, Et) were obtained by treating their chloride analogues (C 5Me 4R) 2UCl 2 (R = Me, Et) with Me 3SiBr. Treatment of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with K(O-2,6- iPr 2C 6H 3) afforded the halide aryloxide mixed-ligand complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(X) (R = Me, Et; X = Cl, Br). Complexes (C 5Me 4R) 2U(O-2,6- iPr 2C 6H 3)(Br) (R = Me, Et) can also be synthesized by treating (C 5Me 4R) 2U(O-2,6-more » iPr 2C 6H 3)(Cl) (R = Me, Et) with Me 3SiBr, respectively. Reduction of (C 5Me 4R) 2UCl 2 and (C 5Me 4R) 2UBr 2 (R = Me, Et) with KC 8 led to isolation of uranium(III) “ate” species [K(THF)][(C 5Me 5) 2UX 2] (X = Cl, Br) and [K(THF) 0.5][(C 5Me 4Et) 2UX 2] (X = Cl, Br), which can be converted to the neutral complexes (C 5Me 4R) 2U[N(SiMe 3) 2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.« less

Synthesis and crystallographic characterization of a mononuclear cobalt(III) complex possessing both thiol­ate and thio­ether donors: reactivity of an thiol­ate-bridged penta­nuclear Co2Ag3 complex with iodo­methane

PubMed Central

Fukuda, Yosuke; Yoshinari, Nobuto; Konno, Takumi

2017-01-01

Treatment of an S-bridged penta­nuclear AgI 3CoIII 2 complex, [Ag3{Co(L)}2]3+ [L 3– = N(CH2NHCH2CH2S−)3], in which two tris­(thiol­ate)-type mononuclear CoIII units ([Co(L)]) are bridged by three AgI ions through S atoms, with iodo­methane (CH3I) gave a new CoIII mononuclear complex, [Co(LMe2)]2+ [LMe2 − = N(CH2NHCH2CH2S−)(CH2NHCH2CH2SCH3)2], systematic name: {2-[(bis{[2-(methylsulfanyl)ethyl]aminomethyl}aminomethyl)amino]ethanethiolato}cobalt(III) bis(hexafluoridophosphate). This cationic complex was crystallized with PF6 − anions to form the title compound, [Co(LMe2)](PF6)2. In the [Co(LMe2)]2+ cation, two of three thiol­ate groups in [Co(L)] are methyl­ated while one thiol­ate group remains unreacted. Although a total of eight stereoisomers are possible for [Co(LMe2)]2+, only a pair of enanti­omers {ΛRR- and ΔSS-[Co(LMe2)]2+} are selectively formed. In the crystal, the complex cations and the PF­6 − anions are connected through weak N—H⋯F, C—H⋯F and C—H⋯S hydrogen bonds into a three-dimensional structure. Two F atoms in one PF6 anion are disordered over two sets of sites with refined occupancies of 0.61 (4) and 0.39 (4) and two F atoms in the other PF6 − anion are disordered over two sets of sites with occupancies of 0.5. PMID:28529774

Correlation Between Quality of Evidence and Number of Citations in Top 50 Cited Articles on Elbow Medial Ulnar Collateral Ligament Surgery.

PubMed

Jack, Robert A; Sochacki, Kyle R; Morehouse, Hannah A; McCulloch, Patrick C; Lintner, David M; Harris, Joshua D

2018-04-01

Several studies have analyzed the most cited articles in shoulder, elbow, pediatrics, and foot and ankle surgery. However, no study has analyzed the quality of the most cited articles in elbow medial ulnar collateral ligament (UCL) surgery. To (1) identify the top 50 most cited articles related to UCL surgery, (2) determine whether there was a correlation between the top cited articles and level of evidence, and (3) determine whether there was a correlation between study methodological quality and the top cited articles. Systematic review. Web of Science and Scopus online databases were searched to identify the top 50 cited articles in UCL surgery. Level of evidence, number of times cited, year of publication, name of journal, country of origin, and study type were recorded for each study. Study methodological quality was analyzed for each article with the Modified Coleman Methodology Score (MCMS) and the Methodological Index for Non-randomized Studies (MINORS). Correlation coefficients were calculated. The 50 most cited articles were published between 1981 and 2015. The number of citations per article ranged from 20 to 301 (mean ± SD, 71 ± 62 citations). Most articles (92%) were from the United States and were level 3 (16%), level 4 (58%), or unclassified (16%) evidence. There were no articles of level 1 evidence quality. The mean MCMS and MINORS scores were 28.1 ± 13.4 (range, 3-52) and 9.2 ± 3.6 (range, 2-19), respectively. There was no significant correlation between the mean number of citations and level of evidence or quality ( r s = -0.01, P = .917), MCMS ( r s = 0.09, P = .571), or MINORS ( r s = -0.26, P = .089). The top 50 cited articles in UCL surgery constitute a low level of evidence and low methodological quality, including no level 1 articles. There was no significant correlation between the mean number of citations and level of evidence or study methodological quality. However, weak correlations were observed for later publication date and improved level of evidence and methodological quality.

Correlation Between Quality of Evidence and Number of Citations in Top 50 Cited Articles on Elbow Medial Ulnar Collateral Ligament Surgery

PubMed Central

Jack, Robert A.; Sochacki, Kyle R.; Morehouse, Hannah A.; McCulloch, Patrick C.; Lintner, David M.; Harris, Joshua D.

2018-01-01

Background: Several studies have analyzed the most cited articles in shoulder, elbow, pediatrics, and foot and ankle surgery. However, no study has analyzed the quality of the most cited articles in elbow medial ulnar collateral ligament (UCL) surgery. Purpose: To (1) identify the top 50 most cited articles related to UCL surgery, (2) determine whether there was a correlation between the top cited articles and level of evidence, and (3) determine whether there was a correlation between study methodological quality and the top cited articles. Study Design: Systematic review. Methods: Web of Science and Scopus online databases were searched to identify the top 50 cited articles in UCL surgery. Level of evidence, number of times cited, year of publication, name of journal, country of origin, and study type were recorded for each study. Study methodological quality was analyzed for each article with the Modified Coleman Methodology Score (MCMS) and the Methodological Index for Non-randomized Studies (MINORS). Correlation coefficients were calculated. Results: The 50 most cited articles were published between 1981 and 2015. The number of citations per article ranged from 20 to 301 (mean ± SD, 71 ± 62 citations). Most articles (92%) were from the United States and were level 3 (16%), level 4 (58%), or unclassified (16%) evidence. There were no articles of level 1 evidence quality. The mean MCMS and MINORS scores were 28.1 ± 13.4 (range, 3-52) and 9.2 ± 3.6 (range, 2-19), respectively. There was no significant correlation between the mean number of citations and level of evidence or quality (rs = –0.01, P = .917), MCMS (rs = 0.09, P = .571), or MINORS (rs = –0.26, P = .089). Conclusion: The top 50 cited articles in UCL surgery constitute a low level of evidence and low methodological quality, including no level 1 articles. There was no significant correlation between the mean number of citations and level of evidence or study methodological quality. However, weak correlations were observed for later publication date and improved level of evidence and methodological quality. PMID:29780841

Theoretical spectroscopy study of the low-lying electronic states of UX and UX{sup +}, X = F and Cl

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

Bross, David H.; Peterson, Kirk A., E-mail: kipeters@wsu.edu

Spectroscopic constants (T{sub e}, r{sub e}, B{sub 0}, ω{sub e}, and ω{sub e}x{sub e}) have been calculated for the low-lying electronic states of UF, UF{sup +}, UCl, and UCl{sup +} using complete active space 2nd-order perturbation theory (CASPT2), with a series of correlation consistent basis sets. The latter included those based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess Hamiltonians for the U atom. Spin orbit (SO) effects were included a posteriori using the state interacting method using both PP and Breit Pauli (BP) operators, as well as from exact two-component methods for U{sup +} and UF{sup +}. Complete basis setmore » (CBS) limits were obtained by extrapolation where possible and the PP and BP calculations were compared at their respective CBS limits. The PP-based method was shown to be reliable in calculating spectroscopic constants, in particular when using the state interacting method with CASPT2 energies (SO-CASPT2). The two component calculations were limited by computational resources and could not include electron correlation from the nominally closed shell 6s and 6p orbitals of U. UF and UCl were both calculated to have Ω = 9/2 ground states. The first excited state of UCl was calculated to be an Ω = 7/2 state at 78 cm{sup −1} as opposed to the same state at 435 cm{sup −1} in UF, and the other low-lying states of UCl showed a similar compression relative to UF. Likewise, UF{sup +} and UCl{sup +} both have Ω = 4 ground states and the manifold of low-lying excited Ω = 3, 2, 1, 0 states was energetically closer together in UCl{sup +} than in UF{sup +}, ranging up to 776 cm{sup −1} in UF{sup +} and only 438 cm{sup −1} in UCl{sup +}. As in previous studies, the final PP-based SO-CASPT2 results for UF{sup +} and UF agree well with experiment and are expected to be predictive for UCl and UCl{sup +}, which are reported here for the first time.« less

Theoretical spectroscopy study of the low-lying electronic states of UX and UX +, X = F and Cl

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

Bross, David H.; Peterson, Kirk A.

Spectroscopic constants (T e, r e, B 0, ω e, ω ex e) have been calculated for the low-lying electronic states of UF, UF +, UCl, and UCl + using complete active space 2nd-order perturbation theory (CASPT2), with a series of correlation consistent basis sets. The latter included those based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess (DK) Hamiltonians for the U atom. Spin orbit effects were included a posteri using the state interacting method using both PP and Breit Pauli (BP) operators, as well as from exact two-component (X2C) methods for U + and UF +. Complete basis setmore » (CBS) limits were obtained by extrapolation where possible and the PP and BP calculations were compared at their respective CBS limits. The PP-based method was shown to be reliable in calculating spectroscopic constants, in particular when using the state interacting method with CASPT2 energies (SO-CASPT2). The two component calculations were limited by computational resources and could not include electron correlation from the nominally closed shell 6s and 6p orbitals of U. UF and UCl were both calculated to have Ω=9/2 ground states. The first excited state of UCl was calculated to be an Ω=7/2 state at 78 cm -1 as opposed to the same state at 435 cm-1 in UF, and the other low-lying states of UCl showed a similar compression relative to UF. Likewise UF+ and UCl+ both have Ω=4 ground states and the manifold of low-lying excited Ω = 3, 2, 1, 0 states were energetically closer together in UCl + than in UF +, ranging up to 776 cm -1 in UF + and only 438 cm -1 in UCl +. As in previous research, the final PP-based SO-CASPT2 results for UF + and UF agree well with experiment, and are expected to be predictive for UCl and UCl +, which are reported here for the first time.« less

Theoretical spectroscopy study of the low-lying electronic states of UX and UX +, X = F and Cl

DOE PAGES

Bross, David H.; Peterson, Kirk A.

2015-11-13

Spectroscopic constants (T e, r e, B 0, ω e, ω ex e) have been calculated for the low-lying electronic states of UF, UF +, UCl, and UCl + using complete active space 2nd-order perturbation theory (CASPT2), with a series of correlation consistent basis sets. The latter included those based on both pseudopotential (PP) and all-electron Douglas-Kroll-Hess (DK) Hamiltonians for the U atom. Spin orbit effects were included a posteri using the state interacting method using both PP and Breit Pauli (BP) operators, as well as from exact two-component (X2C) methods for U + and UF +. Complete basis setmore » (CBS) limits were obtained by extrapolation where possible and the PP and BP calculations were compared at their respective CBS limits. The PP-based method was shown to be reliable in calculating spectroscopic constants, in particular when using the state interacting method with CASPT2 energies (SO-CASPT2). The two component calculations were limited by computational resources and could not include electron correlation from the nominally closed shell 6s and 6p orbitals of U. UF and UCl were both calculated to have Ω=9/2 ground states. The first excited state of UCl was calculated to be an Ω=7/2 state at 78 cm -1 as opposed to the same state at 435 cm-1 in UF, and the other low-lying states of UCl showed a similar compression relative to UF. Likewise UF+ and UCl+ both have Ω=4 ground states and the manifold of low-lying excited Ω = 3, 2, 1, 0 states were energetically closer together in UCl + than in UF +, ranging up to 776 cm -1 in UF + and only 438 cm -1 in UCl +. As in previous research, the final PP-based SO-CASPT2 results for UF + and UF agree well with experiment, and are expected to be predictive for UCl and UCl +, which are reported here for the first time.« less

Length estimations of presumed upward connecting leaders in lightning flashes to flat water and flat ground

NASA Astrophysics Data System (ADS)

Stolzenburg, Maribeth; Marshall, Thomas C.; Karunarathne, Sumedhe; Orville, Richard E.

2018-10-01

Using video data recorded at 50,000 frames per second for nearby negative lightning flashes, estimates are derived for the length of positive upward connecting leaders (UCLs) that presumably formed prior to new ground attachments. Return strokes were 1.7 to 7.8 km distant, yielding image resolutions of 4.25 to 19.5 m. No UCLs are imaged in these data, indicating those features were too transient or too dim compared to other lightning processes that are imaged at these resolutions. Upper bound lengths for 17 presumed UCLs are determined from the height above flat ground or water of the successful stepped leader tip in the image immediately prior to (within 20 μs before) the return stroke. Better estimates of maximum UCL lengths are determined using the downward stepped leader tip's speed of advance and the estimated return stroke time within its first frame. For 17 strokes, the upper bound length of the possible UCL averages 31.6 m and ranges from 11.3 to 50.3 m. Among the close strokes (those with spatial resolution <8 m per pixel), the five which connected to water (salt water lagoon) have UCL upper bound estimates averaging significantly shorter (24.1 m) than the average for the three close strokes which connected to land (36.9 m). The better estimates of maximum UCL lengths for the eight close strokes average 20.2 m, with slightly shorter average of 18.3 m for the five that connected to water. All the better estimates of UCL maximum lengths are <38 m in this dataset

The UCL EdD: An Apprenticeship for the Future Educational Professional?

ERIC Educational Resources Information Center

Taylor, Susan

2018-01-01

In 2001, the Institute of Education (now the UCL Institute of Education (UCL IOE)) became one of only three internationally accredited centres for the training of Reading Recovery trainers. To achieve accreditation, the training programme was required by the International Reading Recovery Trainers Organization to be linked to the IOE doctor of…

Magnetic circular dichroism of UCl 6– in the ligand-to-metal charge-transfer spectral region

DOE PAGES

Gendron, Frederic; Fleischauer, Valerie R.; Duignan, Thomas J.; ...

2017-06-23

Here, we present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl 6- complex ion in the UV-Vis spectral region. The ground state is an orbitally non-degenerate doublet E 5/2u and the MCD is a $C$-term spectrum caused by spin–orbit coupling. Calculations of the electronic spectrum at various levels of theory indicate that differential dynamic electron correlation has a strong influence on the energies of the dipole-allowed transitions and the envelope of the MCD spectrum. The experimentally observed bands are assigned to dipole-allowed ligand-to-metal charge transfer into the 5f shell,more » and 5f to 6d transitions. Charge transfer excitations into the U 6d shell appear at much higher energies. The MCD-allowed transitions can be assigned via their signs of the $C$-terms: Under O h double group symmetry, E 5/2u → E 5/2g transitions have negative $C$-terms whereas E 5/2u → F 3/2g transitions have positive $C$-terms if the ground state g-factor is negative, as it is the case for UCl 6-.« less

Efficacies of gentamicin-loaded magnetite block ionomer complexes against chronic Brucella melitensis infection

NASA Astrophysics Data System (ADS)

Jain-Gupta, Neeta; Pothayee, Nipon; Pothayee, Nikorn; Tyler, Ronald; Caudell, David L.; Balasubramaniam, Sharavanan; Hu, Nan; Davis, Richey M.; Riffle, Judy S.; Sriranganathan, Nammalwar

2013-11-01

Anionic copolymers can enable intracellular delivery of cationic drugs which otherwise cannot cross cell membrane barriers. We tested the efficacy of gentamicin-loaded magnetite block ionomer complexes (MBICs) against intracellular Brucella melitensis. Anionic block copolymers were used to coat nanomagnetite through adsorption of a portion of anions on the particle surfaces, then the remaining anions were complexed with 30-32 weight percentage of gentamicin. The zeta potential changed from -39 to -13 mV after encapsulation of the drug with complementary charge. The gentamicin-loaded MBICs had intensity average hydrodynamic diameters of 62 nm, while the polymer-coated nanomagnetite particles without drug were 34 nm in size. No toxicity as measured by a MTS assay was observed upon incubation of the MBICs with J774A.1 murine macrophage-like cells. Confocal microscopic images showed that the MBICs were taken up by the macrophages and distributed in the cell cytoplasm and endosomal/lysosomal compartments. Upon treatment with gentamicin-loaded MBICs (3.5 Log10), B. melitensis-infected macrophages showed significantly higher clearance of Brucella compared to the treatment with free g (0.9 Log10). Compared to doxycycline alone, a combination of doxycycline and gentamicin (either free or encapsulated in MBICs) showed significantly higher clearance of B. melitensis from chronically infected mice. Histopathological examination of kidneys from the MBICs-treated mice revealed multifocal infiltration of macrophages containing intracytoplasmic iron (MBICs) in peri-renal adipose. Although MBICs showed similar efficacy as free gentamicin against Brucella in mice, our strategy presents an effective way to deliver higher loads of drugs intracellularly and ability to study the bio-distribution of drug carriers.

M2+ Doping Induced Simultaneous Phase/Size Control and Remarkable Enhanced Upconversion Luminescence of NaLnF4 Probes for Optical-Guided Tiny Tumor Diagnosis.

PubMed

Li, Youbin; Li, Xiaolong; Xue, Zhenluan; Jiang, Mingyang; Zeng, Songjun; Hao, Jianhua

2017-05-01

Doping has played a vital role in constructing desirable hybrid materials with tunable functions and properties via incorporating atoms into host matrix. Herein, a simple strategy for simultaneously modifying the phase, size, and upconversion luminescence (UCL) properties of the NaLnF 4 (Ln = Y, Yb) nanocrystals by high-temperature coprecipitation through nonequivalent M 2+ doping (M = Mg 2+ , Co 2+ ) has been demonstrated. The phase transformation from cubic to hexagonal is readily achieved by doping M 2+ . Compared with Mg-free sample, a remarkable enhancement of overall UCL (≈27.5 times) is obtained by doping Mg 2+ . Interestingly, owing to the efficient UCL, red UCL-guided tiny tumor (down to 3 mm) diagnosis is demonstrated for the first time. The results open up a new way of designing high efficient UCL probe with combination of hexagonal phase and small size for tiny tumor detection. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NREL, NASA, and UCL Team Up to Make Lithium-Ion Batteries Safer on Earth

Science.gov Websites

and in Space | News | NREL NREL, NASA, and UCL Team Up to Make Lithium-Ion Batteries Safer on Earth and in Space NREL, NASA, and UCL Team Up to Make Lithium-Ion Batteries Safer on Earth and in Space . NREL joined forces with NASA in finding new, more precise ways to trigger internal short circuits

Biomechanical differences of the anterior and posterior bands of the ulnar collateral ligament of the elbow.

PubMed

Jackson, Timothy J; Jarrell, Shelby E; Adamson, Gregory J; Chung, Kyung Chil; Lee, Thay Q

2016-07-01

The main purpose of this study was to examine the functional characteristics of the anterior and posterior bands of the anterior bundle of the ulnar collateral ligament (UCL). Six cadaveric elbows were tested using a digital tracking system to measure the strain in the anterior band and posterior band of the anterior bundle of the UCL throughout a flexion/extension arc. The specimens were then placed in an Instron materials testing machine and loaded to failure to determine yield load and ultimate load of the UCL. The posterior band showed a linear increase in strain with increasing degrees of elbow flexion while the anterior band showed minimal change in strain throughout. The bands showed similar strain at yield load and ultimate load, demonstrating similar intrinsic properties. The anterior band of the anterior bundle of the UCL shows an isometric strain pattern through elbow range of motion, while the posterior band shows an increasing strain pattern in higher degrees of elbow flexion. Both bands show similar strain in a load to failure model, indicating insertion point, not intrinsic differences, of the bands determine the function of the anterior bundle of the UCL. This demonstrates a biomechanical rationale for UCL reconstructions using single point anatomical insertion points.

Electrochemical studies and analysis of 1-10 wt% UCl3 concentrations in molten LiCl-KCl eutectic

NASA Astrophysics Data System (ADS)

Hoover, Robert O.; Shaltry, Michael R.; Martin, Sean; Sridharan, Kumar; Phongikaroon, Supathorn

2014-09-01

Three electrochemical methods - cyclic voltammetry (CV), chronopotentiometry (CP), and anodic stripping voltammetry (ASV) - were applied to solutions of up to 10 wt% UCl3 in the molten LiCl-KCl eutectic salt at 500 °C to determine electrochemical properties and behaviors and to help provide a scientific basis for the development of an in situ electrochemical probe for determining the concentration of uranium in a used nuclear fuel electrorefiner. Diffusion coefficients of UCl4 and UCl3 were calculated to be (6.72 ± 0.360) × 10-6 cm2/s and (1.04 ± 0.17) × 10-5 cm2/s, respectively. Apparent standard reduction potentials were determined to be (-0.381 ± 0.013) V and (-1.502 ± 0.076) V vs. 5 mol% Ag/AgCl or (-1.448 ± 0.013) V and (-2.568 ± 0.076) V vs. Cl2/Cl- for the U(IV)/U(III) and U(III)/U redox couples, respectively. In comparing this data with supercooled thermodynamic data to determine activity coefficients, the thermodynamic database used was important with resulting activity coefficients ranging from 2.34 × 10-3 to 1.08 × 10-2 for UCl4 and 4.94 × 10-5 to 4.50 × 10-4 for UCl3. Of anodic stripping voltammetry and cyclic voltammetry anodic or cathodic peaks, the CV cathodic peak height divided by square root of scan rate was shown to be the most reliable method of determining UCl3 concentration in the molten salt.

Exploratory Solid-State Synthesis of Uranium Chalcogenides and Mixed Anion Uranium Chalcogenides

NASA Astrophysics Data System (ADS)

Ward, Matthew David

Several uranium chalcogenides and mixed anion uranium chalcogenides have been synthesized by solid-state synthetic methods. Structural determinations were carried out via single-crystal X-ray diffraction. Some of these compounds have been further characterized by magnetic measurements, optical properties measurements, Raman spectroscopy, resistivity measurements, XANES and XPS. Eight compounds of the composition MU8Q17 were synthesized and characterized by single-crystal X-ray diffraction. All of these compounds crystallize in the CrU8S17 structure type. XANES measurements indicate that ScU8S17 contains Sc3+ and must be charge balanced with some amount of U 3+. Two compounds of the composition ATiU3Te9 crystallize as black rectangular plates. From single-crystal magnetic measurements, CsTiU 3Te9 is consistent with antiferromagnetic coupling between magnetic U atoms. The uranium chalcogenide compounds NiUS3 and Cr4US 8 were synthesized from reaction of the elements in various fluxes. NiUS3 crystallizes in the GdFeO3 structure type. Cr 4US8 crystallizes in the orthorhombic space group D - Pnma and its structure is related to that of Li4UF 8. The compounds Rh2U6S15, Cs 2Ti2U6Se15, and Cs2Cr 2U6Se15 crystallize as black prisms in the cubic space group O-Im3m. Magnetic measurements on Cs 2Cr2U6Se15 give a value for the Weiss temperature, θWeiss, of 57.59 K, indicative of ferromagnetic coupling. Black plates of CsScU(Se2)Se3 were synthesized from the reaction of the elements in a CsCl flux. CsScU(Se2)Se 3 crystallizes in the orthorhombic space group D- Cmcm . Magnetic susceptibility measurements on CsScU(Se2)Se 3 indicate three regions of magnetic response. The uranium double salt Cs5[U2(μ-S 2)2Cl8]I crystallizes as red plates. Cs 5[U2(μ-S2)2Cl 8]I displays optical anisotropy with band gap energies of 1.99 eV and 2.08 eV along the [001] and [100] polarizations. The uranium oxychalcogenides U7O2Se12 and Na2Ba2(UO2)S4 were synthesized by intentional oxygen contamination. The structure of U7O 2Se12 is related to the previously reported U7Q 12. Na2Ba2(UO2)S4 contains isolated uranyl polyhedra in which each uranium atom may be assigned an oxidation state of +6. The four uranium(IV) chlorophosphates, UCl4(POCl3), [U2Cl9][PCl4], UCl3(PO2Cl 2), and U2Cl8(POCl3) were synthesized in an effort to synthesize new novel uranyl sulfides. All are unstable, but UCl4(POCl3) is the thermodynamically favorable phase.

Ultra-clean Layers (UCLs) and Low Albedo Clouds ("gray clouds") in the Marine Boundary Layer - CSET aircraft data, 2-D bin spectral cloud parcel model, large eddy simulation and satellite observations from CALIPSO, MODIS and COSMIC

NASA Astrophysics Data System (ADS)

O, K. T.; Wood, R.; Bretherton, C. S.; Eastman, R. M.; Tseng, H. H.

2016-12-01

During the 2015 Cloud System Evolution in the Trades (CSET) field program (CSET, Jul-Aug 2015, subtropical NE Pacific), the NSF/NCAR G-V aircraft frequently encountered ultra clean layers (hereafter UCLs) with extremely low accumulation mode aerosol (i.e. diameter da> 100nm) concentration (hereafter Na), and low albedo ( 0.2) warm clouds (termed "gray clouds" in our study) with low droplet concentration (hereafter Nd). The analysis of CSET aircraft data shows that (1) UCLs and gray clouds are mostly commonly found at a height of 1.5-2km, typically close to the top of the MBL, (2) UCLs and gray cloud coverage as high as 40-60% between 135W and 155W (i.e. Sc-Cu transition region) but occur very infrequently east of 130W (i.e. shallow, near-coastal stratocumulus region), and (3) UCLs and gray clouds exhibit remarkably low turbulence compared with non-UCL clear sky and clouds. It should be noted that most previous aircraft sampling of low clouds occurred close to the Californian coast, so the prevalence of UCLs and gray clouds has not been previously noted. Based on the analysis of aircraft data, we hypothesize that gray clouds result from detrainment of cloud close to the top of precipitating trade cumuli, and UCLs are remnants of these layers when gray clouds evaporates. The simulations in our study are performed using 2-D bin spectral cloud parcel model and version 6.9 of the System for Atmospheric Modeling (SAM). Our idealized simulations suggest that collision-coalescence plays a crucial role in reducing Nd such that gray clouds can easily form via collision-coalescence in layers detrained from the cloud top at trade cumulus regime, but can not form at stratocumulus regime. Upon evaporation of gray clouds, only few accumulation mode aerosols are returned to the clear sky, leaving horizontally-extensive UCLs (i.e. clean clear sky). Analysis of CSET flight data and idealized model simulations both suggest cloud top/PBL height may play an important role in the formation of UCLs and gray clouds. In our satellite observation study, the comparison between PBL height (from COSMIC and MODIS) and fraction of low optical depth cloud (from MODIS and CALIPSO) at NEP trade cumulus regime (20-35N, 140-155W) also suggest a strong positive correlation.

Unravelling the spin-state of solvated [Fe(bpp)2]2+ spin-crossover complexes: structure-function relationship.

PubMed

Giménez-López, Maria Del Carmen; Clemente-León, Miguel; Giménez-Saiz, Carlos

2018-05-23

This paper reports firstly the syntheses, crystal structures, and thermal and magnetic properties of spin crossover salts of formulae [Fe(bpp)2]3[Cr(CN)6]2·13H2O (1) and [Fe(bpp)2][N(CN)2]2·H2O (2) (bpp = 2,6-bis(pyrazol-3-yl)pyridine) exhibiting hydrogen-bonded networks of low-spin [Fe(bpp)2]2+ complexes and [Cr(CN)6]3- or [N(CN)2]- anions, with solvent molecules located in the voids. Desolvation of 1 is accompanied by a complete low-spin (LS) to a high-spin (HS) transformation that becomes reversible after rehydration by exposing the sample to the humidity of air. The influence of the lattice water on the magnetic properties of spin-crossover [Fe(bpp)2]X2 complex salts has been documented. In most cases, it stabilises the LS state over the HS one. In other cases, it is rather the contrary. The second part of this paper is devoted to unravelling the reasons why the lattice solvent stabilises one form over the other through magneto-structural correlations of [Fe(bpp)2]2+ salts bearing anions with different charge/size ratios (Xn-). The [Fe(bpp)2]2+ stacking explaining these two different behaviours is correlated here with the composition of the second coordination sphere of the Fe centers and the ability of these anions to form hydrogen bonds and/or π-π stacking interactions between them or the bpp ligand.

Effect of distal ulnar collateral ligament tear pattern on contact forces and valgus stability in the posteromedial compartment of the elbow.

PubMed

Hassan, Sheref E; Parks, Brent G; Douoguih, Wiemi A; Osbahr, Daryl C

2015-02-01

It is not known whether the pattern of ulnar collateral ligament (UCL) tear affects elbow biomechanics. There will be a significant change in elbow biomechanics with 50% proximal but not 50% distal simulated rupture of the UCL. Controlled laboratory study. Pressure sensors in the posteromedial elbow joint of 25 male cadaveric elbows (average age, 54.9 years; range, 26-66 years) were used to measure contact area, pressure, and valgus torque at 90° and 30° of elbow flexion. Thirteen specimens were tested with the UCL intact, then with proximal-to-distal detachment of 50%, and then with proximal-to-distal detachment of 100% of the anterior band of the UCL from the ulnar attachment. This method was repeated in the remaining 12 specimens in a distal-to-proximal direction. With 50% proximal-to-distal detachment, contact area decreased significantly versus intact at 90° (91.3 ± 23.6 vs 112.2 ± 26.0 mm(2); P < .001) and 30° (69.3 ± 14.8 vs 83.1 ± 21.6 mm(2); P < .001) of elbow flexion; the center of pressure (COP) moved significantly proximally versus intact at 90° (3.8 ± 2.5 vs 5.4 ± 2.3 mm; P < .001) and 30° (5.9 ± 2.8 vs 7.4±1.9 mm; P < .001). With 50% distal-to-proximal UCL detachment versus intact, no significant change was observed in contact area, movement of the COP, or valgus laxity at either flexion position. With 100% proximal-to-distal and distal-to-proximal detachment, significant change in contact area, movement of the COP, and valgus laxity versus intact was found at 90° and 30° of elbow flexion (P < .05). No significant difference in contact pressure was observed in any test conditions. Significant change in contact area and proximal movement of the COP with 50% proximal UCL detachment and the lack of significant change with 50% distal UCL detachment suggest that the proximal half of the UCL ulnar footprint has a primary role in maintaining posteromedial elbow biomechanics. The findings suggest that surgical reconstruction should aim to reestablish at least the proximal 50% of the UCL ulnar footprint. © 2014 The Author(s).

Biomechanical comparison of graft fixation at 30° and 90° of elbow flexion for ulnar collateral ligament reconstruction by the docking technique.

PubMed

Cohen, Steven B; Woods, Daniel P; Siegler, Sorin; Dodson, Christopher C; Namani, Ramya; Ciccotti, Michael G

2015-02-01

Ulnar collateral ligament (UCL) injuries have been successfully treated by the docking reconstruction. Although fixation of the graft has been suggested at 30° of elbow flexion, no quantitative biomechanical data exist to provide guidelines for the optimal elbow flexion angle for graft fixation. Testing was conducted on 10 matched pairs of cadaver elbows with use of a loading system and optoelectric tracking device. After biomechanical data on the native UCL were obtained, reconstruction by the docking technique was performed with use of palmaris longus autograft with one elbow fixated at 30° and the contralateral elbow at 90° of elbow flexion. Biomechanical testing was undertaken on these specimens. The load to failure of the native UCL (mean, 20.1 N-m) was significantly higher (P = .004) than that of the reconstructed UCL (mean, 4.6 N-m). There was no statistically significant difference in load to failure of the UCL reconstructions fixated at 30° of elbow flexion (average, 4.86 N-m) compared with those at 90° (average, 4.35 N-m). Elbows reconstructed at 30° and 90° of elbow flexion produced similar kinematic coupling and valgus laxity characteristics compared with each other and with the intact UCL. Although not statistically significant, the reconstructions fixated at 30° more closely resembled the biomechanical characteristics of the intact elbow than did reconstructions fixated at 90°. No statistically significant difference was found in comparing the docking technique of UCL reconstruction with graft fixation at 30° vs. 90° of elbow flexion. Copyright © 2015 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Elsevier Inc. All rights reserved.

The morphologic change of the ulnar collateral ligament of elbow in high school baseball pitchers, with and without symptoms, by sonography.

PubMed

Tajika, Tsuyoshi; Yamamoto, Atsushi; Oya, Noboru; Ichinose, Tsuyoshi; Shimoyama, Daisuke; Sasaki, Tsuyoshi; Shitara, Hitoshi; Kitagawa, Takanori; Saito, Kenichi; Osawa, Takashi; Takagishi, Kenji

2016-08-01

Few reports in the literature relate morphologic changes of the ulnar collateral ligament (UCL) to prior elbow symptoms. This study used ultrasonography (US) to assess the ulnohumeral joint space width, with and without stress, and elucidate morphologic changes of the UCL of the elbow in high school pitchers with and without a history of elbow symptoms. Each of 122 high school baseball pitchers who underwent US of the medial aspect of both elbows completed a self-administered questionnaire related to the self-satisfaction score (0-100) for pitching performance and throwing-related elbow joint pain sustained during the prior 3 years. We conducted gravity stress US elbow examination with 30° of flexion with and without valgus stress. Comparisons of the UCL thickness and ulnohumeral joint space width, with and without valgus stress, were made among the 122 high school pitchers with and without a history of elbow symptoms. Pitchers with an elbow symptom history exhibited a greater difference between the UCL thickness on the throwing side than those with no elbow symptom history (P = .0013). A negative significant association was found between UCL thickness on the pitching side and the self-evaluation score for pitching performance (r = -0.20, P = .04). US assessment demonstrated that the UCL in the dominant side with elbow symptom history was thicker than that with no elbow symptom history. The UCL thickness might reflect the prior pitching condition of high school baseball pitchers. Copyright © 2016 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Elsevier Inc. All rights reserved.

Does posteromedial chondromalacia reduce rate of return to play after ulnar collateral ligament reconstruction?

PubMed

Osbahr, Daryl C; Dines, Joshua S; Rosenbaum, Andrew J; Nguyen, Joseph T; Altchek, David W

2012-06-01

Biomechanical studies suggest ulnohumeral chondral and ligamentous overload (UCLO) explains the development of posteromedial chondromalacia (PMC) in throwing athletes with ulnar collateral ligament (UCL) insufficiency. UCL reconstruction reportedly allows 90% of baseball players to return to prior or a higher level of play; however, players with concomitant posteromedial chondromalacia may experience lower rates of return to play. The purpose of this investigation is to determine: (1) the rates of return to play of baseball players undergoing UCL reconstruction and posteromedial chondromalacia; and (2) the complications occurring after UCL reconstruction in the setting of posteromedial chondromalacia. We retrospectively reviewed 29 of 161 (18%) baseball players who were treated for the combined posteromedial chondromalacia and UCL injury. UCL reconstruction was accomplished with the docking technique, and the PMC was addressed with nothing or débridement if Grade 2 or 3 and with débridement or microfracture if Grade 4. The mean age was 19.6 years (range, 16-23 years). Most players were college athletes (76%) and pitchers (93%). We used a modified four-level scale of Conway et al. to assess return to play with 1 being the highest level (return to preinjury level of competition or performance for at least one season after UCL reconstruction). The minimum followup was 24 months (mean, 37 months; range, 24-52 months). Return to play was Level 1 in 22 patients (76%), Level 2 in four patients (14%), Level 3 in two patients (7%), and Level 4 in one (3%) patient. Our data suggest baseball players with concomitant PMC, may have lower rates of return to the same or a higher level of play compared with historical controls. Level IV, case series. See Guidelines for Authors for a complete description of levels of evidence.

Cubic sub-20 nm NaLuF(4)-based upconversion nanophosphors for high-contrast bioimaging in different animal species.

PubMed

Yang, Tianshe; Sun, Yun; Liu, Qian; Feng, Wei; Yang, Pengyuan; Li, Fuyou

2012-05-01

A new upconversion luminescence (UCL) nanophosphors based on host matrix of cubic NaLuF(4) with bright luminescence have been synthesized by a solvothermal method, facilitate the nanocrystals potential candidates for imaging in vivo, especially large-animals. The sub-20 nm NaLuF(4) co-doped Yb(3+) and Er(3+) (Tm(3+)) showed about 10-fold stronger UCL emission than that of corresponding hexagonal NaYF(4)-based nanocrystals with a 20 nm diameter. Near-infrared to near-infrared (NIR-to-NIR) UCL emission of PAA-coated NaLuF(4):20%Yb,1%Tm (PAA-Lu(Tm)) can penetrate >1.5 cm tissue of pork with high contrast. Based on super-strong UCL emission and deep penetration, PAA-Lu(Tm) as optical bioprobe has been demonstrated by in vivo UCL imaging of a normal black mouse, even rabbit with excellent signal-to-noise ratio. Furthermore, such cubic NaLuF(4)-based nanophosphor was applied in lymph node imaging of live Kunming mouse with rich white fur. Copyright © 2012 Elsevier Ltd. All rights reserved.

Tris(phosphinoamide)-supported uranium-cobalt heterobimetallic complexes featuring Co → U dative interactions.

PubMed

Napoline, J Wesley; Kraft, Steven J; Matson, Ellen M; Fanwick, Phillip E; Bart, Suzanne C; Thomas, Christine M

2013-10-21

A series of tris- and tetrakis(phosphinoamide) U/Co complexes has been synthesized. The uranium precursors, (η(2)-Ph2PN(i)Pr)4U (1), (η(2)-(i)Pr2PNMes)4U (2), (η(2)-Ph2PN(i)Pr)3UCl (3), and (η(2)-(i)Pr2PNMes)3UI (4), were easily accessed via addition of the appropriate stoichiometric equivalents of [Ph2PN(i)Pr]K or [(i)Pr2PNMes]K to UCl4 or UI4(dioxane)2. Although the phosphinoamide ligands in 1 and 4 have been shown to coordinate to U in an η(2)-fashion in the solid state, the phosphines are sufficiently labile in solution to coordinate cobalt upon addition of CoI2, generating the heterobimetallic Co/U complexes ICo(Ph2PN(i)Pr)3U[η(2)-Ph2PN(i)Pr] (5), ICo((i)Pr2PNMes)3U[η(2)-((i)Pr2PNMes)] (6), ICo(Ph2PN(i)Pr)3UI (7), and ICo((i)Pr2PNMes)3UI (8). Structural characterization of complexes 5 and 7 reveals reasonably short Co-U interatomic distances, with 7 exhibiting the shortest transition metal-uranium distance ever reported (2.874(3) Å). Complexes 7 and 8 were studied by cyclic voltammetry to examine the influence of the metal-metal interaction on the redox properties compared with both monometallic Co and heterobimetallic Co/Zr complexes. Theoretical studies are used to further elucidate the nature of the transition metal-actinide interaction.

A Comparison of Presentation Levels to Maximize Word Recognition Scores

PubMed Central

Guthrie, Leslie A.; Mackersie, Carol L.

2010-01-01

Background While testing suprathreshold word recognition at multiple levels is considered best practice, studies on practice patterns do not suggest that this is common practice. Audiologists often test at a presentation level intended to maximize recognition scores, but methods for selecting this level are not well established for a wide range of hearing losses. Purpose To determine the presentation level methods that resulted in maximum suprathreshold phoneme-recognition scores while avoiding loudness discomfort. Research Design Performance-intensity functions were obtained for 40 participants with sensorineural hearing loss using the Computer-Assisted Speech Perception Assessment. Participants had either gradually sloping (mild, moderate, moderately severe/severe) or steeply sloping losses. Performance-intensity functions were obtained at presentation levels ranging from 10 dB above the SRT to 5 dB below the UCL (uncomfortable level). In addition, categorical loudness ratings were obtained across a range of intensities using speech stimuli. Scores obtained at UCL – 5 dB (maximum level below loudness discomfort) were compared to four alternative presentation-level methods. The alternative presentation-level methods included sensation level (SL; 2 kHz reference, SRT reference), a fixed-level (95 dB SPL) method, and the most comfortable loudness level (MCL). For the SL methods, scores used in the analysis were selected separately for the SRT and 2 kHz references based on several criteria. The general goal was to choose levels that represented asymptotic performance while avoiding loudness discomfort. The selection of SLs varied across the range of hearing losses. Results Scores obtained using the different presentation-level methods were compared to scores obtained using UCL – 5 dB. For the mild hearing loss group, the mean phoneme scores were similar for all presentation levels. For the moderately severe/severe group, the highest mean score was obtained using UCL - 5 dB. For the moderate and steeply sloping groups, the mean scores obtained using 2 kHz SL were equivalent to UCL - 5 dB, whereas scores obtained using the SRT SL were significantly lower than those obtained using UCL - 5 dB. The mean scores corresponding to MCL and 95 dB SPL were significantly lower than scores for UCL - 5 dB for the moderate and the moderately severe/severe group. Conclusions For participants with mild to moderate gradually sloping losses and for those with steeply sloping losses, the UCL – 5 dB and the 2 kHz SL methods resulted in the highest scores without exceeding listeners' UCLs. For participants with moderately severe/severe losses, the UCL - 5 dB method resulted in the highest phoneme recognition scores. PMID:19594086

Return-to-Play Outcomes in Professional Baseball Players After Medial Ulnar Collateral Ligament Injuries: Comparison of Operative Versus Nonoperative Treatment Based on Magnetic Resonance Imaging Findings.

PubMed

Ford, Gregory M; Genuario, James; Kinkartz, Jason; Githens, Thomas; Noonan, Thomas

2016-03-01

The medial ulnar collateral ligament (UCL) is the primary static stabilizer to valgus stress of the elbow. Injuries to the UCL are common in baseball pitchers. In the 1970s, reconstructive surgery was developed. Return-to-play (RTP) rates of 67% to 95% after reconstruction have been reported. There is a paucity of published studies among professional baseball players reporting RTP with nonoperative treatment. To identify professional baseball players' ability to RTP after the nonoperative treatment of UCL injuries based on the magnetic resonance imaging (MRI) grade. Case series; Level of evidence, 4. A review of elbow injuries among a professional baseball organization from 2006 to 2011 was performed. MRI was performed on all players. Forty-three UCL injuries were diagnosed. Treatment included rehabilitation, surgery, or both. Rates of RTP and return to the same level of play or higher (RTSP) were calculated and correlated with the MRI grade, location of injury, and player position. MRI grading was as follows: I, intact ligament with or without edema; IIA, partial tear; IIB, chronic healed injury; and III, complete tear. Forty-three UCL injuries in 43 players were diagnosed. Eight had complete tears (grade III), were treated operatively with UCL reconstruction, and had an RTP rate of 75% and RTSP rate of 63% (5/8 returned to the same level and 1 to a lower level). All 8 were pitchers. The remaining 35 players had incomplete injuries (4 grade I, 8 grade IIA, and 23 grade IIB), consisting of 24 pitchers and 11 positional players. Of these 35 players, 1 underwent surgery without attempted rehabilitation, 3 initiated rehabilitation until MRI was performed and then underwent surgery, and 3 underwent surgery after failed rehabilitation. The 7 players who underwent UCL reconstruction surgery had an RTP rate of 100% and RTSP rate of 86% (6/7 returned to the same level and 1 to a lower level). The remaining 28 with nonoperative treatment had both RTP and RTSP rates of 93% (26/28 returned to the same level and 0 to a lower level). Of these, 10 were positional players with an RTSP rate of 90%, and 18 were pitchers with an RTSP rate of 94%. Of all players with incomplete UCL injuries who completed nonoperative rehabilitative treatment (n = 31), 26 had a successful RTSP (84%). Incomplete UCL injuries in professional baseball players can be successfully treated nonoperatively in the majority of cases. Pitchers are more likely to have complete tears leading to surgery. MRI grading of UCL injuries can help predict RTP and the need for surgery. © 2016 The Author(s).

Squeezed between shells? The origin of the Lupus I molecular cloud. II. APEX CO and GASS H I observations

NASA Astrophysics Data System (ADS)

Gaczkowski, B.; Roccatagliata, V.; Flaischlen, S.; Kröll, D.; Krause, M. G. H.; Burkert, A.; Diehl, R.; Fierlinger, K.; Ngoumou, J.; Preibisch, T.

2017-12-01

Context. Lupus I cloud is found between the Upper Scorpius (USco) and Upper Centaurus-Lupus (UCL) subgroups of the Scorpius-Centaurus OB association, where the expanding USco H I shell appears to interact with a bubble currently driven by the winds of the remaining B stars of UCL. Aims: We investigate whether the Lupus I molecular could have formed in a colliding flow, and in particular, how the kinematics of the cloud might have been influenced by the larger scale gas dynamics. Methods: We performed APEX 13CO(2-1)and C18O(2-1) line observations of three distinct parts of Lupus I that provide kinematic information on the cloud at high angular and spectral resolution. We compare those results to the atomic hydrogen data from the GASS H I survey and our dust emission results presented in the previous paper. Based on the velocity information, we present a geometric model for the interaction zone between the USco shell and the UCL wind bubble. Results: We present evidence that the molecular gas of Lupus Iis tightly linked to the atomic material of the USco shell. The CO emission in Lupus Iis found mainly at velocities between vLSR = 3-6 km s-1, which is in the same range as the H I velocities. Thus, the molecular cloud is co-moving with the expanding USco atomic H I shell. The gas in the cloud shows a complex kinematic structure with several line-of-sight components that overlay each other. The nonthermal velocity dispersion is in the transonic regime in all parts of the cloud and could be injected by external compression. Our observations and the derived geometric model agree with a scenario in which Lupus Iis located in the interaction zone between the USco shell and the UCL wind bubble. Conclusions: The kinematics observations are consistent with a scenario in which the Lupus Icloud formed via shell instabilities. The particular location of Lupus I between USco and UCL suggests that counterpressure from the UCL wind bubble and pre-existing density enhancements, perhaps left over from the gas stream that formed the stellar subgroups, may have played a role in its formation. This publication is based on data acquired with the Atacama Pathfinder Experiment (APEX), which is a collaboration between the Max-Planck-Institut fur Radioastronomie, the European Southern Observatory, and the Onsala Space Observatory.The 13CO(2-1) and C18O(2-1) spectral cubes are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/608/A102

ProUCL version 4.1.00 Documentation Downloads

EPA Pesticide Factsheets

ProUCL version 4.1.00 represents a comprehensive statistical software package equipped with statistical methods and graphical tools needed to address many environmental sampling and statistical issues as described in various these guidance documents.

Homoleptic 2,2'-bipyridine metalates(-I) of iron and cobalt, one cocrystallized with an anthracene radical anion and the other with neutral anthracene.

PubMed

Brennessel, William W; Ellis, John E

2014-08-01

Homoleptic 2,2'-bipyridine (bipy) metalates of iron and cobalt have been synthesized directly from the corresponding homoleptic anthracene metalates. In the iron structure, bis[([2.2.2]cryptand)potassium(I)] tris(2,2'-bipyridine)ferrate(-I) anthracene(-I), [K(C18H36N2O6)]2[Fe(C10H8N2)3](C14H10), the asymmetric unit contains one potassium complex cation in a general position, the Fe center and one and a half bipy ligands of the ferrate complex on a crystallographic twofold axis that includes the Fe atom, and one half of an anthracene radical anion whose other half is generated by a crystallographic inversion center. The cations and anions are well separated and the geometry about the Fe center is essentially octahedral. In the cobalt structure, ([2.2.2]cryptand)potassium(I) bis(2,2'-bipyridine)cobaltate(-I) anthracene hemisolvate tetrahydrofuran (THF) disolvate, [K(C18H36N2O6)][Co(C10H8N2)2]·0.5C14H10·2C4H8O, the asymmetric unit contains the cation, anion, and both cocrystallized THF solvent molecules in general positions, and one half of a cocrystallized anthracene molecule whose other half is generated by a crystallographic inversion center. The cation and anion are well separated and the ligand planes in the cobaltate anion are periplanar. Each anthracene molecule is midway between and is oriented perpendicular to a pair of symmetry-related bipy ligands such that aromatic donor-acceptor interactions may play a role in the packing arrangement. The lengths of the bonds that connect the bipy rings support the assertion that the ligands are bipy radical anions in the iron structure. However, in the case of cobalt, these lengths are between the known ranges for a bipy radical anion and a bipy dianion, and therefore no conclusion can be made from the crystallography alone. One cocrystallized THF solvent molecule in the cobalt structure was modeled as disordered over three positions with appropriate geometric and thermal restraints, which resulted in a refined component mass ratio of 0.412 (4):0.387 (3):0.201 (3).

The Use of an Orthopaedic Rating System in Major League Baseball

PubMed Central

McGahan, Patrick J.; Fronek, Jan; Hoenecke, Heinz R.; Keefe, Daniel

2014-01-01

Background: Although the majority of Major League Baseball teams use an orthopaedic rating system to evaluate draft picks, little has been published on the topic. Hypothesis: Our goal was to assess the attitudes among Major League Baseball physicians regarding 3 common diagnoses in pitching prospects, through the use of an orthopaedic rating system. Our hypothesis was that the assigned orthopaedic grades would vary among physicians, diagnoses, and operative-versus-nonoperative and recent-versus-past treatment. Study Design: Survey. Level of Evidence: Level 4. Methods: A survey in the form of 12 clinical vignettes was used to query Major League Baseball physicians regarding ulnar collateral ligament (UCL) injuries, type II superior labrum anterior posterior (SLAP) tears, and internal impingement. Respondents graded draft picks using an orthopaedic rating system. The vignettes covered both operative and nonoperative and recent and past treatment (successful return to pitching for 1 year). Results: The orthopaedic grades assigned by respondents were as follows (minimal, moderate, severe risk): past UCL reconstruction (73%, 27%, 0%), recent UCL reconstruction (19%, 77%, 4%), past UCL strain (28%, 60%, 12%), recent UCL strain (0%, 48%, 52%), past SLAP repair (52%, 48%, 0%), recent SLAP repair (4%, 64%, 32%), past SLAP nonoperative (28%, 60%, 12%), recent SLAP nonoperative (0%, 36%, 64%), past internal impingement operative (24%, 68%, 8%), recent internal impingement operative (8%, 32%, 60%), past internal impingement nonoperative (24%, 68%, 8%), and recent internal impingement nonoperative (4%, 48%, 44%). Conclusion: Team physicians are optimistic regarding the outcome of UCL reconstruction. In contrast, UCL strains, type II SLAP lesions, and internal impingement carry a guarded prognosis. For all diagnoses, regardless of treatment, the prognosis improved if a player returned to pitching for 1 full season. Clinical Relevance: This study represents a first step toward developing a standardized orthopaedic rating system that will facilitate more accurate player assessment and clearer communication among physicians. PMID:25177423

ProUCL version 4.00.05 Documentation Downloads

EPA Pesticide Factsheets

ProUCL 4.00.05 serves as a companion software package for Calculating Upper Confidence Limits for Exposure Point Concentrations at Hazardous Waste Sites and Guidance for Comparing Background and Chemical Concentrations in Soil for CERCLA Sites.

Theoretical study of X⁻ · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH₂ and AsH₂): noncovalently electron-withdrawing effects on anion-arene interactions.

PubMed

Chen, Yishan; Yao, Lifeng

2014-01-01

The ternary complexes X(-) · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH2 and AsH2) have been investigated by MP2 calculations to understand the noncovalently electron-withdrawing effects on anion-arene interactions. The results indicate that in binary complexes (1 · X(-)), both weak σ-type and anion-π complexes can be formed for Cl(-) and Br(-), but only anion-π complex can be formed for I(-). Moreover, the hydrogen-bonding complex is the global minimum for all three halides in binary complexes. However, in ternary complexes, anion-π complex become unstable and only σ complex can retain in many cases for Cl(-) and Br(-). Anion-π complex keeps stable only when YF = HF. In contrast with binary complexes, σ complex become the global minimum for Cl(-) and Br(-) in ternary complexes. These changes in binding mode and strength are consistent with the results of covalently electron-withdrawing effects. However, in contrast with the covalently electron-withdrawing substituents, Cl(-) and Br(-) can attack the aromatic carbon atom to form a strong σ complex when the noncovalently electron-withdrawing effect is induced by halogen bonding. The binding behavior for I(-) is different from that for Cl(-) and Br(-) in two aspects. First, the anion-π complex for I(-) can also keep stable when the noncovalent interaction is halogen bonding. Second, the anion-π complex for I(-) is the global minimum when it can retain as a stable structure.

Factors Related to Increased Ulnar Collateral Ligament Thickness on Stress Sonography of the Elbow in Asymptomatic Youth and Adolescent Baseball Pitchers.

PubMed

Atanda, Alfred; Averill, Lauren W; Wallace, Maegen; Niiler, Tim A; Nazarian, Levon N; Ciccotti, Michael G

2016-12-01

Stress ultrasound (SUS) of the elbow has demonstrated changes in the anterior band of the ulnar collateral ligament (UCL) in professional and high school-aged pitchers. However, there have been no large reports correlating pitching history data with SUS changes in youth and adolescent baseball pitchers. Changes of the UCL on SUS will correlate with pitching volume in youth and adolescent baseball pitchers. Cross-sectional study; Level of evidence, 3. SUS of the elbow was performed in both elbows of 102 youth and adolescent baseball pitchers. UCL thickness and the width of the ulnohumeral joint, at rest and with 150 N of valgus stress, were measured using a standardized, instrumented device. Demographic data, arm measurements, and a pitching history questionnaire were recorded as well. The pitchers were separated into 2 groups based on age: group 1 (12-14 years) and group 2 (15-18 years). SUS findings of the dominant elbows were compared between the 2 groups. Correlation analysis and linear regression were used to identify relationships between SUS findings and pitching history data. In all pitchers, the mean UCL thickness was 4.40 mm in the dominant elbow and 4.11 mm in the nondominant elbow (P =.03). There was no significant difference between elbows in any joint space characteristics. A comparison of group 1 versus group 2 demonstrated significant differences in UCL thickness (4.13 vs 4.96 mm; P < .001), resting joint space width (6.56 vs 4.04 mm; P < .001), and stressed joint space width (7.68 vs 4.07 mm; P < .001). There was no difference in the change in joint space width between the 2 groups (1.11 vs 0.76 mm; P = .05). The UCL was significantly thicker in pitchers who threw more than 67 pitches per appearance (4.69 vs 4.14 mm), who pitched more than 5 innings per appearance (4.76 vs 4.11 mm), and who had more than 5.5 years of pitching experience (4.71 vs 4.07 mm; P < .001). Linear regression demonstrated that age, weight, and pitches per appearance (R 2 = 0.114, 0.370, and 0.326, respectively) significantly correlated with UCL thickness. These findings suggest that UCL thickness increases as pitchers get older and heavier and as they increase their pitch volumes. © 2016 The Author(s).

STATISTICAL ANALYSIS OF TANK 5 FLOOR SAMPLE RESULTS

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

Shine, E.

2012-03-14

Sampling has been completed for the characterization of the residual material on the floor of Tank 5 in the F-Area Tank Farm at the Savannah River Site (SRS), near Aiken, SC. The sampling was performed by Savannah River Remediation (SRR) LLC using a stratified random sampling plan with volume-proportional compositing. The plan consisted of partitioning the residual material on the floor of Tank 5 into three non-overlapping strata: two strata enclosed accumulations, and a third stratum consisted of a thin layer of material outside the regions of the two accumulations. Each of three composite samples was constructed from five primarymore » sample locations of residual material on the floor of Tank 5. Three of the primary samples were obtained from the stratum containing the thin layer of material, and one primary sample was obtained from each of the two strata containing an accumulation. This report documents the statistical analyses of the analytical results for the composite samples. The objective of the analysis is to determine the mean concentrations and upper 95% confidence (UCL95) bounds for the mean concentrations for a set of analytes in the tank residuals. The statistical procedures employed in the analyses were consistent with the Environmental Protection Agency (EPA) technical guidance by Singh and others [2010]. Savannah River National Laboratory (SRNL) measured the sample bulk density, nonvolatile beta, gross alpha, radionuclide, inorganic, and anion concentrations three times for each of the composite samples. The analyte concentration data were partitioned into three separate groups for further analysis: analytes with every measurement above their minimum detectable concentrations (MDCs), analytes with no measurements above their MDCs, and analytes with a mixture of some measurement results above and below their MDCs. The means, standard deviations, and UCL95s were computed for the analytes in the two groups that had at least some measurements above their MDCs. The identification of distributions and the selection of UCL95 procedures generally followed the protocol in Singh, Armbya, and Singh [2010]. When all of an analyte's measurements lie below their MDCs, only a summary of the MDCs can be provided. The measurement results reported by SRNL are listed in Appendix A, and the results of this analysis are reported in Appendix B. The data were generally found to follow a normal distribution, and to be homogeneous across composite samples.« less

Scalable web services for the PSIPRED Protein Analysis Workbench.

PubMed

Buchan, Daniel W A; Minneci, Federico; Nugent, Tim C O; Bryson, Kevin; Jones, David T

2013-07-01

Here, we present the new UCL Bioinformatics Group's PSIPRED Protein Analysis Workbench. The Workbench unites all of our previously available analysis methods into a single web-based framework. The new web portal provides a greatly streamlined user interface with a number of new features to allow users to better explore their results. We offer a number of additional services to enable computationally scalable execution of our prediction methods; these include SOAP and XML-RPC web server access and new HADOOP packages. All software and services are available via the UCL Bioinformatics Group website at http://bioinf.cs.ucl.ac.uk/.

MaizeGDB video tutorials, feedback booth and introducing the agBioData working group

USDA-ARS?s Scientific Manuscript database

As datasets get larger and more complex, it becomes more difficult for MaizeGDB users to be aware of all the tools and services MaizeGDB provides. In order to help our users, we have made a YouTube channel (https://www.youtube.com/channel/UClV7hOrmTtWjB6fgo_gT_dg) where we are loading all new, short...

A FORMATION SCENARIO OF YOUNG STELLAR GROUPS IN THE REGION OF THE SCORPIO CENTAURUS OB ASSOCIATION

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

Ortega, V. G.; Jilinski, E.; De la Reza, R.

2009-04-15

The main objective of this work is to investigate the role played by Lower Centaurus Crux (LCC) and Upper Centaurus Lupus (UCL), both subcomponents of the Scorpio Centaurus OB association (Sco-Cen), in the formation of the groups {beta} Pictoris, TW Hydrae, and the {eta} Chamaeleontis cluster. The dynamical evolution of all the stellar groups involved and of the bubbles and shells blown by LCC and UCL are calculated, and followed from the past to the present. This leads to a formation scenario in which (1) the groups {beta} Pictoris, TW Hydrae were formed in the wake of the shells createdmore » by LCC and UCL, (2) the young cluster {eta} Chamaeleontis was born as a consequence of the collision of the shells of LCC and UCL, and (3) the formation of Upper Scorpius (US), the other main subcomponent of the Sco-Cen association, may have been started by the same process that created {eta} Chamaeleontis.« less

Method for making a uranium chloride salt product

DOEpatents

Miller, William E [Naperville, IL; Tomczuk, Zygmunt [Lockport, IL

2004-10-05

The subject apparatus provides a means to produce UCl.sub.3 in large quantities without incurring corrosion of the containment vessel or associated apparatus. Gaseous Cl is injected into a lower layer of Cd where CdCl.sub.2 is formed. Due to is lower density, the CdCl.sub.2 rises through the Cd layer into a layer of molten LiCl--KCL salt where a rotatable basket containing uranium ingots is suspended. The CdCl.sub.2 reacts with the uranium to form UCl.sub.3 and Cd. Due to density differences, the Cd sinks down to the liquid Cd layer and is reused. The UCl.sub.3 combines with the molten salt. During production the temperature is maintained at about 600.degree. C. while after the uranium has been depleted the salt temperature is lowered, the molten salt is pressure siphoned from the vessel, and the salt product LiCl--KCl-30 mol % UCl.sub.3 is solidified.

Counter anion effect on structural, opto-electronic and charge transport properties of fused π-conjugated imidazolium compound

NASA Astrophysics Data System (ADS)

Vinodha, M.; Senthilkumar, K.

2018-05-01

The structure-activity relationship of fused π-conjugated imidazolium cation with three counter anion molecules, BF4-, CF3SO3- and (CF3SO2)2N-, was studied using electronic structure calculations. The structural, opto-electronic and charge transport properties of these complexes were studied. The charge transfer from π-conjugated imidazolium(I) to counter anion was confirmed in all the studied complexes. Interaction energy varies significantly depending on the counter anion and the stability was found higher for I-BF4 complex than both I-CF3SO3 and I-(CF3SO2)2N complexes. The strong (C-H)+...F- hydrogen bond of length 1.95 Å between fused π-conjugated imidazolium and BF-4 anion is the driving force for the strongest interaction energy in I-BF4 complex. The energy decomposition analysis confirms that the interaction between imidazolium and counter anion is mainly driven by electrostatic and orbital interaction. It has been observed that the absorption spectra of the complex are independent of anion nature but the influence of anion character is observed on frontier molecular orbital pattern. The charge transport property of I-BF4 complex was studied by using tight-binding Hamiltonian approach and found that the hole mobility in I-BF4 is 1.13 × 10-4 cm2 V-1 s-1.

Performance and Return to Sport After Tommy John Surgery Among Major League Baseball Position Players.

PubMed

Jack, Robert A; Burn, Matthew B; Sochacki, Kyle R; McCulloch, Patrick C; Lintner, David M; Harris, Joshua D

2018-06-01

The anterior bundle of the medial ulnar collateral ligament (UCL) is the primary restraint to valgus stress at the elbow and is often injured among overhead throwing athletes. Despite prevention strategies, injuries to the elbow UCL are on the rise. To determine (1) the return-to-sport (RTS) rate of Major League Baseball (MLB) position players after elbow medial UCL reconstruction, (2) postoperative career length and games per season, (3) pre- and postoperative performance, (4) postoperative performance versus matched control players, and (5) whether position players changed positions after UCL reconstruction. Cohort study; Level of evidence, 3. MLB players who underwent elbow UCL reconstruction were identified (cases). Demographic and performance data were collected for each player. Matched controls were identified. RTS in MLB was defined as playing in at least 1 MLB game after UCL reconstruction. Comparisons between case and control groups and pre- and postoperative time points were made via paired samples Student t tests. Thirty-three players (34 surgical procedures) were identified with a mean ± SD age of 30.2 ± 4.2 years and a mean experience in the MLB of 6.3 ± 3.9 years at the time of surgery. Twenty-eight players (84.8%) were able to RTS in MLB at a mean 336.9 ± 121.8 days. However, players ≥30 years old demonstrated a significantly lower RTS rate (53.3%) than players <30 years old (89.4%; P < .05). Catchers had a significantly shorter postoperative career length (2.8 ± 1.8 years) versus matched controls (6.1 ± 1.9 years; P < .05). Outfielders had a significantly lower wins above replacement postoperatively (0.8 ± 0.7) versus preoperatively (1.5 ± 1.1; P < .05). There were no performance differences between cases and matched controls. Twelve players (48%) returned to a different position postoperatively. The RTS rate for MLB position players after elbow UCL reconstruction is similar to that of pitchers. Catchers had a significantly shorter career length than that of matched controls. Outfielders performed worse postoperatively versus preoperatively. There is a high rate of position change after Tommy John surgery for infielders and outfielders.

Media perceptions of Tommy John surgery.

PubMed

Conte, Stan A; Hodgins, Justin L; ElAttrache, Neal S; Patterson-Flynn, Nancy; Ahmad, Christopher S

2015-11-01

The prevalence of medial ulnar collateral ligament (UCL) reconstruction is increasing in professional athletes and the delivery of baseball news by the media exerts a powerful influence on public opinion of the injury and surgery. The purpose of this investigation was to examine the media's perception regarding the causes of UCL injury as well as the indications, risks, benefits, and rehabilitation related to UCL reconstruction. Cross-sectional survey study, Level 3. This study utilized an online thirty-question survey designed to assess an individual's perception of UCL reconstruction with regard to risk factors for injury, indications, benefits, surgical details, and rehabilitation. Eligible study participants were members of the media including print, internet, radio and/or television directly involved in the coverage of Major League Baseball (MLB). A total of 516 members of the media with a mean age of 43.6 years completed the survey. In nearly half (47.8%), professional baseball represented 76-100% of their total sports coverage responsibility. although the majority answered correctly, 45% did not know if an athlete needed an elbow injury as a prerequisite for UCL reconstruction and 25% believed the primary indication was performance enhancement. As percentage of baseball coverage increased, media members were less likely to believe that an elbow injury was not required (p = 0.038). eighty percent recognized that pitching speed is typically reduced following surgery, but the remaining 20% felt that velocities actually increased compared with pre-injury velocities. Return to play: fifty-two percent overestimated the ability of pitchers to return to back to professional baseball and 51.2% believed return would occur in 12 or less months. Estimates were higher in those of older age (p = 0.032) and increased percentage of baseball coverage (p < 0.001). Overuse injuries: less than half (48.4%) believed the use of pitch counts to be important in the prevention of UCL injury and 33.2% felt that throwing injuries were not preventable in adolescent baseball. Common misconceptions exist regarding UCL reconstruction within the professional baseball media. Efforts for physicians to educate the media on the risks of overuse throwing injuries with emphasis on accurate indications, outcomes, and recovery of Tommy John Surgery are encouraged.

Elbow ulnar collateral ligament injuries in athletes: Can we improve our outcomes?

PubMed Central

Redler, Lauren H; Degen, Ryan M; McDonald, Lucas S; Altchek, David W; Dines, Joshua S

2016-01-01

Injury to the ulnar collateral ligament (UCL) most commonly occurs in the overhead throwing athlete. Knowledge surrounding UCL injury pathomechanics continues to improve, leading to better preventative treatment strategies and rehabilitation programs. Conservative treatment strategies for partial injuries, improved operative techniques for reconstruction in complete tears, adjunctive treatments, as well as structured sport specific rehabilitation programs including resistive exercises for the entire upper extremity kinetic chain are all important factors in allowing for a return to throwing in competitive environments. In this review, we explore each of these factors and provide recommendations based on the available literature to improve outcomes in UCL injuries in athletes. PMID:27114930

Epidemiology of Ulnar Collateral Ligament Reconstruction in Major and Minor League Baseball Pitchers: Comprehensive Report on 1,313 Cases

PubMed Central

Camp, Christopher L.; Conte, Stan; D’Angelo, John; Fealy, Stephen

2017-01-01

Objectives: Although much as been done to better understand and characterize the epidemic of UCL reconstruction in pitchers, a comprehensive review of all UCL reconstructions performed in professional baseball pitchers is surprisingly lacking. Accordingly, the purpose of this work was to provide an epidemiologic report on every UCL reconstruction ever performed in professional baseball with a special focus on outcomes (return to play rates and time) and overall survivorship. Methods: Three resources (including the Major League Baseball [MLB] injury tracking system) were combined and cross-referenced to identify all professional baseball players who had ever undergone primary UCL reconstruction (1974 to 2015). Variables analyzed included the date of injury, date of surgery, time out of play, geographical region, and revision status. Trends over time were analyzed collectively and based on level of play at the time of surgery. A minimum of 2 years of follow up was required to determine return to play status. Revision free Kaplan-Meier survivor analysis was performed. Results: A total of 1,313 UCL reconstructions were identified. The annual rate of primary and revision UCL reconstructions rose significantly for all levels of play from 1974 to 2015 and from (p<0.001). The overall mean time to return to play (RTP) was 436 days (range 98 to 1,643). The rate of RTP to any level was 93.9% for MLB pitchers vs. 76.3% for MiLB pitchers (p<0.001), and MLB pitchers RTP at the MLB level in 73.1% of cases. The time to RTP was longer (by 54 days) for revisions (p=0.025) compared to primaries, and MLB pitchers RTP from primary surgery 95.6% of the time but only 81.8% for revision surgery (p=0.008). The revision rate was 10.7%, and the percentage of players free of revision and still playing professional baseball was 92% at 2 years, 53% at 5 years, and 17% at 10 years. Survivorship was improved for players undergoing UCL reconstruction before age 25 opposed to after 25. Conclusion: This study represents the most robust epidemiologic report of UCL reconstruction in baseball to date, and a number of novel findings are reported. A number of key differences in MLB and MiLB, as well as primary and revision surgeries, were identified. Although the revision rate (10.7%) is higher than prior reports, 75% of players who had surgery before age of 25 are revision free and still playing professional baseball four years post operative.

Collaborations, Courses, and Competitions: Developing Entrepreneurship Programmes at UCL

ERIC Educational Resources Information Center

Chapman, David; Skinner, Jeff

2006-01-01

Purpose: This paper aims to detail a range of collaborative programmes developed by University College London (UCL) and the London Business School (LBS). These schemes have been developed to exploit synergies between the two institutions with the aim of promoting entrepreneurship within the fields of science and technology.…

DFT Study on the Complexation of Bambus[6]uril with the Perchlorate and Tetrafluoroborate Anions.

PubMed

Toman, Petr; Makrlík, Emanuel; Vaňura, Petr

2011-12-01

By using quantum mechanical DFT calculations, the most probable structures of the bambus[6]uril.ClO4- and bambus[6]uril.BF4- anionic complex species were derived. In these two complexes having C3 symmetry, each of the considered anions, included in the macrocyclic cavity, is bound by 12 weak hydrogen bonds between methine hydrogen atoms on the convex face of glycoluril units and the respective anion.

Theoretical study on complexation of the perchlorate, permanganate, pertechnate and perrhenate anions with dodecabenzylbambus[6]uril

NASA Astrophysics Data System (ADS)

Böhm, Stanislav; Makrlík, Emanuel; Vaňura, Petr

2017-07-01

By using quantum chemical calculations, the most probable structures of the anionic complex species dodecabenzylbambus[6]uril-ClO4-, dodecabenzylbambus[6]uril-MnO4-, dodecabenzylbambus[6]uril-TcO4- and dodecabenzylbambus[6]uril-ReO4- were derived. In these four complexes, each of the considered anions, included in the macrocyclic cavity, is bound by 12 weak hydrogen bonds between methine hydrogen atoms on the convex face of glycoluril units and the respective anion. Further, the corresponding interaction energies of the investigated four anionic complexes were calculated; the absolute values of these calculated energies increase in the series of ReO4- < TcO4- < MnO4- < ClO4-.

Possibility of using salivary ultra-weak chemiluminescence as a biomarker for feelings of anxiety in hospital settings.

PubMed

Hiramatsu, Mitsuo; Chida, Kingo; Hashimoto, Dai; Takamoto, Hisayoshi; Honzawa, Katsu; Okada, Hiroyuki; Nakamura, Kimitsugu; Takagi, Kuniaki

2016-11-01

The aim of this study was to assess whether a particular value of noninvasive salivary ultra-weak chemiluminescence (UCL) could be used as a biomarker of psychological stress. Our study covered two groups. Group 1 comprised six healthy volunteers who stayed in a hospital for one night and group 2 comprised 15 patients with lung cancer and 24 patients with respiratory diseases other than lung cancer who were in hospital for an extended stay. First, we evaluated the UCL of saliva from six healthy volunteers before and after one night in hospital. Immunoglobulin A (IgA) concentrations were also measured. The integrated intensity value of UCL was correlated with the IgA concentration (correlation coefficient 0.90). Second, in the case of a long hospital stay, we found that the maximum salivary UCL intensities were higher in patients with lung cancer than in those with respiratory diseases other than lung cancer or in 28 healthy controls. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Thermochemical cycles for the production of hydrogen

DOEpatents

Steinberg, M.; Dang, V.D.

Two-step processes for the preparation of hydrogen are described: CrCl/sub 3/(g) ..-->.. CrCl/sub 2/(g) + 1/2Cl/sub 2/(g) and CrCl/sub 2/(s) + HCl(g) reversible CrCl/sub 3/(s) + 1/2H/sub 2/(g); UCl/sub 4/(g) ..-->.. UCl/sub 3/(g) + 1/2Cl/sub 2/(g) and UCl/sub 3/(s) + HCl(g) ..-->.. UCl/sub 4/(s) + 1/2H/sub 2/(g); and CaSO/sub 4/(s) ..-->.. CaO(s) + SO/sub 2/(g) + 1/2O/sub 2/(g) and CaO(s) + SO/sub 2/(g) + H/sub 2/O(l) ..-->.. CaSO/sub 4/(s) + H/sub 2/(g). The high temperature available from solar collectors, high temperature gas reactors or fusion reactors is utilized in the first step in which the reaction is endothermic. The efficiency is at least 60% and with process heat recovery, the efficiency may be increased up to 74.4%. An apparatus fr carrying out the process in conjunction with a fusion reactor, is described.

Lanthanide-Doped KLu2F7 Nanoparticles with High Upconversion Luminescence Performance: A Comparative Study by Judd-Ofelt Analysis and Energy Transfer Mechanistic Investigation

NASA Astrophysics Data System (ADS)

Xu, Dekang; Li, Anming; Yao, Lu; Lin, Hao; Yang, Shenghong; Zhang, Yueli

2017-02-01

The development, design and the performance evaluation of rare-earth doped host materials is important for further optical investigation and industrial applications. Herein, we successfully fabricate KLu2F7 upconversion nanoparticles (UCNPs) through hydrothermal synthesis by controlling the fluorine-to-lanthanide-ion molar ratio. The structural and morphological results show that the samples are orthorhombic-phase hexagonal-prisms UCNPs, with average side length of 80 nm and average thickness of 110 nm. The reaction time dependent crystal growth experiment suggests that the phase transformation is a thermo-dynamical process and the increasing F-/Ln3+ ratio favors the formation of the thermo-dynamical stable phase - orthorhombic KLu2F7 structure. The upconversion luminescence (UCL) spectra display that the orthorhombic KLu2F7:Yb/Er UCNPs present stronger UCL as much as 280-fold than their cubic counterparts. The UCNPS also display better UCL performance compared with the popular hexagonal-phase NaREF4 (RE = Y, Gd). Our mechanistic investigation, including Judd-Ofelt analysis and time decay behaviors, suggests that the lanthanide tetrad clusters structure at sublattice level accounts for the saturated luminescence and highly efficient UCL in KLu2F7:Yb/Er UCNPs. Our research demonstrates that the orthorhombic KLu2F7 is a promising host material for UCL and can find potential applications in lasing, photovoltaics and biolabeling techniques.

Inositol Pyrophosphate Profiling of Two HCT116 Cell Lines Uncovers Variation in InsP8 Levels

PubMed Central

Gu, Chunfang; Wilson, Miranda S. C.; Jessen, Henning J.; Saiardi, Adolfo; Shears, Stephen B.

2016-01-01

The HCT116 cell line, which has a pseudo-diploid karotype, is a popular model in the fields of cancer cell biology, intestinal immunity, and inflammation. In the current study, we describe two batches of diverged HCT116 cells, which we designate as HCT116NIH and HCT116UCL. Using both gel electrophoresis and HPLC, we show that HCT116UCL cells contain 6-fold higher levels of InsP8 than HCT116NIH cells. This observation is significant because InsP8 is one of a group of molecules collectively known as ‘inositol pyrophosphates’ (PP-InsPs)—highly ‘energetic’ and conserved regulators of cellular and organismal metabolism. Variability in the cellular levels of InsP8 within divergent HCT116 cell lines could have impacted the phenotypic data obtained in previous studies. This difference in InsP8 levels is more remarkable for being specific; levels of other inositol phosphates, and notably InsP6 and 5-InsP7, are very similar in both HCT116NIH and HCT116UCL lines. We also developed a new HPLC procedure to record 1-InsP7 levels directly (for the first time in any mammalian cell line); 1-InsP7 comprised <2% of total InsP7 in HCT116NIH and HCT116UCL lines. The elevated levels of InsP8 in the HCT116UCL lines were not due to an increase in expression of the PP-InsP kinases (IP6Ks and PPIP5Ks), nor to a decrease in the capacity to dephosphorylate InsP8. We discuss how the divergent PP-InsP profiles of the newly-designated HCT116NIH and HCT116UCL lines should be considered an important research opportunity: future studies using these two lines may uncover new features that regulate InsP8 turnover, and may also yield new directions for studying InsP8 function. PMID:27788189

Upconversion luminescence and blackbody radiation in tetragonal YSZ co-doped with Tm(3+) and Yb(3+).

PubMed

Soares, M R N; Ferro, M; Costa, F M; Monteiro, T

2015-12-21

Lanthanide doped inorganic nanoparticles with upconversion luminescence are of utmost importance for biomedical applications, solid state lighting and photovoltaics. In this work we studied the downshifted luminescence, upconversion luminescence (UCL) and blackbody radiation of tetragonal yttrium stabilized zirconia co-doped with Tm(3+) and Yb(3+) single crystals and nanoparticles produced by laser floating zone and laser ablation in liquids, respectively. The photoluminescence (PL) and PL excitation (PLE) were investigated at room temperature (RT). PL spectra exhibit the characteristic lines in UV, blue/green, red and NIR regions of the Tm(3+) (4f(12)) under resonant excitation into the high energy (2S+1)LJ multiplets. Under NIR excitation (980 nm), the samples placed in air display an intense NIR at ∼800 nm due to the (1)G4→(3)H5/(3)H4→(3)H6 transitions. Additionally, red, blue/green and ultraviolet UCL is observed arising from higher excited (1)G4 and (1)D2 multiplets. The power excitation dependence of the UCL intensity indicated that 2-3 low energy absorbed photons are involved in the UCL for low power levels, while for high powers, the identified saturation is dependent on the material size with a enhanced effect on the NPs. The temperature dependence of the UCL was investigated for single crystals and targets used in the ablation. An overall increase of the integrated intensity was found to occur between 12 K and the RT. The thermally activated process is described by activation energies of 10 meV and 30 meV for single crystals and targets, respectively. For the NPs, the UCL was found to be strongly sensitive to pressure conditions. Under vacuum conditions, instead of the narrow lines of the Tm(3+), a wide blackbody radiation was detected, responsible for the change in the emission colour from blue to orange. This phenomenon is totally reversible when the NPs are placed at ambient pressure. The UCL/blackbody radiation in the nanosized material exhibits non-contact pressure colour-based sensor characteristics. Moreover, tuning the color of the blackbody radiation in the nanoparticles by harvesting the low energy photons into the visible spectral region was found to be possible by adjusting the excitation power, paving the way for further developments of these nanoparticles for lighting and photovoltaic applications.

Baseball Players With an Ulnar Collateral Ligament Tear Display Increased Nondominant Arm Humeral Torsion Compared With Healthy Baseball Players.

PubMed

Meyer, Casey J; Garrison, J Craig; Conway, John E

2017-01-01

Previous work has suggested that an increase in the amount of developmentally acquired, dominant arm humeral retrotorsion (D HRT) in the thrower's shoulder may be a potentially protective mechanism. Although the relationship between HRT and shoulder injuries has been reported, the relationship between HRT and ulnar collateral ligament (UCL) tears in baseball players is not known. To determine whether D HRT and nondominant arm HRT (ND HRT) measurements in baseball players with a UCL tear differ statistically from a matched healthy cohort. Case-control study; Level of evidence, 3. D HRT and ND HRT were measured in 112 male competitive high school and collegiate baseball players seen over an 18-month period from 2013 to 2015. A total of 56 participants with a clinical and magnetic resonance imaging-confirmed diagnosis of a throwing-arm UCL tear (UCLInj group) were compared with 56 healthy baseball players with no history of an elbow injury who were matched for age, experience, and position (NUCLInj group). The mean ages in the UCLInj and NUCLInj groups were 17.9 ± 2.2 and 17.6 ± 2.8 years, respectively. Using a previously validated ultrasound method, D HRT and ND HRT were measured in the supine position, and the HRT side-to-side difference (D HRT - ND HRT) was calculated. A 1-way multivariate analysis of variance was used to determine the mean statistical differences between groups ( P < .05). Baseball players with a UCL tear displayed significantly more humeral torsion (ie, less retrotorsion) in their nondominant arm compared with healthy baseball players (UCLInj = 33.27° ± 10.27°, NUCLInj = 27.82° ± 10.88°; P = .007). Baseball players with a UCL tear did not display any differences in D HRT compared with healthy baseball players (UCLInj = 18.67° ± 9.41°, NUCLInj = 17.09° ± 9.92°; P = .391). Significant side-to-side differences in HRT existed between groups (UCLInj = -14.60° ± 6.72°, NUCLInj = -10.72° ± 6.88°; P = .003). There was a significant increase in mean nondominant arm humeral torsion (ie, less retrotorsion) in the UCL tear group, but there was no significant difference in the mean D HRT between the injured and uninjured groups. A greater HRT side-to-side difference was displayed in the UCL tear group. The extent to which a thrower has developmentally acquired both D HRT and ND HRT may affect elbow UCL tear risk. Furthermore, it is possible that the extent of genetically predisposed ND HRT may influence the throwing-related increase in D HRT.

The impact of ionic liquids on the coordination of anions with solvatochromic copper complexes.

PubMed

Kuzmina, O; Hassan, N H; Patel, L; Ashworth, C; Bakis, E; White, A J P; Hunt, P A; Welton, T

2017-09-28

Solvatochromic transition metal (TM)-complexes with weakly associating counter-anions are often used to evaluate traditional neutral solvent and anion coordination ability. However, when employed in ionic liquids (IL) many of the common assumptions made are no longer reliable. This study investigates the coordinating ability of weakly coordinating IL anions in traditional solvents and within IL solvents employing a range of solvatochromic copper complexes. Complexes of the form [Cu(acac)(tmen)][X] (acac = acetylacetonate, tmen = tetramethylethylenediamine) where [X] - = [ClO 4 ] - , Cl - , [NO 3 ] - , [SCN] - , [OTf] - , [NTf 2 ] - and [PF 6 ] - have been synthesised and characterised both experimentally and computationally. ILs based on these anions and imidazolium and pyrrolidinium cations, some of which are functionalised with hydroxyl and nitrile groups, have been examined. IL-anion coordination has been investigated and compared to typical weakly coordinating anions. We have found there is potential for competition at the Cu-centre and cases of anions traditionally assigned as weakly associating that demonstrate a stronger than expected level of coordinating ability within ILs. [Cu(acac)(tmen)][PF 6 ] is shown to contain the least coordinating anion and is established as the most sensitive probe studied here. Using this probe, the donor numbers (DNs) of ILs have been determined. Relative donor ability is further confirmed based on the UV-Vis of a neutral complex, [Cu(sacsac) 2 ] (sacsac = dithioacetylacetone), and DNs evaluated via 23 Na NMR spectroscopy. We demonstrate that ILs can span a wide donor range, similar in breadth to conventional solvents.

Modernization at the Y-12 National Security Complex: A Case for Additional Experimental Benchmarks

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

Thornbury, M. L.; Juarez, C.; Krass, A. W.

Efforts are underway at the Y-12 National Security Complex (Y-12) to modernize the recovery, purification, and consolidation of un-irradiated, highly enriched uranium metal. Successful integration of advanced technology such as Electrorefining (ER) eliminates many of the intermediate chemistry systems and processes that are the current and historical basis of the nuclear fuel cycle at Y-12. The cost of operations, the inventory of hazardous chemicals, and the volume of waste are significantly reduced by ER. It also introduces unique material forms and compositions related to the chemistry of chloride salts for further consideration in safety analysis and engineering. The work hereinmore » briefly describes recent investigations of nuclear criticality for 235UO2Cl2 (uranyl chloride) and 6LiCl (lithium chloride) in aqueous solution. Of particular interest is the minimum critical mass of highly enriched uranium as a function of the molar ratio of 6Li to 235U. The work herein also briefly describes recent investigations of nuclear criticality for 235U metal reflected by salt mixtures of 6LiCl or 7LiCl (lithium chloride), KCl (potassium chloride), and 235UCl3 or 238UCl3 (uranium tri-chloride). Computational methods for analysis of nuclear criticality safety and published nuclear data are employed in the absence of directly relevant experimental criticality benchmarks.« less

Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu(-)(cytidine) and Cu(-)(uridine).

PubMed

Li, Xiang; Ko, Yeon-Jae; Wang, Haopeng; Bowen, Kit H; Guevara-García, Alfredo; Martínez, Ana

2011-02-07

The copper-nucleoside anions, Cu(-)(cytidine) and Cu(-)(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu(-)(cytidine) and Cu(-)(uridine), respectively. According to our calculations, Cu(-)(cytidine) and Cu(-)(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostatic interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu(-)(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.

Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu-(cytidine) and Cu-(uridine)

NASA Astrophysics Data System (ADS)

Li, Xiang; Ko, Yeon-Jae; Wang, Haopeng; Bowen, Kit H.; Guevara-García, Alfredo; Martínez, Ana

2011-02-01

The copper-nucleoside anions, Cu-(cytidine) and Cu-(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu-(cytidine) and Cu-(uridine), respectively. According to our calculations, Cu-(cytidine) and Cu-(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostatic interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu-(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.

NREL Wins Prestigious UK "Academy Award" for Engineering | News | NREL

Science.gov Websites

College London (UCL), along with NASA, The European Synchrotron, and the UK National Physical Laboratory impressive company." UCL, NREL, NASA, and their partners were recognized in the category of Safety and Device developed by NREL and NASA to study failure mechanisms in Li-ion batteries and then recorded their

Using the Behaviour Change Wheel in infection prevention and control practice

PubMed Central

Atkins, Lou

2015-01-01

The Centre for Behaviour Change at University College London (UCL) is a new venture that has grown out of the work that we have been doing in the Health Psychology Research Group at UCL and seeks to harness the different pockets of behaviour change work in different disciplines across UCL. A lot of our work in health focuses on the adoption of evidence-based guidelines in practice; not just designing and evaluating interventions, but also developing usable tools for people who are tasked with changing behaviours. These tools aim to enable those who do not necessarily have a background in behavioural science to understand the behaviours they are trying to change and design appropriate interventions. PMID:28989457

Ruthenium(II) 2,2'-bibenzimidazole complex as a second-sphere receptor for anions interaction and colorimeter.

PubMed

Cui, Ying; Niu, Yan-Li; Cao, Man-Li; Wang, Ke; Mo, Hao-Jun; Zhong, Yong-Rui; Ye, Bao-Hui

2008-07-07

A ruthenium(II) complex [Ru(bpy) 2(H 2bbim)](PF 6) 2 ( 1) as anions receptor has been exploited, where Ru(II)-bpy moiety acts as a chromophore and the H 2bbim ligand as an anion binding site. A systematic study suggests that 1 interacts with the Cl (-), Br (-), I (-), NO 3 (-), HSO 4 (-), and H 2PO 4 (-) anions via the formation of hydrogen bonds. Whereas 1 undergoes a stepwise process with the addition of F (-) and OAc (-) anions: formation of the monodeprotonated complex [Ru(bpy) 2(Hbbim)] with a low anion concentration, followed by the double-deprotonated complex [Ru(bpy) 2(bbim)], in the presence of a high anion concentration. These stepwise processes concomitant with the changes of vivid colors from yellow to orange brown and then to violet can be used for probing the F (-) and OAc (-) anions by naked eye. The deprotonation processes are not only determined by the basicity of the anion but also related to the strength of hydrogen bonding, as well as the stability of the formed compounds. Moreover, a double-deprotonated complex [Ru(bpy) 2(bbim)].CH 3OH.H 2O ( 3) has been synthesized, and the structural changes induced by the deprotonation has also been investigated. In addition, complexes [Ru(bpy) 2(Hbbim)] 2(HOAc) 3Cl 2.12H 2O ( 2), [Ru(bpy) 2(Hbbim)](HCCl 3CO 2)(CCl 3CO 2).2H 2O ( 4), and [Ru(bpy) 2(H 2bbim)](CF 3CO 2) 2.4H 2O ( 5) have been synthesized to observe the second sphere coordination between the Ru(II)-H 2bbim moiety and carboxylate groups via hydrogen bonds in the solid state.

Porphyrin-Sensitized Evolution of Hydrogen using Dawson and Keplerate Polyoxometalate Photocatalysts.

PubMed

Panagiotopoulos, Athanassios; Douvas, Antonios M; Argitis, Panagiotis; Coutsolelos, Athanassios G

2016-11-23

Hydrogen evolution using photocatalytic systems based on artificial photosynthesis is a major approach toward solar energy conversion and storage. In the polyoxometalate-based photocatalytic systems proposed in the past, middle/near UV light irradiation and noble-metal catalysts were mainly used. Although recently polyoxometalates were sensitized in visible light, photosensitizers or catalysts based on noble metals, and/or poor activity of polyoxometalates were generally obtained. Here we show the highly efficient [turnover number (TON)=215] hydrogen evolution induced by the zinc(II) mesotetrakis(N-methyl-pyridinium-4-yl)porphyrin (ZnTMPyP 4+ ) sensitization of a series of polyoxometalate catalysts (two Dawson type, P 2 Mo 18 O 62 6- and P 2 W 18 O 62 6- anions, and one Keplerate {Mo 132 } cluster) in a visible-light-driven, noble-metal-free, and fully water-soluble system. We attributed the high efficiency for hydrogen evolution to the multi-electron reduction of polyoxometalates and found that: (a) both Dawson polyoxometalates exhibit higher hydrogen evolution efficiency upon ZnTMPyP 4+ sensitization in relation to the direct photoreduction of those compounds; (b) the P 2 Mo 18 O 62 6- anion is more efficient (TON=65 vs. 38, respectively) for hydrogen evolution than the P 2 W 18 O 62 6- anion; and (c) the high nuclearity Keplerate {Mo 132 } cluster exhibits the highest efficiency (TON=215) for hydrogen evolution compared with the polyoxometalates studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

μ-Hexa-thio-metadiphosphato-bis-[(1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane-κ(6) O)rubidium] aceto-nitrile disolvate.

PubMed

Gjikaj, Mimoza; Pook, Niels-Patrick; Qarri, Flora

2013-12-01

The asymmetric unit of the title compound, [Rb2(P2S6)(C12H24O6)2]·2CH3CN, contains one half of an [Rb(18-crown-6)2]2[P2S6] unit and one aceto-nitrile solvent mol-ecule. The [Rb(18-crown-6)]2[P2S6] unit is completed by inversion symmetry. Its Rb(+) ion is situated near the centre of the macrocyclic cavity, but is displaced by 0.8972 (1) Å from the O atoms of the crown in the direction of the [P2S6](2-) moiety. The overall coordination number of the cation is eight, defined by the six crown ether O atoms and by two terminal S atoms of the [P2S6](2-) anion. The hexa-thio-metadiphosphate anion is built up from two tetra-hedral PS4 units joined together by a common edge. The crystal structure is characterized by alternating layers of [Rb(18-crown-6)]2[P2S6] and aceto-nitrile solvent mol-ecules stacked along [010].

Reliability and precision of stress sonography of the ulnar collateral ligament.

PubMed

Bica, David; Armen, Joseph; Kulas, Anthony S; Youngs, Kevin; Womack, Zachary

2015-03-01

Musculoskeletal sonography has emerged as an additional diagnostic tool that can be used to assess medial elbow pain and laxity in overhead throwers. It provides a dynamic, rapid, and noninvasive modality in the evaluation of ligamentous structural integrity. Many studies have demonstrated the utility of dynamic sonography for medial elbow and ulnar collateral ligament (UCL) integrity. However, evaluating the reliabilityand precision of these measurements is critical if sonography is ultimately used as a clinical diagnostic tool. The purpose of this study was to evaluate the reliability and precision of stress sonography applied to the medial elbow. We conducted a cross-sectional study during the 2011 baseball off-season. Eighteen National Collegiate Athletic Association Division I pitchers were enrolled, and 36 elbows were studied. Using sonography, the medial elbow was assessed, and measurements of the UCL length and ulnohumeral joint gapping were performed twice under two conditions (unloaded and loaded) and bilaterally. Intraclass correlation coefficients (0.72-0.94) and standard errors of measurements (0.3-0.9 mm) for UCL length and ulnohumeral joint gapping were good to excellent. Mean differences between unloaded and loaded conditions for the dominant arms were 1.3 mm (gapping; P < .001) and 1.4 mm (UCL length; P < .001). Medial elbow stress sonography is a reliable and precise method for detecting changes in ulnohumeral joint gapping and UCL lengthening. Ultimately, this method may provide clinicians valuable information regarding the medial elbow's response to valgus loading and may help guide treatment options. © 2015 by the American Institute of Ultrasound in Medicine.

The triel bond: a potential force for tuning anion-π interactions

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Mousavian, Parisasadat

2018-02-01

Using ab-initio calculations, the mutual influence between anion-π and B···N or B···C triel bond interactions is investigated in some model complexes. The properties of these complexes are studied by molecular electrostatic potential, noncovalent interaction index, quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. According to the results, the formation of B···N or B···C triel bond interactions in the multi-component systems makes a significant shortening of anion-π distance. Such remarkable variation in the anion-π distances has not been reported previously. The strengthening of the anion-π bonding in the multi-component systems depend significantly on the nature of the anion, and it becomes larger in the order Br- > Cl- > F-. The parameters derived from the QTAIM and NBO methodologies are used to study the mechanism of the cooperativity between the anion-π and triel bond interactions in the multi-component complexes.

Simultaneous separation of inorganic anions and metal-citrate complexes on a zwitterionic stationary phase with on-column complexation.

PubMed

Nesterenko, Ekaterina P; Nesterenko, Pavel N; Paull, Brett

2008-12-05

The retention and separation selectivity of inorganic anions and on-column derivatised negatively charged citrate or oxalate metal complexes on reversed-phase stationary phases dynamically coated with N-(dodecyl-N,N-dimethylammonio)undecanoate (DDMAU) has been investigated. The retention mechanism for the metal-citrate complexes was predominantly anion exchange, although the amphoteric/zwitterionic nature of the stationary phase coating undoubtedly also contributed to the unusual separation selectivity shown. A mixture of 10 inorganic anions and metal cations was achieved using a 20 cm monolithic DDMAU modified column and a 1 mM citrate eluent, pH 4.0, flow rate equal to 0.8 mL/min. Selectivity was found to be strongly pH dependent, allowing additional scope for manipulation of solute retention, and thus application to complex samples. This is illustrated with the analysis of an acidic mine drainage sample with a range of inorganic anions and transition metal cations, varying significantly in their concentrations levels.

Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu{sup -}(cytidine) and Cu{sup -}(uridine)

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

Li Xiang; Ko, Yeon-Jae; Wang Haopeng

2011-02-07

The copper-nucleoside anions, Cu{sup -}(cytidine) and Cu{sup -}(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu{sup -}(cytidine) and Cu{sup -}(uridine), respectively. According to our calculations, Cu{sup -}(cytidine) and Cu{sup -}(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostaticmore » interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu{sup -}(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.« less

Process for recovering uranium

DOEpatents

MacWood, G. E.; Wilder, C. D.; Altman, D.

1959-03-24

A process useful in recovering uranium from deposits on stainless steel liner surfaces of calutrons is presented. The deposit is removed from the stainless steel surface by washing with aqueous nitric acid. The solution obtained containing uranium, chromium, nickel, copper, and iron is treated with an excess of ammonium hydroxide to precipitnte the uranium, iron, and chromium and convert the nickel and copper to soluble ammonio complexions. The precipitated material is removed, dried and treated with carbon tetrachloride at an elevated temperature of about 500 to 600 deg C to form a vapor mixture of UCl/ sub 4/, UCl/sub 5/, FeCl/sub 3/, and CrCl/sub 4/. The UCl/sub 4/ is separated from this vapor mixture by selective fractional condensation at a temperature of about 500 to 400 deg C.

ChAMP: updated methylation analysis pipeline for Illumina BeadChips.

PubMed

Tian, Yuan; Morris, Tiffany J; Webster, Amy P; Yang, Zhen; Beck, Stephan; Feber, Andrew; Teschendorff, Andrew E

2017-12-15

The Illumina Infinium HumanMethylationEPIC BeadChip is the new platform for high-throughput DNA methylation analysis, effectively doubling the coverage compared to the older 450 K array. Here we present a significantly updated and improved version of the Bioconductor package ChAMP, which can be used to analyze EPIC and 450k data. Many enhanced functionalities have been added, including correction for cell-type heterogeneity, network analysis and a series of interactive graphical user interfaces. ChAMP is a BioC package available from https://bioconductor.org/packages/release/bioc/html/ChAMP.html. a.teschendorff@ucl.ac.uk or s.beck@ucl.ac.uk or a.feber@ucl.ac.uk. Supplementary data are available at Bioinformatics online. © The Author(s) 2017. Published by Oxford University Press.

PROCESS FOR RECOVERING URANIUM

DOEpatents

MacWood, G.E.; Wilder, C.D.; Altman, D.

1959-03-24

A process is described for recovering uranium from deposits on stainless steel liner surfaces of calutrons. The deposit is removed from the stainless steel surface by washing with aqueous nitric acid. The solution obtained containing uranium, chromium, nickels copper, and iron is treated with excess of ammonium hydroxide to precipitatc the uranium, irons and chromium and convert thc nickel and copper to soluble ammonia complexions. The precipitated material is removed, dried, and treated with carbon tetrachloride at an elevated temperature of about 500 to 600 deg C to form a vapor mixture of UCl/sub 4/, UCl/sub 5/, FeCl/ sub 3/, and CrCl/sub 4/. The UCl/sub 4/ is separated from this vapor mixture by selective fractional condensation at a temprrature of about 300 to400 deg C.

Non-covalent interactions in 2-methylimidazolium copper(II) complex (MeImH)2[Cu(pfbz)4]: Synthesis, characterization, single crystal X-ray structure and packing analysis

NASA Astrophysics Data System (ADS)

Sharma, Raj Pal; Saini, Anju; Kumar, Santosh; Kumar, Jitendra; Sathishkumar, Ranganathan; Venugopalan, Paloth

2017-01-01

A new anionic copper(II) complex, (MeImH)2 [Cu(pfbz)4] (1) where, MeImH = 2-methylimidazolium and pfbz = pentafluorobenzoate has been isolated by reacting copper(II) sulfate pentahydrate, pentafluorobenzoic acid and 2-methylimidazole in ethanol: water mixture in 1:2:2 molar ratio. This complex 1 has been characterized by elemental analysis, thermogravimetric analysis, spectroscopic techniques (UV-Vis, FT-IR) and conductance measurements. The complex salt crystallizes in monoclinic crystal system with space group C2/c. Single crystal X-ray structure determination revealed the presence of discrete ions: [Cu(pfbz)4]2- anion and two 2-methylimidazolium cation (C4H7N2)+. The crystal lattice is stabilized by strong hydrogen bonding and F⋯F interactions between cationic-anionic and the anionic-anionic moieties respectively, besides π-π interactions.

A simple and efficient anionic chromogenic chemosensor based on 2,4-dinitrodiphenylamine in dimethyl sulfoxide and in dimethyl sulfoxide-water mixtures

NASA Astrophysics Data System (ADS)

Marini, Vanderléia Gava; Zimmermann, Lizandra Maria; Machado, Vanderlei Gageiro

2010-02-01

Solutions of 2,4-dinitrodiphenylamine ( 1) in dimethylsulfoxide (DMSO) are colorless but upon deprotonation they become red. Addition of various anionic species (HSO 4-, H 2PO 4-, NO 3-, CN -, CH 3COO -, F -, Cl -, Br -, and I -) to solutions of 1 revealed that only CN -, F -, CH 3COO -, and H 2PO 4- led to the appearance of the red color in solution. The presence of increasing amounts of water in solutions containing 1 made it progressively selective toward CN - and the system with the addition of 4.3% (v/v) of water was highly selective for CN - among all anions studied. The experimental data collected indicated that proton transfer from 1 to the anion occurs, and a model was used to explain the experimental results, which considers two 1:anion stoichiometries, 1:1 and 1:2. For the latter, the data suggest that the anion forms firstly a hydrogen-bonded complex with a second anion equivalent necessary for the abstraction of the proton, with the formation of a [HA 2] - complex. The study performed here demonstrates the important role of the environment of the anion and 1 for the efficiency of the chromogenic chemosensor. Besides the different affinities of each anion for water, the solvation of both the anion and 1 is responsible for reducing the interaction between these species. In small amounts, water or hydrogen-bonded DMSO-water complexes are able to stabilize the conjugated base of 1 through hydrogen bonding, making 1 more acidic, which explains the change from 1:1 and 1:2 toward 1:1 1:anion stoichiometry upon addition of water. In addition, water is able to solvate the anion and also 1, which hinders the formation of 1:1 hydrogen-bonded 1:anion complexes prior to the abstraction of the proton.

A simple and efficient anionic chromogenic chemosensor based on 2,4-dinitrodiphenylamine in dimethyl sulfoxide and in dimethyl sulfoxide-water mixtures.

PubMed

Marini, Vanderléia Gava; Zimmermann, Lizandra Maria; Machado, Vanderlei Gageiro

2010-02-01

Solutions of 2,4-dinitrodiphenylamine (1) in dimethylsulfoxide (DMSO) are colorless but upon deprotonation they become red. Addition of various anionic species (HSO(4)(-), H(2)PO(4)(-), NO(3)(-), CN(-), CH(3)COO(-), F(-), Cl(-), Br(-), and I(-)) to solutions of 1 revealed that only CN(-), F(-), CH(3)COO(-), and H(2)PO(4)(-) led to the appearance of the red color in solution. The presence of increasing amounts of water in solutions containing 1 made it progressively selective toward CN(-) and the system with the addition of 4.3% (v/v) of water was highly selective for CN(-) among all anions studied. The experimental data collected indicated that proton transfer from 1 to the anion occurs, and a model was used to explain the experimental results, which considers two 1:anion stoichiometries, 1:1 and 1:2. For the latter, the data suggest that the anion forms firstly a hydrogen-bonded complex with a second anion equivalent necessary for the abstraction of the proton, with the formation of a [HA(2)](-) complex. The study performed here demonstrates the important role of the environment of the anion and 1 for the efficiency of the chromogenic chemosensor. Besides the different affinities of each anion for water, the solvation of both the anion and 1 is responsible for reducing the interaction between these species. In small amounts, water or hydrogen-bonded DMSO-water complexes are able to stabilize the conjugated base of 1 through hydrogen bonding, making 1 more acidic, which explains the change from 1:1 and 1:2 toward 1:1 1:anion stoichiometry upon addition of water. In addition, water is able to solvate the anion and also 1, which hinders the formation of 1:1 hydrogen-bonded 1:anion complexes prior to the abstraction of the proton. Copyright (c) 2009 Elsevier B.V. All rights reserved.

Pharmacological Role of Anions (Sulphate, Nitrate, Oxalate and Acetate) on the Antibacterial Activity of Cobalt(II), Copper(II) and Nickel(II) Complexes With Nicotinoylhydrazine-Derived ONO, NNO and SNO Ligands

PubMed Central

Rauf, Abdur

1996-01-01

Mixed ligands biologically active complexes of cobalt(II), copper(II) and nickel(II) with nicotinoylhydrazine-derived ONO, NNO and SNO donor schiff-base ligands having the same metal ion but different anions such as sulphate, nitrate, oxalate and acetate have been synthesised and characterised on the basis of their physical, analytical and spectral data. In order to evaluate the role of anions on their bioability, these ligands and their synthesised metal complexes with various anions have been screened against bacterial species such as Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus and the title studies have proved a definative role of anions in increasing the biological activity PMID:18472896

A computational study of anion-modulated cation-π interactions.

PubMed

Carrazana-García, Jorge A; Rodríguez-Otero, Jesús; Cabaleiro-Lago, Enrique M

2012-05-24

The interaction of anions with cation-π complexes formed by the guanidinium cation and benzene was thoroughly studied by means of computational methods. Potential energy surface scans were performed in order to evaluate the effect of the anion coming closer to the cation-π pair. Several structures of guanidinium-benzene complexes and anion approaching directions were examined. Supermolecule calculations were performed on ternary complexes formed by guanidinium, benzene, and one anion and the interaction energy was decomposed into its different two- and three-body contributions. The interaction energies were further dissected into their electrostatic, exchange, repulsion, polarization and dispersion contributions by means of local molecular orbital energy decomposition analysis. The results confirm that, besides the electrostatic cation-anion attraction, the effect of the anion over the cation-π interaction is mainly due to polarization and can be rationalized following the changes in the anion-π and the nonadditive (three-body) terms of the interaction. When the cation and the anion are on the same side of the π system, the three-body interaction is anticooperative, but when the anion and the cation are on opposite sides of the π system, the three-body interaction is cooperative. As far as we know, this is the first study where this kind of analysis is carried out with a structured cation as guanidinium with a significant biological interest.

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

Gendron, Frederic; Fleischauer, Valerie R.; Duignan, Thomas J.

Here, we present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl 6- complex ion in the UV-Vis spectral region. The ground state is an orbitally non-degenerate doublet E 5/2u and the MCD is a $C$-term spectrum caused by spin–orbit coupling. Calculations of the electronic spectrum at various levels of theory indicate that differential dynamic electron correlation has a strong influence on the energies of the dipole-allowed transitions and the envelope of the MCD spectrum. The experimentally observed bands are assigned to dipole-allowed ligand-to-metal charge transfer into the 5f shell,more » and 5f to 6d transitions. Charge transfer excitations into the U 6d shell appear at much higher energies. The MCD-allowed transitions can be assigned via their signs of the $C$-terms: Under O h double group symmetry, E 5/2u → E 5/2g transitions have negative $C$-terms whereas E 5/2u → F 3/2g transitions have positive $C$-terms if the ground state g-factor is negative, as it is the case for UCl 6-.« less

Charge Transfer Salts of BO with Paramagnetic Isothiocyanato Complex Anions: (BO)[ M(isoq) 2(NCS) 4]; M=Cr III or Fe III, isoq=isoquinoline and BO=Bis(ethylenedioxo)tetrathiafulvalene

NASA Astrophysics Data System (ADS)

Setifi, Fatima; Ota, Akira; Ouahab, Lahcéne; Golhen, Stèphane; Yamochi, Hideki; Saito, Gunzi

2002-11-01

The preparation, X-ray structures and magnetic properties of two isostructural new charge transfer salts: (BO)[ M(isoq) 2(NCS) 4]; M=Cr III(1), Fe III(2) and isoq=isoquinoline are reported. Their structure consists of alternate organic and inorganic layers, each layer being formed by mixed columns of BO radical cations and paramagnetic metal complex anions. There are short intermolecular contacts between donor and anion (S2 anion· · ·S4 BO<3.5 Å) and between adjacent BO molecules (O· · · O1<3.2 Å). The two compounds are insulators. ESR measurements show single signal without separating the donor and anion spins. The magnetic measurements obey the Curie-Weiss law and revealed dominant antiferromagnetic interactions between anion spin and donor spin, but long-range magnetic ordering did not occur down to 2 K. This is directly related to structural reasons which were deduced from a comparison of the title compounds with other 1:1 salts containing same anion complexes and different donors.

Reagent Anions for Charge Inversion of Polypeptide/Protein Cations in the Gas Phase

PubMed Central

He, Min; Emory, Joshua F.; McLuckey, Scott A.

2005-01-01

Various reagent anions capable of converting polypeptide cations to anions via ion/ion reactions have been investigated. The major charge inversion reaction channels include multiple proton transfer and adduct formation. Dianions composed of sulfonate groups as the negative charge carriers show essentially exclusive adduct formation in converting protonated peptides and proteins to anions. Dianions composed of carboxylate groups, on the other hand, show far more charge inversion via multiple proton transfer, with the degree of adduct formation dependent upon both the size of the polypeptide and the spacings between carboxylate groups in the dianion. More highly charged carboxylate-containing anions, such as those derived from carboxylate-terminated polyamidoamine half-generation dendrimers show charge inversion to give anion charges as high in magnitude as −4, with the degree of adduct formation being inversely related to dendrimer generation. All observations can be interpreted on the basis of charge inversion taking place via a long-lived chemical complex. The lifetime of this complex is related to the strengths and numbers of the interactions of the reactants in the complex. Calculations with model systems are fully consistent with sulfonate groups giving rise to more stable complexes. The kinetic stability of the complex can also be affected by the presence of electrostatic repulsion if it is multiply charged. In general, this situation destabilizes the complex and reduces the likelihood for observation of adducts. The findings highlight the characteristics of multiply charged anions that play roles in determining the nature of charge inversion products associated with protonated peptides and proteins. PMID:15889906

10 CFR Appendix B to Subpart F of... - Sampling Plan For Enforcement Testing

Code of Federal Regulations, 2011 CFR

2011-01-01

... performance of the n 1 units in the first sample as follows: ER18MR98.012 Step 5. Compute the upper control limit (UCL1) and lower control limit (LCL1) for the mean of the first sample using the applicable DOE... the mean of the first sample (x 1) with the upper and lower control limits (UCL1 and LCL1) to...

Two-photon absorption and upconversion luminescence of colloidal CsPbX3 quantum dots

NASA Astrophysics Data System (ADS)

Han, Qiuju; Wu, Wenzhi; Liu, Weilong; Yang, Qingxin; Yang, Yanqiang

2018-01-01

The nonlinear optical and the upconversion luminescence (UCL) properties of CsPbX3 (X = Br or its binary mixtures with Cl, I) quantum dots (QDs) are investigated by femtosecond open-aperture (OA) Z-scan and time-resolved luminescence techniques in nonresonant spectral region. The OA Z-scan results show that CsPbX3 QDs have strong reverse saturable absorption (RSA), which is ascribed to two-photon absorption. Partially changing halide composition from Cl to Br, to I, two-photon absorption cross sections become larger at the same laser excitation intensity. The composition-tunable nonlinear absorption should be attributed to the gradual decrease of the lowest direct band gaps with the halide substitute. Moreover, the strong UCL can be observed under near infrared femtosecond laser excitation. Halide composition-tunable UCL dynamics of CsPbX3 QDs is analyzed by use of two-exponential fitting with deconvolution. When CsPbX3 QDs have similar sizes (10-13 nm), with partially changing halide composition from Cl to Br, to I, the average UCL lifetime becomes longer due to the variation of Kane energy. Our findings suggest all-inorganic perovskite QDs can be used as excellent gain medium for high-performance frequency-upconversion lasers and provide reference to engineer such QDs toward practical optoelectronic applications.

μ-Hexa­thio­metadiphosphato-bis­[(1,4,7,10,13,16-hexa­oxa­cyclo­octa­decane-κ6 O)rubidium] aceto­nitrile disolvate

PubMed Central

Gjikaj, Mimoza; Pook, Niels-Patrick; Qarri, Flora

2013-01-01

The asymmetric unit of the title compound, [Rb2(P2S6)(C12H24O6)2]·2CH3CN, contains one half of an [Rb(18-crown-6)2]2[P2S6] unit and one aceto­nitrile solvent mol­ecule. The [Rb(18-crown-6)]2[P2S6] unit is completed by inversion symmetry. Its Rb+ ion is situated near the centre of the macrocyclic cavity, but is displaced by 0.8972 (1) Å from the O atoms of the crown in the direction of the [P2S6]2− moiety. The overall coordination number of the cation is eight, defined by the six crown ether O atoms and by two terminal S atoms of the [P2S6]2− anion. The hexa­thio­metadiphosphate anion is built up from two tetra­hedral PS4 units joined together by a common edge. The crystal structure is characterized by alternating layers of [Rb(18-crown-6)]2[P2S6] and aceto­nitrile solvent mol­ecules stacked along [010]. PMID:24860286

Eu(III) complexes as Anion-responsive Luminescent Sensors and PARACEST Agents

PubMed Central

Hammell, Jacob; Buttarazzi, Leandro; Huang, Ching-Hui; Morrow, Janet R.

2011-01-01

The Eu(III) complex of (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) is studied as a sensor for biologically relevant anions. Anion interactions produce changes in the luminescence emission spectrum of the Eu(III) complex, in the 1H NMR spectrum, and correspondingly, in the PARACEST spectrum of the complex (PARACEST = paramagnetic chemical exchange saturation transfer). Direct excitation spectroscopy and luminescence lifetime studies of Eu(S-THP) give information about the speciation and nature of anion interactions including carbonate, acetate, lactate, citrate, phosphate and methylphosphate at pH 7.2. Data is consistent with the formation of both innersphere and outersphere complexes of Eu(S-THP) with acetate, lactate and carbonate. These anions have weak dissociation constants that range from 19–38 mM. Citrate binding to Eu(S-THP) is predominantly innersphere with a dissociation constant of 17 μM. Luminescence emission peak changes upon addition of anion to Eu(S-THP) show that there are two distinct binding events for phosphate and methylphosphate with dissociation constants of 0.3 mM and 3.0 mM for phosphate and 0.6 mM and 9.8 mM for methyl phosphate. Eu(THPC) contains an appended carbostyril derivative as an antenna to sensitize Eu(III) luminescence. Eu(THPC) binds phosphate and citrate with dissociation constants that are 10-fold less than that of the Eu(S-THP) parent, suggesting that functionalization through a pendent group disrupts the anion binding site. Eu(S-THP) functions as an anion responsive PARACEST agent through exchange of the alcohol protons with bulk water. The alcohol proton resonances of Eu(S-THP) shift downfield in the presence of acetate, lactate, citrate and methylphosphate, giving rise to distinct PARACEST peaks. In contrast, phosphate binds to Eu(S-THP) to suppress the PARACEST alcohol OH peak and carbonate does not markedly change the alcohol peak at 5 mM Eu(S-THP), 15 mM carbonate at pH 6.5 or 7.2. This work shows that the Eu(S-THP) complex has unique selectivity toward binding of biologically relevant anions and that anion binding results in changes in both the luminescence and PARACEST spectra of the complex. PMID:21548563

Eu(III) complexes as anion-responsive luminescent sensors and paramagnetic chemical exchange saturation transfer agents.

PubMed

Hammell, Jacob; Buttarazzi, Leandro; Huang, Ching-Hui; Morrow, Janet R

2011-06-06

The Eu(III) complex of (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) is studied as a sensor for biologically relevant anions. Anion interactions produce changes in the luminescence emission spectrum of the Eu(III) complex, in the (1)H NMR spectrum, and correspondingly, in the PARACEST spectrum of the complex (PARACEST = paramagnetic chemical exchange saturation transfer). Direct excitation spectroscopy and luminescence lifetime studies of Eu(S-THP) give information about the speciation and nature of anion interactions including carbonate, acetate, lactate, citrate, phosphate, and methylphosphate at pH 7.2. Data is consistent with the formation of both innersphere and outersphere complexes of Eu(S-THP) with acetate, lactate, and carbonate. These anions have weak dissociation constants that range from 19 to 38 mM. Citrate binding to Eu(S-THP) is predominantly innersphere with a dissociation constant of 17 μM. Luminescence emission peak changes upon addition of anion to Eu(S-THP) show that there are two distinct binding events for phosphate and methylphosphate with dissociation constants of 0.3 mM and 3.0 mM for phosphate and 0.6 mM and 9.8 mM for methyl phosphate. Eu(THPC) contains an appended carbostyril derivative as an antenna to sensitize Eu(III) luminescence. Eu(THPC) binds phosphate and citrate with dissociation constants that are 10-fold less than that of the Eu(S-THP) parent, suggesting that functionalization through a pendent group disrupts the anion binding site. Eu(S-THP) functions as an anion responsive PARACEST agent through exchange of the alcohol protons with bulk water. The alcohol proton resonances of Eu(S-THP) shift downfield in the presence of acetate, lactate, citrate, and methylphosphate, giving rise to distinct PARACEST peaks. In contrast, phosphate binds to Eu(S-THP) to suppress the PARACEST alcohol OH peak and carbonate does not markedly change the alcohol peak at 5 mM Eu(S-THP), 15 mM carbonate at pH 6.5 or 7.2. This work shows that the Eu(S-THP) complex has unique selectivity toward binding of biologically relevant anions and that anion binding results in changes in both the luminescence and the PARACEST spectra of the complex. © 2011 American Chemical Society

Reactions of molybdenum-sulphur compounds with cyanide: chemical evolution and deactivation of molybdoenzymes.

PubMed

Mitchell, P C; Pygall, C F

1979-08-01

Reactions of molybdenum-sulphur compounds with cyanide are reported which may be relevant to (1) the chemical evolution of molybdoenzymes and (2) deactivation of molybdoenzymes by cyanide. (1) With aqueous cyanide MoS2 gave thio-bridged complex anions [(Mo(CN)6)2(mu-S)]6- and [(Mo(CN)4(mu-S))2]6-. Under prebiotic conditions such complexes could have been formed similarly from molybdenite and may have been precursors of molybdoenzymes. (2) Only those compounds which contained terminal sulphur bound to molybdenum (i.e., Mo = S groups), viz. oxothiomolybdates and the complex [(Mo(mu-S)(S)(Et2NCS2))2], reacted with cyanide; thiocyanate was formed and the molybdenum underwent two-electron reduction. That the cyanolysable sulphur of xanthine oxidase reacts in the same way with cyanide suggests the presence of a Mo = S group which could be a structural feature of the enzyme or could have been formed by initial cyanolysis of a bound persulphide or cysteine residue.

Ab initio theoretical study of dipole-bound anions of molecular complexes: (HF)3- and (HF)4- anions

NASA Astrophysics Data System (ADS)

Ramaekers, Riet; Smith, Dayle M. A.; Smets, Johan; Adamowicz, Ludwik

1997-12-01

Ab initio calculations have been performed to determine structures and vertical electron detachment energy (VDE) of the hydrogen fluoride trimer and tetramer anions, (HF)3- and (HF)4-. In these systems the excess electron is bound by the dipole field of the complex. It was determined that, unlike the neutral complexes which prefer the cyclic structures, the equilibrium geometries of the anions have "zig-zag" shapes. For both complexes the predicted VDEs are positive [210 meV and 363 meV for (HF)3- and (HF)4-, respectively], indicating that the anions are stable systems with respect to the vertical electron detachment. These results were obtained at the coupled-cluster level of theory with single, double and triple excitations [CCSD(T) method; the triple-excitation contribution in this method is calculated approximately using the perturbation approach] with the anion geometries obtained using the second-order Møller-Plesset perturbation theory (MP2) method. The same approach was also used to determine the adiabatic electron affinities (AEA) of (HF)3 and (HF)4. In addition to the electronic contribution, we also calculated the contributions (using the harmonic approximation) resulting from different zero-point vibration energies of the neutral and anionic clusters. The calculations predicted that while the AEA of (HF)3 is positive (44 meV), the AEA for (HF)4 is marginally negative (-16 meV). This suggests that the (HF)3- anion should be a stable system, while the (HF)4- is probably metastable.

Dimension-controlled assemblies of anion-responsive π-electronic systems bearing aryl substituents with fan-shaped geometries.

PubMed

Lakshmi, Vellanki; Haketa, Yohei; Yamakado, Ryohei; Yasuda, Nobuhiro; Maeda, Hiromitsu

2017-03-30

Pyrrole-4-aryl-substituted dipyrrolyldiketone BF 2 complexes as anion-responsive π-electronic molecules were synthesized via a 3,5-dimethylpyrrole precursor. Mesophases were observed in derivatives that possessed long alkyl chains on the pyrrole-4-aryl groups along with their anion complexes as ion-pairing assemblies in combination with appropriate cations.

Methods for preparation of cyclopentadienyliron (II) arenes

DOEpatents

Keipert, Steven J.

1991-01-01

Two improved methods for preparation of compounds with the structure shown in equation X [(Cp)--Fe--(Ar)].sup.+.sub.b X.sup.b- (X) where Cp is an eta.sup.5 complexed, substituted or unsubstituted, cyclopentadienyl or indenyl anion, Ar is an eta.sup.6 complexed substituted or unsubstituted, pi-arene ligand anad X is a b-valent anion where b is an integer between 1 and 3. The two methods, which differ in the source of the cyclopentadienyl anion - Lewis acid complex, utilize a Lewis acid assisted ligand transfer reaction. The cyclopentadienyl anion ligand, assisted by a Lewis acid is transferred to ferrous ion in the presence of an arene. In the first method, the cyclopentadienyl anion is derived from ferrocene and ferrous chloride. In this reaction, the cyclopentadienyliron (II) arene product is derived partially from ferrocene and partially from the ferrous salt. In the second method, the cyclopentadienyl anion - Lewis acid complex is formed by direct reaction of the Lewis acid with an inorganic cyclopentadienide salt. The cyclopentadienyliron (II) arene product of this reaction is derived entirely from the ferrous salt. Cyclopentadienyliron (II) arene cations are of great interest due to their utility as photoactivatable catalysts for a variety of polymerization reactions.

Investigations on Mg-borate kinetics and mechanisms during evaporation, dilution and crystallization by Raman spectroscopy

NASA Astrophysics Data System (ADS)

Peng, Jiaoyu; Chen, Jing; Dong, Yaping; Li, Wu

2018-06-01

Raman spectra of boron-concentrated, diluted, and corresponding mother solutions of brine were recorded at 298.15 K. The main polyborate anions present and their interactions in brine during evaporation and dilution were proposed according to the Raman spectra. The polyborate anions B(OH)3, B3O3(OH)4-, B5O6(OH)4-, and B6O7(OH)62- were found to be the main forms in boron-concentrated brine with B3O3(OH)4- ion being the principal form. Diluting brines with water accelerated depolymerization of B5O6(OH)4- and B6O7(OH)62- anions into B(OH)3 and B3O3(OH)4- ions and generated OH- ions, causing the pH of the solutions to increase from 4.2 to almost 8.0. Mg-borates precipitated from all diluted solutions could be classified as either hexaborates or triborates. A mechanism of solid phase transformation was also proposed and discussed based on Raman spectra analysis and solid species and solution pH data.

AOM reconciling of crystal field parameters for UCl 3, UBr 3, UI 3 series

NASA Astrophysics Data System (ADS)

Gajek, Z.; Mulak, J.

1990-07-01

Available inelastic neutron scattering interpretations of crystal field effect in the uranium trihalides have been verified in terms of Angular Overlap Model. For UCl 3 a good reconciling of both INS and optical interpretations of crystal field effect has been obtained. On the contrary, the parameterizations for UBr 3 and UI 3 were found to be highly artificial and suggestion is given to experimentalists to reinterpret their INS spectra.

Synthesis, characterization, and reactivity of arylpalladium cyanoalkyl complexes: selection of catalysts for the alpha-arylation of nitriles.

PubMed

Culkin, Darcy A; Hartwig, John F

2002-08-14

A new coupling process, the palladium-catalyzed alpha-arylation of nitriles, was developed by exploring the structure and reactivity of arylpalladium cyanoalkyl complexes. Complexes of 1,2-bis(diphenylphosphino)benzene (DPPBz), 1,1'-bis(di-i-propylphosphino)ferrocene (D(i)()PrPF), racemic-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), and diphenylethylphosphine (PPh(2)Et) were prepared. Coordination to palladium through the alpha-carbon was observed for DPPBz-ligated complexes and for complexes of primary and benzylic nitrile anions. However, the anion of isobutyronitrile was coordinated to palladium through the cyano-nitrogen when the complex was ligated by D(i)()PrPF. The isobutyronitrile anion displaced a phosphine ligand to form a C,N-bridged dimer when generated from PPh(2)Et-ligated palladium. These results suggest that the nitrile anion preferentially coordinates to palladium through the carbon atom in the absence of steric effects. Thermolysis of the arylpalladium cyanoalkyl complexes led to reductive elimination that formed alpha-aryl nitriles. The high yields and short reaction times observed for BINAP-ligated complexes suggested that BINAP-ligated palladium catalysts might be appropriate for the arylation of nitriles. Initial results on a palladium-catalyzed process for the direct coupling of aryl bromides and primary, benzylic, and secondary nitrile anions to form alpha-aryl nitriles in good yields are reported.

Coping behavior and loneliness among obese patients.

PubMed

Hörchner, Rogier; Tuinebreijer, Wim E; Kelder, Hans; van Urk, Elly

2002-12-01

Morbid obesity can be accompanied by physical and social problems that may influence interpersonal relationships and the recruitment of social support. The problems can be tackled with a variety of coping strategies. 104 patients with a body mass index (BMI) 32-64 kg/m2 and mean age 36 yr were presented with the Utrecht Coping List (UCL) and the Loneliness Scale. Of these patients, 94 were female, and this cohort was analyzed more extensively. Patients exhibited elevated values on the Loneliness Scale and in the UCL sub-scales palliative response, avoidance / wait-and-see, passive / depressive response pattern and expression of emotions / anger. The active approach UCL sub-scale scored lower than in a control group. Obese female patients displayed avoidance, wait-and-see and passive response pattern as coping behavior, experiencing their intimate relationships as relatively unreliable and not very intimate. More research is needed to determine the effect of coping behavior on therapeutic effect.

Bismuth generator method

DOEpatents

Bray, Lane Allan; DesChane, Jaquetta R.

1998-01-01

A method for separating .sup.213 Bi from a solution of radionuclides wherein the solution contains a concentration of the chloride ions and hydrogen ions adjusted to allow the formation of a chloride complex. The solution is then brought into contact with an anion exchange resin, whereupon .sup.213 Bi is absorbed from the solution and adhered onto the anion exchange resin in the chloride complex. Other non-absorbing radionuclides such as .sup.225 Ra, .sup.225 Ac, and .sup.221 Fr, along with HCl are removed from the anion exchange resin with a scrub solution. The .sup.213 Bi is removed from the anion exchange resin by washing the anion exchange resin with a stripping solution free of chloride ions and with a reduced hydrogen ion concentration which breaks the chloride anionic complex, releasing the .sup.213 Bi as a cation. In a preferred embodiment of the present invention, the anion exchange resin is provided as a thin membrane, allowing for extremely rapid adherence and stripping of the .sup.213 Bi. A preferred stripping solution for purification of .sup.213 Bi for use in medical applications includes sodium acetate, pH 5.5. A protein conjugated with bifunctional chelating agents in vivo with the NaOAc, to receive the .sup.213 Bi as it is being released from the anion exchange resin.

Bismuth generator method

DOEpatents

Bray, L.A.; DesChane, J.R.

1998-05-05

A method is described for separating {sup 213}Bi from a solution of radionuclides wherein the solution contains a concentration of the chloride ions and hydrogen ions adjusted to allow the formation of a chloride complex. The solution is then brought into contact with an anion exchange resin, whereupon {sup 213}Bi is absorbed from the solution and adhered onto the anion exchange resin in the chloride complex. Other non-absorbing radionuclides such as {sup 225}Ra, {sup 225}Ac, and {sup 221}Fr, along with HCl are removed from the anion exchange resin with a scrub solution. The {sup 213}Bi is removed from the anion exchange resin by washing the anion exchange resin with a stripping solution free of chloride ions and with a reduced hydrogen ion concentration which breaks the chloride anionic complex, releasing the {sup 213}Bi as a cation. In a preferred embodiment of the present invention, the anion exchange resin is provided as a thin membrane, allowing for extremely rapid adherence and stripping of the {sup 213}Bi. A preferred stripping solution for purification of {sup 213}Bi for use in medical applications includes sodium acetate, pH 5.5. A protein conjugated with bifunctional chelating agents in vivo with the NaOAc receives the {sup 213}Bi as it is being released from the anion exchange resin. 10 figs.

Transformation of [M + 2H](2+) Peptide Cations to [M - H](+), [M + H + O](+), and M(+•) Cations via Ion/Ion Reactions: Reagent Anions Derived from Persulfate.

PubMed

Pilo, Alice L; Bu, Jiexun; McLuckey, Scott A

2015-07-01

The gas-phase oxidation of doubly protonated peptides is demonstrated here using ion/ion reactions with a suite of reagents derived from persulfate. Intact persulfate anion (HS2O8(-)), peroxymonosulfate anion (HSO5(-)), and sulfate radical anion (SO4(-•)) are all either observed directly upon negative nanoelectrospray ionization (nESI) or easily obtained via beam-type collisional activation of persulfate into the mass spectrometer. Ion/ion reactions between each of these reagents and doubly protonated peptides result in the formation of a long-lived complex. Collisional activation of the complex containing a peroxymonosulfate anion results in oxygen transfer from the reagent to the peptide to generate the [M + H + O](+) species. Activation of the complex containing intact persulfate anion either results in oxygen transfer to generate the [M + H + O](+) species or abstraction of two hydrogen atoms and a proton to generate the [M - H](+) species. Activation of the complex containing sulfate radical anion results in abstraction of one hydrogen atom and a proton to form the peptide radical cation, [M](+•). This suite of reagents allows for the facile transformation of the multiply protonated peptides obtained via nESI into a variety of oxidized species capable of providing complementary information about the sequence and structure of the peptide.

Anionic pH-Sensitive Lipoplexes.

PubMed

Mignet, Nathalie; Scherman, Daniel

2017-01-01

To provide long circulating nanoparticles able to carry a gene to tumors, we have designed anionic pegylated lipoplexes which are pH sensitive. Anionic pegylated lipoplexes have been prepared from the combined formulation of cationic lipoplexes and pegylated anionic liposomes. The neutralization of the particle surface charge as a function of the pH was monitored by light scattering in order to determine the ratio between anionic and cationic lipids that would give pH sensitive complexes. This ratio has been optimized to form particles sensitive to pH change in the range 5.5-6.5. Compaction of DNA into these newly formed anionic complexes is checked by DNA accessibility to picogreen. The transfection efficiency and pH sensitive property of these formulations has been shown in vitro using bafilomycin, a vacuolar H + -ATPase inhibitor.

Synthesis, crystallographic and spectral studies of homochiral cobalt(II) and nickel(II) complexes of a new terpyridylaminoacid ligand

NASA Astrophysics Data System (ADS)

Wang, Xing; Gao, Chang-Qing; Gao, Zhi-Yang; Wu, Ben-Lai; Niu, Yun-Yin

2018-04-01

Based on a chiral terpyridylaminoacid ligand, a series of homochiral Co(II) and Ni(II) complexes, namely, [Co(H2L)(HL)]·Cl·(PF6)2·2H2O (1), [Ni(H2L)(HL)]·Cl·(PF6)2 (2), [Co2(L)2(CH3OH)(H2O)]·(PF6)2·CH3OH (3), [Ni2(L)2(CH3OH)2]·(PF6)2·2CH3OH (4), [Co2(L)2(N3)2]·3H2O (5), and [Ni2(L)2(SCN)2]·4H2O (6) have been successfully synthesized and characterized by elemental analysis, TGA, spectroscopic methods (IR, CD and electronic absorption spectra) and single-crystal X-ray diffraction structural analysis (HL = (S)-2-((4-([2,2':6‧,2″-terpyridin]-4‧-yl)benzyl)amino)-4-methylpentanoic acid). In the acidic reaction conditions, one protonated (H2L)+ and one zwitterionic HL only used their terpyridyl groups to chelate one metal ion Co(II) or Ni(II), forming chiral mononuclear cationic complexes 1 or 2. But in the basic and hydro(solvo)thermal reaction conditions, deprotonated ligands (L)‒ acting as bridges used their terpyridyl and amino acid groups to link with two Co(II) or Ni(II) ions, fabricating chiral dinuclear metallocyclic complexes 3-6. Those chiral mononuclear and dinuclear complexes whose chirality originates in the homochiral ligand HL further self-assemble into higher-dimensional homochiral supramolecular frameworks through intermolecular hydrogen-bonding and π···π interactions. Notably, the coordination mode, hydrogen-bonding site, and existence form of HL ligand can be controlled by the protonation of its amino group, and the architectural diversity of those supramolecular frameworks is adjusted by pH and counter anions. Very interestingly, the 3D porous supramolecular frameworks built up from the huge chiral mononuclear cationic complexes 1 and 2 have novel helical layers only formed through every right-handed helical chain intertwining with two adjacent same helical chains, and the 2D supramolecular helicate 5 consists of two types of left-handed helical chains.

Inorganic anion-dependent assembly of zero-, one-, two- and three-dimensional Cu(II)/Ag(I) complexes under the guidance of the HSAB theory: Synthesis, structure, and magnetic property

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

Liu, Yaru; Xing, Zhiyan; Zhang, Xiao

To systematically explore the influence of inorganic anions on building coordination complexes, five novel complexes based on 1-(benzotriazole-1-methyl)−2-propylimidazole (bpmi), [Cu(bpmi){sub 2}(Ac){sub 2}]·H{sub 2}O (1), [Cu(bpmi){sub 2}(H{sub 2}O){sub 2}]·2NO{sub 3}·2H{sub 2}O (2), [Cu(bpmi)(N{sub 3}){sub 2}] (3), [Ag(bpmi)(NO{sub 3})] (4) and [Cu{sub 3}(bpmi){sub 2}(SCN){sub 4}(DMF)] (5) (Ac{sup −}=CH{sub 3}COO{sup −}, DMF=N,N-Dimethylformamide) are synthesized through rationally introducing Cu(II) salts and Ag(I) salt with different inorganic anions. X-ray single-crystal analyses reveal that these complexes show interesting structural features from mononuclear (1), one-dimensional (2 and 3), two-dimensional (4) to three-dimensional (5) under the influence of inorganic anions with different basicities. The structural variation can bemore » explained by the hard-soft-acid-base (HSAB) theory. Magnetic susceptibility measurement indicates that complex 3 exhibits an antiferromagnetic coupling between adjacent Cu(II) ions. - Graphical abstract: Five new Cu(II)/Ag(I) complexes show interesting structural features from mononuclear, one-dimension, two-dimension to three-dimension under the influence of inorganic anions. The structural variation can be explained by the HSAB theory. - Highlights: • Five inorganic anion-dependent complexes are synthesized. • Structural variation can be explained by the hard-soft-acid-base (HSAB) theory. • The magnetic property of complex has been studied.« less

Treatment of partial ulnar collateral ligament tears in the elbow with platelet-rich plasma.

PubMed

Podesta, Luga; Crow, Scott A; Volkmer, Dustin; Bert, Timothy; Yocum, Lewis A

2013-07-01

Studies have demonstrated the potential of platelet-rich plasma (PRP) to heal damaged tissue. To date, there are no published reports of clinical outcomes of partial ulnar collateral ligament (UCL) tears of the elbow treated with PRP. Platelet-rich plasma will promote the healing of partial UCL tears and allow a return to play. Case series; Level of evidence, 4. Thirty-four athletes with a partial-thickness UCL tear confirmed on magnetic resonance imaging were prospectively followed. All patients had failed at least 2 months of nonoperative treatment and an attempt to return to play. Baseline questionnaires, including the Kerlan-Jobe Orthopaedic Clinic Shoulder and Elbow (KJOC) and Disabilities of the Arm, Shoulder and Hand (DASH) measures, were completed by each patient before injection. Baseline ultrasound measurement of the humeral-ulnar joint space was assessed with 10 lb of valgus stress on the elbow. Each patient received a single type 1A PRP injection at the UCL under ultrasound guidance. The same treating physician at a single institution performed all injections with the same PRP preparation used. Patients completed a course of guided physical therapy and were allowed to return to play based on their symptoms and physical examination findings. Outcome scores, including KJOC and DASH scores, were collected after return to play and were compared with baseline scores. Ultrasound measurements were collected at final follow-up and compared with preinjection values. At an average follow-up of 70 weeks (range, 11-117 weeks), 30 of 34 athletes (88%) had returned to the same level of play without any complaints. The average time to return to play was 12 weeks (range, 10-15 weeks). The average KJOC score improved from 46 to 93 (P < .0001). The average DASH score improved from 21 to 1 (P < .0001). The sports module of the DASH questionnaire improved from 69 to 3 (P < .0001). Medial elbow joint space opening with valgus stress decreased from 28 to 20 mm at final follow-up (P < .0001). The difference in medial elbow joint space opening (stressed vs nonstressed) decreased from 7 to 2.5 mm at final follow-up (P < .0001). One player had persistent UCL insufficiency and underwent ligament reconstruction at 31 weeks after injection. The results of this study indicate that PRP is an effective option to successfully treat partial UCL tears of the elbow in athletes.

CHRONIC UCL INJURY: A MULTIMODAL APPROACH TO CORRECTING ALTERED MECHANICS AND IMPROVING HEALING IN A COLLEGE ATHLETE— A CASE REPORT

PubMed Central

Patrick, Rachel; McGinty, Josh; Lucado, Ann; Collier, Beth

2016-01-01

ABSTRACT Background Ulnar collateral ligament (UCL) tears and associated Tommy Johns surgical intervention from excessive and poor quality pitching has increased immensely—with more college and professional pitchers undergoing the surgery in 2014 alone than in the 1990s as a whole.1 Faulty mechanics developed at young ages are often well-engrained by the late adolescent years and the minimal healing ability of the largely avascular UCL often leads to delayed safe return to sport.2 Purpose The purpose of this case study was to describe an innovative, multimodal approach to conservative management of a chronic UCL injury in a college-aged baseball pitcher. This innovative approach utilizes both contractile and non-contractile dry needling to enhance soft tissue healing combined with standard conservative treatment to decrease pain and improve sport performance as measured by the Disabilities of Arm, Shoulder and Hand (DASH), Numeric Pain Report Scale (NPRS), and return to sport. Study Design Retrospective Case Report Case Description A collegiate athlete presented to an outpatient orthopedic physical therapy clinic for treatment of UCL sprain approximately six weeks post-injury and platelet-rich plasma injection. Diagnostic testing revealed chronic ligamentous microtrauma. Impairments at evaluation included proximal stabilizing strength deficits, myofascial trigger points throughout the dominant upper extremity, improper pitching form, and inability to pitch in game conditions due to severe pain. Interventions included addressing strength deficits throughout the body, dry needling, and sport-specific biomechanical training with pitching form analysis and correction. Outcomes Conventional DASH and Sport-Specific scale on the DASH and the numeric pain rating scale improved beyond both the minimally clinically important difference and minimal detectable change over the 12 week treatment3,4 At 24-week follow up, conventional DASH scores decreased from 34.20% disability to 3.33% disability while sport-specific DASH scores decreased from 100% disability to 31.25% disability. Although initially unable to compete due to high pain levels, the subject is currently completing his pitching role full-time with 1/10 max pain. Discussion The approach used in this case study provides an innovative approach to conservative UCL partial tear treatment. Dry needling of both contractile and non-contractile tissue in combination with retraining of faulty mechanics may encourage chronically injured ligamentous tissue healing and encourage safe return to sport. Level of evidence Level 4 PMID:27525185

Incidence of Elbow Ulnar Collateral Ligament Surgery in Collegiate Baseball Players.

PubMed

Rothermich, Marcus A; Conte, Stan A; Aune, Kyle T; Fleisig, Glenn S; Cain, E Lyle; Dugas, Jeffrey R

2018-04-01

Recent reports have highlighted the progressive increase in the incidence of ulnar collateral ligament (UCL) injuries to the elbow in baseball players of all levels. However, knowledge of the incidence and other epidemiological factors regarding UCL injuries, specifically in college baseball players, is currently lacking. To evaluate, over a period of 1 year, the incidence of UCL injuries requiring surgery in National Collegiate Athletic Association (NCAA) Division I baseball programs. Descriptive epidemiology study. A total of 155 Division I collegiate baseball programs agreed to participate in the study. Demographics (position, year, background [location of high school]) for all players on these rosters were obtained from public websites. At the conclusion of the 2017 collegiate baseball season, the athletic trainer for each program entered anonymous, detailed information on injured players through an electronic survey into a secured database. All 155 teams enrolled in the study completed the electronic survey. Of the 5295 collegiate baseball players on these rosters, 134 underwent surgery for an injured UCL (2.5% of all eligible athletes), resulting in a team surgery rate of 0.86 per program for 1 year. These 134 players came from 88 teams, thus 56.8% of the study teams underwent at least 1 surgery during the year. The surgery rate was 2.5 per 100 player-seasons for all players and was significantly higher among pitchers (4.4/100 player-seasons) than nonpitchers (0.7/100 player-seasons). The surgery rate was also significantly higher in underclassmen (3.1/100 player-seasons among freshmen and sophomores) than upperclassmen (1.9/100 player-seasons among juniors and seniors) (incidence rate ratio, 1.7; 95% CI, 1.1-2.4). Players from traditionally warm-weather states did not undergo UCL surgery at a significantly different rate from players from traditionally cold-weather states (2.7/100 player-seasons vs 2.1/100 player-seasons, respectively). Nearly half of surgeries (48.5%) were performed during the baseball season. The incidence of UCL surgeries in NCAA Division I collegiate baseball players represents substantial morbidity to this young athletic population. Risk factors for injuries requiring surgery include being a pitcher and an underclassman. Awareness of these factors should be considered in injury prevention programs. Furthermore, this initial study can serve as a foundation for tracking these surgical injuries in future years and then identifying trends over time.

Syntheses, crystal structures and properties of novel copper(II) complexes obtained by reactions of copper(II) sulfate pentahydrate with tripodal ligands.

PubMed

Zhao, Wei; Fan, Jian; Song, You; Kawaguchi, Hiroyuki; Okamura, Taka-aki; Sun, Wei-Yin; Ueyama, Norikazu

2005-04-21

Three novel metal-organic frameworks (MOFs), [Cu(1)SO4].H2O (4), [Cu2(2)2(SO4)2].4H2O (5) and [Cu(3)(H2O)]SO4.5.5H2O (6), were obtained by hydrothermal reactions of CuSO4.5H2O with the corresponding ligands, which have different flexibility. The structures of the synthesized complexes were determined by single-crystal X-ray diffraction analyses. Complex 4 has a 2D network structure with two types of metallacycles. Complex 5 also has a 2D network structure in which each independent 2D sheet contains two sub-layers bridged by oxygen atoms of the sulfate anions. Complex 6 has a 2D puckered structure in which the sulfate anions serve as counter anions, which are different from those in complexes 4 (terminators) and 5 (bridges). The different structures of complexes 4, 5 and 6 indicate that the nature of organic ligands affected the structures of the assemblies greatly. The magnetic behavior of complex 5 and anion-exchange properties of complex 6 were investigated.

Templated synthesis of copper(II) azacyclam complexes using urea as a locking fragment and their metal-enhanced binding tendencies towards anions.

PubMed

Boiocchi, Massimo; Fabbrizzi, Luigi; Garolfi, Mauro; Licchelli, Maurizio; Mosca, Lorenzo; Zanini, Cristina

2009-10-26

Copper(II) azacyclam complexes 3(2+) and 4(2+) were obtained through a metal-templated procedure involving the pertinent open-chain tetramine, formaldehyde and a phenylurea derivative as a locking fragment. Both metal complexes can establish interactions with anions through the metal centre and the amide NH group. Equilibrium studies in DMSO by a spectrophotometric titration technique were carried out to assess the affinity of 3(2+) and 4(2+) towards anions. While the NH group of an amide model compound and the metal centre of the plain Cu(II)(azacyclam)(2+) complex do not interact at all with anions, 3(2+) and 4(2+) establish strong interactions with oxo anions, profiting from a pronounced cooperative effect. In particular, 1) they form stable 1:1 and 1:2 complexes with H(2)PO(4) (-) ions in a stepwise mode with both hydrogen-bonding and metal-ligand interactions, and 2) in the presence of CH(3)COO(-), they undergo deprotonation of the amido NH group and thus profit from axial coordination of the partially negatively charged carbonyl oxygen atom in a scorpionate binding mode.

A carbohydrate-anion recognition system in aprotic solvents.

PubMed

Ren, Bo; Dong, Hai; Ramström, Olof

2014-05-01

A carbohydrate-anion recognition system in nonpolar solvents is reported, in which complexes form at the B-faces of β-D-pyranosides with H1-, H3-, and H5-cis patterns similar to carbohydrate-π interactions. The complexation effect was evaluated for a range of carbohydrate structures; it resulted in either 1:1 carbohydrate-anion complexes, or 1:2 complex formation depending on the protection pattern of the carbohydrate. The interaction was also evaluated with different anions and solvents. In both cases it resulted in significant binding differences. The results indicate that complexation originates from van der Waals interactions or weak CH⋅⋅⋅A(-) hydrogen bonds between the binding partners and is related to electron-withdrawing groups of the carbohydrates as well as increased hydrogen-bond-accepting capability of the anions. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

Investigation of residual anode material after electrorefining uranium in molten chloride salt

NASA Astrophysics Data System (ADS)

Rose, M. A.; Williamson, M. A.; Willit, J.

2015-12-01

A buildup of material at uranium anodes during uranium electrorefining in molten chloride salts has been observed. Potentiodynamic testing has been conducted using a three electrode cell, with a uranium working electrode in both LiCl/KCl eutectic and LiCl each containing ∼5 mol% UCl3. The anodic current response was observed at 50° intervals between 450 °C and 650 °C in the eutectic salt. These tests revealed a buildup of material at the anode in LiCl/KCl salt, which was sampled at room temperature, and analyzed using ICP-MS, XRD and SEM techniques. Examination of the analytical data, current response curves and published phase diagrams has established that as the uranium anode dissolves, the U3+ ion concentration in the diffusion layer surrounding the electrode rises precipitously to levels, which may at low temperatures exceed the solubility limit for UCl3 or in the case of the eutectic salt for K2UCl5. The reduction in current response observed at low temperature in eutectic salt is eliminated at 650 °C, where K2UCl5 is absent due to its congruent melting and only simple concentration polarization effects are seen. In LiCl similar concentration effects are seen though significantly longer time at applied potential is required to effect a reduction in the current response as compared to the eutectic salt.

Dynamics of dipole- and valence bound anions in iodide-adenine binary complexes: A time-resolved photoelectron imaging and quantum mechanical investigation

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

Stephansen, Anne B.; King, Sarah B.; Li, Wei-Li

2015-09-14

Dipole bound (DB) and valence bound (VB) anions of binary iodide-adenine complexes have been studied using one-color and time-resolved photoelectron imaging at excitation energies near the vertical detachment energy. The experiments are complemented by quantum chemical calculations. One-color spectra show evidence for two adenine tautomers, the canonical, biologically relevant A9 tautomer and the A3 tautomer. In the UV-pump/IR-probe time-resolved experiments, transient adenine anions can be formed by electron transfer from the iodide. These experiments show signals from both DB and VB states of adenine anions formed on femto- and picosecond time scales, respectively. Analysis of the spectra and comparison withmore » calculations suggest that while both the A9 and A3 tautomers contribute to the DB signal, only the DB state of the A3 tautomer undergoes a transition to the VB anion. The VB anion of A9 is higher in energy than both the DB anion and the neutral, and the VB anion is therefore not accessible through the DB state. Experimental evidence of the metastable A9 VB anion is instead observed as a shape resonance in the one-color photoelectron spectra, as a result of UV absorption by A9 and subsequent electron transfer from iodide into the empty π-orbital. In contrast, the iodide-A3 complex constitutes an excellent example of how DB states can act as doorway state for VB anion formation when the VB state is energetically available.« less

Nitrite oxidation in ion chromatography-electrospray ionization-tandem mass spectrometry (IC-ESI-MS/MS).

PubMed

Farhat, Ali; Dooley, Alek N; Ahmad, Farrukh

2011-07-01

Nitrite anions are formed in the human body and in the natural environment as intermediate chemical compounds during the reduction of nitrate, a ubiquitous anthropogenic contaminant introduced into the environment primarily through fertilizer use. Multiple reaction monitoring (MRM) in ion chromatography-electrospray ionization-tandem mass spectrometry (IC-ESI-MS/MS) is a promising new technique for quantifying and confirming the identity of anions in complex aqueous mixtures. In this article, we present the results of a short investigation devised to: (1) compare the signal generated by the MRM transitions for nitrite with those for nitrate, (2) isolate the source of the signal from these MRM transitions occurring within the IC-ESI-MS/MS instrument and (3) assess the relationship between the observed MRM signals for nitrite. The MRM transitions used in this study were m/z 62 (NO(3)(-))→m/z 46 (NO(2)(-)) and m/z 46 (NO(2)(-))→m/z 46 (NO(2)(-)). Results of the investigation revealed the association of both MRM transitions with the nitrite chromatographic peak, indicating the occurrence of nitrite oxidation to nitrate at the ESI interface before the first quadrupole. Calibrations for both MRM signals, as well as their sum, were found to be linear. However, the ratio of m/z 62→m/z 46 to m/z 46→m/z 46 (indicating an extent of oxidation) ranged from 35 to 56% over a nitrite concentration range of 10 to 100 ppm, showing no clear trend associated with concentration. Copyright © 2011 John Wiley & Sons, Ltd.

Ion exchange polymers for anion separations

DOEpatents

Jarvinen, Gordon D.; Marsh, S. Fredric; Bartsch, Richard A.

1997-01-01

Anion exchange resins including at least two positively charged sites and a ell-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

Ion exchange polymers for anion separations

DOEpatents

Jarvinen, G.D.; Marsh, S.F.; Bartsch, R.A.

1997-09-23

Anion exchange resins including at least two positively charged sites and a well-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

Bambus[6]uril as a novel macrocyclic receptor for the nitrate anion.

PubMed

Toman, Petr; Makrlík, Emanuel; Vanura, Petr

2013-01-01

By using quantum mechanical DFT calculations, the most probable structure of the bambus[6]uril x NO3(-) anionic complex species was derived. In this complex having C3 symmetry, the nitrate anion NO3(-), included in the macrocyclic cavity, is bound by twelve weak hydrogen bonds between methine hydrogen atoms on the convex face of glycoluril units and the considered NO3(-) ion.

Nuclear reactor cooling system decontamination reagent regeneration. [PWR; BWR

DOEpatents

Anstine, L.D.; James, D.B.; Melaika, E.A.; Peterson, J.P. Jr.

1980-06-06

An improved method for decontaminating the coolant system of water-cooled nuclear power reactors and for regenerating the decontamination solution is described. A small amount of one or more weak-acid organic complexing agents is added to the reactor coolant, and the pH is adjusted to form a decontamination solution which is circulated throughout the coolant system to dissolve metal oxides from the interior surfaces and complex the resulting metal ions and radionuclide ions. The coolant containing the complexed metal ions and radionuclide ions is passed through a strong-base anion exchange resin bed which has been presaturated with a solution containing the complexing agents in the same ratio and having the same pH as the decontamination solution. As the decontamination solution passes through the resin bed, metal-complexed anions are exchanged for the metal-ion-free anions on the bed, while metal-ion-free anions in the solution pass through the bed, thus removing the metal ions and regenerating the decontamination solution.

Nuclear reactor cooling system decontamination reagent regeneration

DOEpatents

Anstine, Larry D.; James, Dean B.; Melaika, Edward A.; Peterson, Jr., John P.

1985-01-01

An improved method for decontaminating the coolant system of water-cooled nuclear power reactors and for regenerating the decontamination solution. A small amount of one or more weak-acid organic complexing agents is added to the reactor coolant, and the pH is adjusted to form a decontamination solution which is circulated throughout the coolant system to dissolve metal oxides from the interior surfaces and complex the resulting metal ions and radionuclide ions. The coolant containing the complexed metal ions and radionuclide ions is passed through a strong-base anion exchange resin bed which has been presaturated with a solution containing the complexing agents in the same ratio and having the same pH as the decontamination solution. As the decontamination solution passes through the resin bed, metal-complexed anions are exchanged for the metal-ion-free anions on the bed, while metal-ion-free anions in the solution pass through the bed, thus removing the metal ions and regenerating the decontamination solution.

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non-Polar Solvents by using Conductometry.

PubMed

Iseda, Kazuya; Kokado, Kenta; Sada, Kazuki

2018-03-01

In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride ( TBACl ) ion-pair salt to the free ions through complexation with meso -octamethylcalix[4]pyrrole ( CP ), which is a well-known receptor for chloride anions. In the presence of CP , the conductivity of TBACl increases in various non-polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non-polar solvents. In other words, CP recognizes chloride as an ion-paired salt as well as a free anion in non-polar solvents. Additionally, the TBA(CP - Cl ) complex exhibited a considerably lower ion-pairing constant ( K ip ) than TBACl in non-polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli-responsive soft materials in organic solvents using coulombic forces.

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non‐Polar Solvents by using Conductometry

PubMed Central

Iseda, Kazuya

2018-01-01

Abstract In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride (TBACl) ion‐pair salt to the free ions through complexation with meso‐octamethylcalix[4]pyrrole (CP), which is a well‐known receptor for chloride anions. In the presence of CP, the conductivity of TBACl increases in various non‐polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non‐polar solvents. In other words, CP recognizes chloride as an ion‐paired salt as well as a free anion in non‐polar solvents. Additionally, the TBA(CP–Cl) complex exhibited a considerably lower ion‐pairing constant (K ip) than TBACl in non‐polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli‐responsive soft materials in organic solvents using coulombic forces. PMID:29610717

Configuration and energy landscape of the benzonitrile anion

NASA Astrophysics Data System (ADS)

Kirnosov, Nikita; Adamowicz, Ludwik

2017-05-01

Quantum chemical calculations are employed to study the configurational isomers of the anion formed by benzene substituted with a cyano group. It is found that an excess electron can form dipole-bound (DB) states with benzonitrile and phenyl-isocyanide isomers. It can also attach to the cyano group, if this group is separated from the benzene ring by some distance, forming a covalent CN- anion. There are four positions at peripherals of the benzene ring where this anion can localize and form stable complexes with the benzene radical. In these complexes CN- is connected to the benzene radical via non-covalent interactions.

Selections from 2017: Discoveries in Titan's Atmosphere

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2017-12-01

Editors note:In these last two weeks of 2017, well be looking at a few selections that we havent yet discussed on AAS Nova from among the most-downloaded paperspublished in AAS journals this year. The usual posting schedule will resume in January.Carbon Chain Anions and the Growth of Complex Organic Molecules in Titans IonospherePublished July2017Main takeaway:Graphic depicting some of the chemical reactions taking place in Titans atmosphere, leading to the generation of organic haze particles. [ESA]In a recently published study led by Ravi Desai (University College London), scientists used data from the Cassini mission to identify negatively charged molecules known as carbon chain anions in the atmosphere of Saturns largest moon, Titan.Why its interesting:Carbon chain anions are the building blocks ofmore complex molecules, and Titans thick nitrogen and methane atmosphere mightmimic the atmosphere of earlyEarth. This first unambiguous detection of carbon chain anions in a planet-like atmosphere might therefore teach us about the conditions and chemical reactions that eventually led to the development of life on Earth. And ifwe can use Titan to learn about how complex molecules grow from these anion chains, we may be able to identify auniversal pathway towards the ingredients for life.What weve learned so far:Cassini measured fewer and fewer lower-mass anions the deeper in Titans ionosphere that it looked and at the same time,an increase in the number of precursors to larger aerosol molecules further down. This tradeoff strongly suggests that the anions are indeed involved in building up the more complex molecules, seeding their eventual growth into the complex organic haze of Titans lower atmosphere.CitationR. T. Desai et al 2017 ApJL 844 L18. doi:10.3847/2041-8213/aa7851

Selective Nitrate Recognition by a Halogen-Bonding Four-Station [3]Rotaxane Molecular Shuttle.

PubMed

Barendt, Timothy A; Docker, Andrew; Marques, Igor; Félix, Vítor; Beer, Paul D

2016-09-05

The synthesis of the first halogen bonding [3]rotaxane host system containing a bis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo-triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the (1) H NMR anion binding results. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

The Thermodynamics of Anion Complexation to Nonpolar Pockets.

PubMed

Sullivan, Matthew R; Yao, Wei; Tang, Du; Ashbaugh, Henry S; Gibb, Bruce C

2018-02-08

The interactions between nonpolar surfaces and polarizable anions lie in a gray area between the hydrophobic and Hofmeister effects. To assess the affinity of these interactions, NMR and ITC were used to probe the thermodynamics of eight anions binding to four different hosts whose pockets each consist primarily of hydrocarbon. Two classes of host were examined: cavitands and cyclodextrins. For all hosts, anion affinity was found to follow the Hofmeister series, with associations ranging from 1.6-5.7 kcal mol -1 . Despite the fact that cavitand hosts 1 and 2 possess intrinsic negative electrostatic fields, it was determined that these more enveloping hosts generally bound anions more strongly. The observation that the four hosts each possess specific anion affinities that cannot be readily explained by their structures, points to the importance of counter cations and the solvation of the "empty" hosts, free guests, and host-guest complexes, in defining the affinity.

Selective Nitrate Recognition by a Halogen‐Bonding Four‐Station [3]Rotaxane Molecular Shuttle

PubMed Central

Barendt, Timothy A.; Docker, Andrew; Marques, Igor; Félix, Vítor

2016-01-01

Abstract The synthesis of the first halogen bonding [3]rotaxane host system containing a bis‐iodo triazolium‐bis‐naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo‐triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion–rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the 1H NMR anion binding results. PMID:27436297

Molecular Dynamics Simulations of Adsorption of Poly(acrylic acid) and Poly(methacrylic acid) on Dodecyltrimethylammonium Chloride Micelle in Water: Effect of Charge Density.

PubMed

Sulatha, Muralidharan S; Natarajan, Upendra

2015-09-24

We have investigated the interaction of dodecyltrimethylammonium chloride (DoTA) micelle with weak polyelectrolytes, poly(acrylic acid) and poly(methacrylic acid). Anionic as well as un-ionized forms of the polyelectrolytes were studied. Polyelectrolyte-surfactant complexes were formed within 5-11 ns of the simulation time and were found to be stable. Association is driven purely by electrostatic interactions for anionic chains whereas dispersion interactions also play a dominant role in the case of un-ionized chains. Surfactant headgroup nitrogen atoms are in close contact with the carboxylic oxygens of the polyelectrolyte chain at a distance of 0.35 nm. In the complexes, the polyelectrolyte chains are adsorbed on to the hydrophilic micellar surface and do not penetrate into the hydrophobic core of the micelle. Polyacrylate chain shows higher affinity for complex formation with DoTA as compared to polymethacrylate chain. Anionic polyelectrolyte chains show higher interaction strength as compared to corresponding un-ionized chains. Anionic chains act as polymeric counterion in the complexes, resulting in the displacement of counterions (Na(+) and Cl(-)) into the bulk solution. Anionic chains show distinct shrinkage upon adsorption onto the micelle. Detailed information about the microscopic structure and binding characteristics of these complexes is in agreement with available experimental literature.

Uranyl coordination in ionic liquids: the competition between ionic liquid anions, uranyl counterions, and Cl- anions investigated by extended X-ray absorption fine structure and UV-visible spectroscopies and molecular dynamics simulations.

PubMed

Gaillard, C; Chaumont, A; Billard, I; Hennig, C; Ouadi, A; Wipff, G

2007-06-11

The first coordination sphere of the uranyl cation in room-temperature ionic liquids (ILs) results from the competition between its initially bound counterions, the IL anions, and other anions (e.g., present as impurities or added to the solution). We present a joined spectroscopic (UV-visible and extended X-ray absorption fine structure)-simulation study of the coordination of uranyl initially introduced either as UO2X2 salts (X-=nitrate NO3-, triflate TfO-, perchlorate ClO4-) or as UO2(SO4) in a series of imidazolium-based ILs (C4mimA, A-=PF6-, Tf2N-, BF4- and C4mim=1-methyl-3-butyl-imidazolium) as well as in the Me3NBuTf2N IL. The solubility and dissociation of the uranyl salts are found to depend on the nature of X- and A-. The addition of Cl- anions promotes the solubilization of the nitrate and triflate salts in the C4mimPF6 and the C4mimBF4 ILs via the formation of chloro complexes, also formed with other salts. The first coordination sphere of uranyl is further investigated by molecular dynamics (MD) simulations on associated versus dissociated forms of UO2X2 salts in C4mimA ILs as a function of A- and X- anions. Furthermore, the comparison of UO2Cl(4)2-, 2 X- complexes with dissociated X- anions, to the UO2X2, 4 Cl- complexes with dissociated chlorides, shows that the former is more stable. The case of fluoro complexes is also considered, as a possible result of fluorinated IL anion's degradation, showing that UO2F42- should be most stable in solution. In all cases, uranyl is found to be solvated as formally anionic UO2XnAmClp2-n-m-p complexes, embedded in a cage of stabilizing IL imidazolium or ammonium cations.

Quality of volatile organic compound data from groundwater and surface water for the National Water-Quality Assessment Program, October 1996–December 2008

USGS Publications Warehouse

Bender, David A.; Zogorski, John S.; Mueller, David K.; Rose, Donna L.; Martin, Jeffrey D.; Brenner, Cassandra K.

2011-01-01

This report describes the quality of volatile organic compound (VOC) data collected from October 1996 to December 2008 from groundwater and surface-water sites for the U.S. Geological Survey's National Water-Quality Assessment (NAWQA) Program. The VOC data described were collected for three NAWQA site types: (1) domestic and public-supply wells, (2) monitoring wells, and (3) surface-water sites. Contamination bias, based on the 90-percent upper confidence limit (UCL) for the 90th percentile of concentrations in field blanks, was determined for VOC samples from the three site types. A way to express this bias is that there is 90-percent confidence that this amount of contamination would be exceeded in no more than 10 percent of all samples (including environmental samples) that were collected, processed, shipped, and analyzed in the same manner as the blank samples. This report also describes how important native water rinsing may be in decreasing carryover contamination, which could be affecting field blanks. The VOCs can be classified into four contamination categories on the basis of the 90-percent upper confidence limit (90-percent UCL) concentration distribution in field blanks. Contamination category 1 includes compounds that were not detected in any field blanks. Contamination category 2 includes VOCs that have a 90-percent UCL concentration distribution in field blanks that is about an order of magnitude lower than the concentration distribution of the environmental samples. Contamination category 3 includes VOCs that have a 90-percent UCL concentration distribution in field blanks that is within an order of magnitude of the distribution in environmental samples. Contamination category 4 includes VOCs that have a 90-percent UCL concentration distribution in field blanks that is at least an order of magnitude larger than the concentration distribution of the environmental samples. Fifty-four of the 87 VOCs analyzed in samples from domestic and public-supply wells were not detected in field blanks (contamination category 1), and 33 VOC were detected in field blanks. Ten of the 33 VOCs had a 90-percent UCL concentration distribution in field blanks that was at least an order of magnitude lower than the concentration distribution in environmental samples (contamination category 2). These 10 VOCs may have had some contamination bias associated with the environmental samples, but the potential contamination bias was negligible in comparison to the environmental data; therefore, the field blanks were assumed to be representative of the sources of contamination bias affecting the environmental samples for these 10 VOCs. Seven VOCs had a 90-percent UCL concentration distribution of the field blanks that was within an order of magnitude of the concentration distribution of the environmental samples (contamination category 3). Sixteen VOCs had a 90-percent UCL concentration distribution in the field blanks that was at least an order of magnitude greater than the concentration distribution of the environmental samples (contamination category 4). Field blanks for these 16 VOCs appear to be nonrepresentative of the sources of contamination bias affecting the environmental samples because of the larger concentration distributions (and sometimes higher frequency of detection) in field blanks than in environmental samples. Forty-three of the 87 VOCs analyzed in samples from monitoring wells were not detected in field blanks (contamination category 1), and 44 VOCs were detected in field blanks. Eight of the 44 VOCs had a 90-percent UCL concentration distribution in field blanks that was at least an order of magnitude lower than concentrations in environmental samples (contamination category 2). These eight VOCs may have had some contamination bias associated with the environmental samples, but the potential contamination bias was negligible in comparison to the environmental data; therefore, the field blanks were assumed to be representative. Seven VOCs had a 90-percent UCL concentration distribution in field blanks that was of the same order of magnitude as the concentration distribution of the environmental samples (contamination category 3). Twenty-nine VOCs had a 90-percent UCL concentration distribution in the field blanks that was an order of magnitude greater than the distribution of the environmental samples (contamination category 4). Field blanks for these 29 VOCs appear to be nonrepresentative of the sources of contamination bias to the environmental samples. Fifty-four of the 87 VOCs analyzed in surface-water samples were not detected in field blanks (category 1), and 33 VOC were detected in field blanks. Sixteen of the 33 VOCs had a 90-percent UCL concentration distribution in field blanks that was at least an order of magnitude lower than the concentration distribution in environmental samples (contamination category 2). These 16 VOCs may have had some contamination bias associated with the environmental samples, but the potential contamination bias was negligible in comparison to the environmental data; therefore, the field blanks were assumed to be representative. Ten VOCs had a 90-percent UCL concentration distribution in field blanks that was similar to the concentration distribution of environmental samples (contamination category 3). Seven VOCs had a 90-percent UCL concentration distribution in the field blanks that was greater than the concentration distribution in environmental samples (contamination category 4). Field-blank samples for these seven VOCs appear to be nonrepresentative of the sources of contamination bias to the environmental samples. The relation between the detection of a compound in field blanks and the detection in subsequent environmental samples appears to be minimal. The median minimum percent effectiveness of native water rinsing is about 79 percent for the 19 VOCs detected in more than 5 percent of field blanks from all three site types. The minimum percent effectiveness of native water rinsing (10 percent) was for toluene in surface-water samples, likely because of the large detection frequency of toluene in surface-water samples (about 79 percent) and in the associated field-blank samples (46.5 percent). The VOCs that were not detected in field blanks (contamination category 1) from the three site types can be considered free of contamination bias, and various interpretations for environmental samples, such as VOC detection frequency at multiple assessment levels and comparisons of concentrations to benchmarks, are not limited for these VOCs. A censoring level for making comparisons at different assessment levels among environmental samples could be applied to concentrations of 9 VOCs in samples from domestic and public-supply wells, 16 VOCs in samples from monitoring wells, and 9 VOCs in surface-water samples to account for potential low-level contamination bias associated with these selected VOCs. Bracketing the potential contamination by comparing the detection and concentration statistics with no censoring applied to the potential for contamination bias on the basis of the 90-percent UCL for the 90th-percentile concentrations in field blanks may be useful when comparisons to benchmarks are done in a study. The VOCs that were not detected in field blanks (contamination category 1) from the three site types can be considered free of contamination bias, and various interpretations for environmental samples, such as VOC detection frequency at multiple assessment levels and comparisons of concentrations to benchmarks, are not limited for these VOCs. A censoring level for making comparisons at different assessment levels among environmental samples could be applied to concentrations of 9 VOCs in samples from domestic and public-supply wells, 16 VOCs in samples from monitoring wells, and 9 VOCs in surface-water samples to account for potential low-level contamination bias associated with these selected VOCs. Bracketing the potential contamination by comparing the detection and concentration statistics with no censoring applied to the potential for contamination bias on the basis of the 90-percent UCL for the 90th-percentile concentrations in field blanks may be useful when comparisons to benchmarks are done in a study.

Are Anion/π Interactions Actually a Case of Simple Charge–Dipole Interactions?†

PubMed Central

Wheeler, Steven E.; Houk, K. N.

2011-01-01

Substituent effects in Cl− ••• C6H6−nXn complexes, models for anion/π interactions, have been examined using density functional theory and robust ab initio methods paired with large basis sets. Predicted interaction energies for 83 model Cl− ••• C6H6−nXn complexes span almost 40 kcal mol−1 and show an excellent correlation (r = 0.99) with computed electrostatic potentials. In contrast to prevailing models of anion/π interactions, which rely on substituent-induced changes in the aryl π-system, it is shown that substituent effects in these systems are due mostly to direct interactions between the anion and the substituents. Specifically, interaction energies for Cl− ••• C6H6−nXn complexes are recovered using a model system in which the substituents are isolated from the aromatic ring and π-resonance effects are impossible. Additionally, accurate potential energy curves for Cl− interacting with prototypical anion-binding arenes can be qualitatively reproduced by adding a classical charge–dipole interaction to the Cl− ••• C6H6 interaction potential. In substituted benzenes, binding of anions arises primarily from interactions of the anion with the local dipoles induced by the substituents, not changes in the interaction with the aromatic ring itself. When designing anion-binding motifs, phenyl rings should be viewed as a scaffold upon which appropriate substituents can be placed, because there are no attractive interactions between anions and the aryl π-system of substituted benzenes. PMID:20433187

Ulnar Collateral Ligament Reconstruction

PubMed Central

Erickson, Brandon J.; Harris, Joshua D.; Chalmers, Peter N.; Bach, Bernard R.; Verma, Nikhil N.; Bush-Joseph, Charles A.; Romeo, Anthony A.

2015-01-01

Context: Ulnar collateral ligament (UCL) injuries lead to pain and loss of performance in the thrower’s elbow. Ulnar collateral ligament reconstruction (UCLR) is a reliable treatment option for the symptomatic, deficient UCL. Injury to the UCL usually occurs because of chronic accumulation of microtrauma, although acute ruptures occur and an acute-on-chronic presentation is also common. Evidence Acquisition: Computerized databases, references from pertinent articles, and research institutions were searched for all studies using the search terms ulnar collateral ligament from 1970 until 2015. Study Design: Clinical review. Level of Evidence: Level 5. Results: All studies reporting outcomes for UCLR are level 4. Most modern fixation methodologies appear to be biomechanically and clinically equivalent. Viable graft choices include ipsilateral palmaris longus tendon autograft, gracilis or semitendinosus autograft, and allograft. Clinical studies report excellent outcomes of UCLR for both recreational and elite level athletes with regard to return to sport and postoperative performance. Complications, although rare, include graft rerupture or attenuation, ulnar nerve symptoms, stiffness, pain, and/or weakness leading to decreased performance. Conclusion: Injuries to the UCL have become commonplace among pitchers. Nonoperative treatment should be attempted, but the limited studies have not shown promising results. Operative treatment can be performed with several techniques, with retrospective studies showing promising results. Complications include ulnar neuropathy as well as failure to return to sport. Detailed preoperative planning, meticulous surgical technique, and a comprehensive rehabilitation program are essential components to achieving a satisfactory result. PMID:26502444

Construction of a Nano Biosensor for Cyanide Anion Detection and Its Application in Environmental and Biological Systems.

PubMed

Dong, Zhen-Zhen; Yang, Chao; Vellaisamy, Kasipandi; Li, Guodong; Leung, Chung-Hang; Ma, Dik-Lung

2017-10-27

We have developed a Ag@Au core-shell nanoparticle (NP)/iridium(III) complex-based sensing platform for the sensitive luminescence "turn-on" sensing of cyanide ions, an acutely toxic pollutant. The assay is based on the quenching effect of Ag@Au NPs on the emission of complex 1, but luminescence is restored after the addition of cyanide anions due to their ability to dissolve the Au shell. Our sensing platform exhibited a high sensitivity toward cyanide anions with a detection limit of 0.036 μM, and also showed high selectivity for cyanide over 10-fold excess amounts of other anions. The sensing platform was also successfully applied to monitor cyanide anions in drinking water and in living cells.

Stability of coordination compounds of Ni2+ and Co2+ ions with succinic acid anion in water-ethanol solvents

NASA Astrophysics Data System (ADS)

Tukumova, N. V.; Dieu Thuan, Tran Thi; Usacheva, T. R.; Koryshev, N. E.; Sharnin, V. A.

2017-04-01

Stability constants of the coordination compounds of nickel(II) and cobalt(II) ions with succinic acid anion in water-ethanol solvents are determined via potentiometric titration at ionic strength of 0.1 and at T = 298.15 K. It is found that logβ values of monoligand complexes of these ions and succinic acid anions rise along with the content of ethanol in solution ( X EtOH = 0-0.7 mole fractions). Based on an analysis of the thermodynamic characteristics of the solvation of the reagents involved in complex formation, it is found that the increased stability of succinate complexes of nickel(II) and cobalt(II) ions in water-ethanol solvents is mainly determined by the weakening of the solvation of succinic acid anion (Y2-).

Incidence of Elbow Ulnar Collateral Ligament Surgery in Collegiate Baseball Players

PubMed Central

Rothermich, Marcus A.; Conte, Stan A.; Aune, Kyle T.; Fleisig, Glenn S.; Cain, E. Lyle; Dugas, Jeffrey R.

2018-01-01

Background: Recent reports have highlighted the progressive increase in the incidence of ulnar collateral ligament (UCL) injuries to the elbow in baseball players of all levels. However, knowledge of the incidence and other epidemiological factors regarding UCL injuries, specifically in college baseball players, is currently lacking. Purpose: To evaluate, over a period of 1 year, the incidence of UCL injuries requiring surgery in National Collegiate Athletic Association (NCAA) Division I baseball programs. Study Design: Descriptive epidemiology study. Methods: A total of 155 Division I collegiate baseball programs agreed to participate in the study. Demographics (position, year, background [location of high school]) for all players on these rosters were obtained from public websites. At the conclusion of the 2017 collegiate baseball season, the athletic trainer for each program entered anonymous, detailed information on injured players through an electronic survey into a secured database. Results: All 155 teams enrolled in the study completed the electronic survey. Of the 5295 collegiate baseball players on these rosters, 134 underwent surgery for an injured UCL (2.5% of all eligible athletes), resulting in a team surgery rate of 0.86 per program for 1 year. These 134 players came from 88 teams, thus 56.8% of the study teams underwent at least 1 surgery during the year. The surgery rate was 2.5 per 100 player-seasons for all players and was significantly higher among pitchers (4.4/100 player-seasons) than nonpitchers (0.7/100 player-seasons). The surgery rate was also significantly higher in underclassmen (3.1/100 player-seasons among freshmen and sophomores) than upperclassmen (1.9/100 player-seasons among juniors and seniors) (incidence rate ratio, 1.7; 95% CI, 1.1-2.4). Players from traditionally warm-weather states did not undergo UCL surgery at a significantly different rate from players from traditionally cold-weather states (2.7/100 player-seasons vs 2.1/100 player-seasons, respectively). Nearly half of surgeries (48.5%) were performed during the baseball season. Conclusion: The incidence of UCL surgeries in NCAA Division I collegiate baseball players represents substantial morbidity to this young athletic population. Risk factors for injuries requiring surgery include being a pitcher and an underclassman. Awareness of these factors should be considered in injury prevention programs. Furthermore, this initial study can serve as a foundation for tracking these surgical injuries in future years and then identifying trends over time. PMID:29687011

The treatment of climate science in Integrated Assessment Modelling: integration of climate step function response in an energy system integrated assessment model.

NASA Astrophysics Data System (ADS)

Dessens, Olivier

2016-04-01

Integrated Assessment Models (IAMs) are used as crucial inputs to policy-making on climate change. These models simulate aspect of the economy and climate system to deliver future projections and to explore the impact of mitigation and adaptation policies. The IAMs' climate representation is extremely important as it can have great influence on future political action. The step-function-response is a simple climate model recently developed by the UK Met Office and is an alternate method of estimating the climate response to an emission trajectory directly from global climate model step simulations. Good et al., (2013) have formulated a method of reconstructing general circulation models (GCMs) climate response to emission trajectories through an idealized experiment. This method is called the "step-response approach" after and is based on an idealized abrupt CO2 step experiment results. TIAM-UCL is a technology-rich model that belongs to the family of, partial-equilibrium, bottom-up models, developed at University College London to represent a wide spectrum of energy systems in 16 regions of the globe (Anandarajah et al. 2011). The model uses optimisation functions to obtain cost-efficient solutions, in meeting an exogenously defined set of energy-service demands, given certain technological and environmental constraints. Furthermore, it employs linear programming techniques making the step function representation of the climate change response adapted to the model mathematical formulation. For the first time, we have introduced the "step-response approach" method developed at the UK Met Office in an IAM, the TIAM-UCL energy system, and we investigate the main consequences of this modification on the results of the model in term of climate and energy system responses. The main advantage of this approach (apart from the low computational cost it entails) is that its results are directly traceable to the GCM involved and closely connected to well-known methods of analysing GCMs with the step-experiments. Acknowledgments: This work is supported by the FP7 HELIX project (www.helixclimate.eu) References: Anandarajah, G., Pye, S., Usher, W., Kesicki, F., & Mcglade, C. (2011). TIAM-UCL Global model documentation. https://www.ucl.ac.uk/energy-models/models/tiam-ucl/tiam-ucl-manual Good, P., Gregory, J. M., Lowe, J. A., & Andrews, T. (2013). Abrupt CO2 experiments as tools for predicting and understanding CMIP5 representative concentration pathway projections. Climate Dynamics, 40(3-4), 1041-1053.

Large Fluorescence Response by Alcohol from a Bis(benzoxazole)-Zinc(II) Complex: The Role of Excited State Intramolecular Proton Transfer

PubMed Central

Wang, Junfeng; Chu, Qinghui; Liu, Xiumin; Wesdemiotis, Chrys

2013-01-01

The formation of a bis(HBO) anion is known to turn-on the fluorescence to give red emission, via controlling the excited-state intramolecular proton transfer (ESIPT). The poor stability of the formed anion, however, hampered its application. The anion stability is found to be greatly improved by attaching the anion to Zn2+ cation (i.e. forming zinc complex), whose emission is at λem ≈ 550 and 760 nm. Interestingly, addition of methanol to the zinc complex induces a remarkable red fluorescence (λem ≈ 630 nm, ϕfl ≈ 0.8). With the aid of spectroscopic studies (1H NMR, UV-vis, fluorescence, and mass spectra), the structures of the zinc complexes are characterized. The emission species is identified as a dimer-like structure. The study thus reveals an effective fluorescence switching mechanism that could further advance the application of ESIPT-based sensors. PMID:23514312

Revisiting caffeate's capabilities as a complexation agent to silver cation in mining processes by means of the dual descriptor--a conceptual DFT approach.

PubMed

Martínez-Araya, Jorge Ignacio

2012-09-01

Caffeic acid (C(9)H(8)O(4)) and its conjugate base C(9)H(7)O(4) (-) (anionic form-known as caffeate) were analyzed computationally through the use of quantum chemistry to assess their intrinsic global and local reactivity using the tools of conceptual density functional theory. The anionic form was found to be better at coordinating the silver cation than caffeic acid thus suggesting the use of caffeate as a complexation agent. The complexation capability of caffeate was compared with that of some of the most common ligand agents used to coordinate silver cations. Local reactivity descriptors allowed identification of the preferred sites on caffeate for silver cation coordination thus generating a plausible silver complex. All silver complexes were analyzed thermodynamically considering interaction energies in both gas and aqueous phases; the complexation free energy in aqueous phase was also determined. These results suggest that more attention be paid to the caffeate anion and its derivatives because this work has shed new light on the behavior of this anion in the recovery of silver cations that could be exploited in silver mining processes in a environmentally friendly way.

Modern views on the composition of anionic oxy-fluoride complexes of aluminium and their rearrangement during the electrolysis of cryolite-alumina melts

NASA Astrophysics Data System (ADS)

Khramov, A. P.; Shurov, N. I.

2014-08-01

Some consequences of the hypothesis of the absence of free F- ions in cryolite-alumina melts are observed. The melt at 1 < CR < 3 is assumed to consist of the complexes AlF{6/3-}, AlF{5/2-}, AlF{4/-}, Al2OF{6/2-}, and Al2O2F{4/2-}, and alkali metal cations. A formal-stoichiometric study of the processes occurring during electrolysis is performed on the basis of the accepted hypothesis. Judgments about some of the features of the electrode reactions and chemical reactions in the electrolyte volume are presented. The reaction schemes for the instances with and without the subsequent/preceding chemical reaction near the electrode or in the molten salt volume are given. The mass flows of various forms of ionic complexes through the electrolyte volume are given for these schemes. Definitive conclusions are not made in the study, but the range of possible variants for the electrochemical routes of the overall chemical reaction in the cell is limited.

Crystal structure of choline fenofibrate (Trilipix®), (C5H14NO) (C17H14ClO4)

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

Kaduk, James A.; Zhong, Kai; Gindhart, Amy M.

2016-04-04

The crystal structure of choline fenofibrate has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Choline fenofibrate crystallizes in space groupPbca(#61) witha= 12.341 03(2),b= 28.568 70(6),c= 12.025 62(2) Å,V= 4239.84(1) Å 3, andZ= 8. The hydroxyl group of the choline anion makes a strong hydrogen bond to the ionized carboxylate group of the fenofibrate anion. Together with C–H···O hydrogen bonds, these link the cations and anions into layers parallel to theac-plane. The powder pattern has been submitted to ICDD for inclusion in the Powder Diffraction File™.

Carbon dioxide is tightly bound in the [Co(Pyridine)(CO2)]- anionic complex

NASA Astrophysics Data System (ADS)

Graham, Jacob D.; Buytendyk, Allyson M.; Zhang, Xinxing; Kim, Seong K.; Bowen, Kit H.

2015-11-01

The [Co(Pyridine)(CO2)]- anionic complex was studied through the combination of photoelectron spectroscopy and density functional theory calculations. This complex was envisioned as a primitive model system for studying CO2 binding to negatively charged sites in metal organic frameworks. The vertical detachment energy (VDE) measured via the photoelectron spectrum is 2.7 eV. Our calculations imply a structure for [Co(Pyridine)(CO2)]- in which a central cobalt atom is bound to pyridine and CO2 moieties on either sides. This structure was validated by acceptable agreement between the calculated and measured VDE values. Based on our calculations, we found CO2 to be bound within the anionic complex by 1.4 eV.

Carbon dioxide is tightly bound in the [Co(Pyridine)(CO2)](-) anionic complex.

PubMed

Graham, Jacob D; Buytendyk, Allyson M; Zhang, Xinxing; Kim, Seong K; Bowen, Kit H

2015-11-14

The [Co(Pyridine)(CO2)](-) anionic complex was studied through the combination of photoelectron spectroscopy and density functional theory calculations. This complex was envisioned as a primitive model system for studying CO2 binding to negatively charged sites in metal organic frameworks. The vertical detachment energy (VDE) measured via the photoelectron spectrum is 2.7 eV. Our calculations imply a structure for [Co(Pyridine)(CO2)](-) in which a central cobalt atom is bound to pyridine and CO2 moieties on either sides. This structure was validated by acceptable agreement between the calculated and measured VDE values. Based on our calculations, we found CO2 to be bound within the anionic complex by 1.4 eV.

CATALYTIC PROMOTION OF THE ADSORPTION OF VANADIUM ON AN ANIONIC EXCHANGE RESIN

DOEpatents

Bailes, R.H.; Ellis, D.A.

1958-08-26

An improvement in the process for the recovery of vanadium from acidic phosphatic solutions is presented. In this process the vanadium is first oxidized to the pentavaleat state, and is then separated by contacting such solutions with an anion exchange resin whereby adsorption of the complexed pentavalent vanadium is effected. The improvement lies in the fact that adsorp tion of the vanadium complex by the anion exchange resin is promoted and improved by providing fiuoride ions in solution to be contacted.

Group transfer and electron transfer reactions of organometallic complexes

NASA Astrophysics Data System (ADS)

Atwood, Jim D.

During 1994, despite the disruptions, the authors have made progress in several aspects of their research on electron transfer reactions between organometallic complexes. This summary covers three areas that are relatively complete: (1) reactions between metal carbonyl anions and metal carbonyl halides, (2) reactions of hydrido- and alkyl-containing anions (RFe(CO)4(-) and RW(CO)5(-) with metal carbonyl cations; and (3) reactions of a seventeen-electron complex (Cp* Cr(CO)3*) with metal carbonyl derivatives. Two areas of examination that have just begun (possible carbene transfer and the possible role of metal carbonyl anions in carbon-hydrogen bond activation) will also be described.

Decay dynamics of nascent acetonitrile and nitromethane dipole-bound anions produced by intracluster charge-transfer

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

Yandell, Margaret A.; King, Sarah B.; Neumark, Daniel M., E-mail: dneumark@berkeley.edu

2014-05-14

Decay dynamics of nascent dipole bound states of acetonitrile and nitromethane are examined using time-resolved photoelectron imaging of iodide-acetonitrile (I{sup −}·CH{sub 3}CN) and iodide-nitromethane (I{sup −}·CH{sub 3}NO{sub 2}) complexes. Dipole-bound anions are created by UV-initiated electron transfer to the molecule of interest from the associated iodide ion at energies just below the vertical detachment energy of the halide-molecule complex. The acetonitrile anion is observed to decay biexponentially with time constants in the range of 4–900 ps. In contrast, the dipole bound state of nitromethane decays rapidly over 400 fs to form the valence bound anion. The nitromethane valence anion speciesmore » then decays biexponentially with time constants of 2 ps and 1200 ps. The biexponential decay dynamics in acetonitrile are interpreted as iodine atom loss and autodetachment from the excited dipole-bound anion, followed by slower autodetachment of the relaxed metastable ion, while the dynamics of the nitromethane system suggest that a dipole-bound anion to valence anion transition proceeds via intramolecular vibrational energy redistribution to nitro group modes in the vicinity of the iodine atom.« less

Decay dynamics of nascent acetonitrile and nitromethane dipole-bound anions produced by intracluster charge-transfer.

PubMed

Yandell, Margaret A; King, Sarah B; Neumark, Daniel M

2014-05-14

Decay dynamics of nascent dipole bound states of acetonitrile and nitromethane are examined using time-resolved photoelectron imaging of iodide-acetonitrile (I(-)·CH3CN) and iodide-nitromethane (I(-)·CH3NO2) complexes. Dipole-bound anions are created by UV-initiated electron transfer to the molecule of interest from the associated iodide ion at energies just below the vertical detachment energy of the halide-molecule complex. The acetonitrile anion is observed to decay biexponentially with time constants in the range of 4-900 ps. In contrast, the dipole bound state of nitromethane decays rapidly over 400 fs to form the valence bound anion. The nitromethane valence anion species then decays biexponentially with time constants of 2 ps and 1200 ps. The biexponential decay dynamics in acetonitrile are interpreted as iodine atom loss and autodetachment from the excited dipole-bound anion, followed by slower autodetachment of the relaxed metastable ion, while the dynamics of the nitromethane system suggest that a dipole-bound anion to valence anion transition proceeds via intramolecular vibrational energy redistribution to nitro group modes in the vicinity of the iodine atom.

Application of surface complexation models to anion adsorption by natural materials

USDA-ARS?s Scientific Manuscript database

Various chemical models of ion adsorption will be presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model w...

Anion-free bambus[6]uril and its supramolecular properties.

PubMed

Svec, Jan; Dusek, Michal; Fejfarova, Karla; Stacko, Peter; Klán, Petr; Kaifer, Angel E; Li, Wei; Hudeckova, Edita; Sindelar, Vladimir

2011-05-09

Methods for the preparation of anion-free bambus[6]uril (BU6) are presented. They are based on the oxidation of iodide anion, which is bound inside the macrocycle, utilizing dark oxidation by hydrogen peroxide or photooxidation in the presence of titanium dioxide. Anion-free BU6 was found to be insoluble in any of the investigated solvents; however, it dissolves in methanol/chloroform (1:1) or acetonitrile/water (1:1) mixtures in the presence of the tetrabutylammonium salt of a suitable anion. The association constants with halide ions, BF(4)(-), NO(3)(-), and CN(-), were measured by (1)H NMR spectroscopy. The highest association constant (8.9×10(5) M(-1)) was found for the 1:1 complex of BU6 with I(-) in acetonitrile/water mixture. A number of crystal structures of BU6 complexes with various anions were obtained. The influence of the anion size on the macrocycle diameter is discussed together with an unusual arrangement of the macrocycles into separate layers. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembled 1D infinite inorganic [2]catenane and 2D sheet framework with calix[8]phenylazoimidazole and [4+4]metallomacrocyclic motifs based on silver and ditopic bis(imidazolyl)methane ligands

NASA Astrophysics Data System (ADS)

Jin, Tianqi; Zhou, Junqiang; Pan, Yangyang; Huang, Yu; Jin, Chuanming

2018-05-01

Three novel supramolecular complexes, [Ag4(2-mBIM)4](ClO4)4(H2O) (1), [Ag2(2-mBIM)2](PF6)2 (2) and [Ag2(PA-BIM)2](ClO4)2(CH2Cl2) (3) (2-mBIM = bis(2-methyl- imidazol-1-yl)methane; PA-BIM = 1,1-bis[(2-phenylazo)imidazol-1-yl]methane), have been prepared and structurally characterized. The reported complexes bear [4+4]metallomacrocyclic motifs comprising four silver atoms and four ditopic bis(imidazolyl)methane ligands. Complex 1 exhibits a rare 1D infinite inorganic [2]catenane structure, which was self-assembled by the interlocking action of [4+4]metallomacrocyclic units. Complex 2 is a 2D layered supramolecular motif containing [4+4]macrometallacycle units with π-π interaction between imidazole rings. Complex 3 has a 2D sheet supramolecular framework through Ag-Ag interactions in [4+4]macrometallacyclic calix [8]phenylazoimidazole with a nanocavity. The results suggest that the bisimidazolium ligands and anions play crucial roles in the formation of the different host structures. The thermal stability and photoluminescence spectra of the synthesized complexes have also been discussed.

Ammonia-hydrogen bromide and ammonia-hydrogen iodide complexes: anion photoelectron and ab initio studies.

PubMed

Eustis, S N; Whiteside, A; Wang, D; Gutowski, M; Bowen, K H

2010-01-28

The ammonia-hydrogen bromide and ammonia-hydrogen iodide, anionic heterodimers were studied by anion photoelectron spectroscopy. In complementary studies, these anions and their neutral counterparts were also investigated via ab initio theory at the coupled cluster level. In both systems, neutral NH(3)...HX dimers were predicted to be linear, hydrogen-bonded complexes, whereas their anionic dimers were found to be proton-transferred species of the form, (NH(4)(+)X(-))(-). Both experimentally measured and theoretically predicted vertical detachment energies (VDE) are in excellent agreement for both systems, with values for (NH(4)(+)Br(-))(-) being 0.65 and 0.67 eV, respectively, and values for (NH(4)(+)I(-))(-) being 0.77 and 0.81 eV, respectively. These systems are discussed in terms of our previous study of (NH(4)(+)Cl(-))(-).

Self-organizing layers from complex molecular anions

DOE PAGES

Warneke, Jonas; McBriarty, Martin E.; Riechers, Shawn L.; ...

2018-05-14

The formation of traditional ionic materials occurs principally via joint accumulation of both anions and cations. Here in this paper, we describe a previously unreported phenomenon by which macroscopic liquid-like thin layers with tunable self-organization properties form through accumulation of stable complex ions of one polarity on surfaces. Using a series of highly stable molecular anions we demonstrate a strong influence of the internal charge distribution of the molecular ions, which is usually shielded by counterions, on the properties of the layers. Detailed characterization reveals that the intrinsically unstable layers of anions on surfaces are stabilized by simultaneous accumulation ofmore » neutral molecules from the background environment. Different phases, self-organization mechanisms and optical properties are observed depending on the molecular properties of the deposited anions, the underlying surface and the coadsorbed neutral molecules. This demonstrates rational control of the macroscopic properties (morphology and size of the formed structures) of the newly discovered anion-based layers.« less

Self-organizing layers from complex molecular anions

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

Warneke, Jonas; McBriarty, Martin E.; Riechers, Shawn L.

The formation of traditional ionic materials occurs principally via joint accumulation of both anions and cations. Here in this paper, we describe a previously unreported phenomenon by which macroscopic liquid-like thin layers with tunable self-organization properties form through accumulation of stable complex ions of one polarity on surfaces. Using a series of highly stable molecular anions we demonstrate a strong influence of the internal charge distribution of the molecular ions, which is usually shielded by counterions, on the properties of the layers. Detailed characterization reveals that the intrinsically unstable layers of anions on surfaces are stabilized by simultaneous accumulation ofmore » neutral molecules from the background environment. Different phases, self-organization mechanisms and optical properties are observed depending on the molecular properties of the deposited anions, the underlying surface and the coadsorbed neutral molecules. This demonstrates rational control of the macroscopic properties (morphology and size of the formed structures) of the newly discovered anion-based layers.« less

Anion-assisted trans-cis isomerization of palladium(II) phosphine complexes containing acetanilide functionalities through hydrogen bonding interactions.

PubMed

Lu, Xiao-Xia; Tang, Hau-San; Ko, Chi-Chiu; Wong, Jenny Ka-Yan; Zhu, Nianyong; Yam, Vivian Wing-Wah

2005-03-28

The anion-assisted shift of trans-cis isomerization equilibrium of a palladium(II) complex containing acetanilide functionalities brought about by allosteric hydrogen bonding interactions has been established by UV/Vis, 1H NMR, 31P NMR and ESI-MS studies.

Determination of phytate in high molecular weight, charged organic matrices by two-dimensional size exclusion-ion chromatography

USDA-ARS?s Scientific Manuscript database

A two-dimensional chromatography method for analyzing anionic targets (specifically phytate) in complex matrices is described. Prior to quantification by anion exchange chromatography, the sample matrix was prepared by size exclusion chromatography, which removed the majority of matrix complexities....

Angular Momentum Evolution of Young Stars in the nearby Scorpius-Centaurus OB Association

NASA Astrophysics Data System (ADS)

Mellon, Samuel N.; Mamajek, Eric E.; Oberst, Thomas E.; Pecaut, Mark J.

2017-07-01

We report the results of a study of archival SuperWASP light curves for stars in Scorpius-Centaurus (Sco-Cen), the nearest OB association. We use SuperWASP time-series photometry to extract rotation periods for 189 candidate members of the Sco-Cen complex and verify that 162 of those are members of the classic Sco-Cen subgroups of Upper Scorpius (US), Upper Centaurus-Lupus (UCL), and Lower Centaurus-Crux (LCC). This study provides the first measurements of rotation periods explicitly for large samples of pre-main-sequence (pre-MS) stars spanning the UCL and LCC subgroups. Our final sample of 157 well-characterized pre-MS stars spans ages of ˜10-20 Myr, spectral types of ˜F3-M0, and masses of M ≃ 0.3-1.5 {{ M }}⊙ {{N}}. For this sample, we find a distribution of stellar rotation periods with a median of P rot ≃ 2.4 days, an overall range of 0.2 < P rot < 8 days, and a fairly well-defined mass-dependent upper envelope of rotation periods. This distribution of periods is consistent with recently developed stellar angular momentum evolution models. These data are significant because they represent an undersampled age range and the number of measurable rotation periods is large compared to recent studies of other regions. We also search for new examples of eclipsing disk or ring systems analogous to 1SWASP J140747.93-394542.6 (J1407), but find none. Our survey yielded five eclipsing binaries, but only one appears to be physically associated with the Sco-Cen complex. V2394 Oph is a heavily reddened (A V ≃ 5 mag) massive contact binary in the LDN 1689 cloud whose Gaia astrometry is clearly consistent with kinematic membership with the Ophiuchus star-forming region.

Lower extremity balance is improved at time of return to throwing in baseball players after an ulnar collateral ligament reconstruction when compared to pre-operative measurements.

PubMed

Hannon, Joseph; Garrison, J Craig; Conway, John

2014-05-01

/ Lower extremity balance deficits have been shown to lead to altered kinematics and increased injury risk in lower extremity athletes. The purpose of this study was to compare lower extremity balance in baseball players with an ulnar collateral ligament (UCL) tear pre-operatively and post-operatively at the beginning of the pre-return to throwing program stage of rehabilitation (3 months). Thirty-three competitive high school and collegiate male baseball players (18.5 ± 3.2) with a diagnosed UCL tear volunteered for the study. Of the 33 baseball players 29 were pitchers, 1 was a catcher, and 3 were infielders. Participants were seen pre-operatively and at 3 months post operatively. This 3 month point was associated with a follow-up visit to the orthopedic surgeon and subsequent release to begin the pre-return to throwing mark for baseball players following their surgery. Following surgery, each participant followed a standard UCL protocol which included focused lower extremity balance and neuromuscular control exercises. Participants were tested for single leg balance using the Y-Balance Test™ - Lower Quadrant (YBT-LQ) on both their lead and stance limbs. YBT-LQ composite scores were calculated for the stance and lead limbs pre- and post-operatively and compared over time. Paired t-tests were used to calculate differences between time 1 and time 2 (p < 0.05). Baseball players with diagnosed UCL tears demonstrated significant balance deficits on their stance (p < .001) and lead (p = .009) limbs prior to surgery compared to balance measures at the 3-month follow up (Stance Pre-Op = 89.4 ± 7.5%; Stance 3 Month = 94.9 ± 9.5%) (Lead Pre-Op = 90.2 ± 6.7%; Lead 3 Month = 93.6 ± 7.2%). Based on the results of this study, lower extremity balance is altered in baseball players with UCL tears prior to surgery. Statistically significant improvements were seen and balance measures improved at the time of return to throwing. Level 2b.

Magnetic Resonance Imaging Predictors of Failure in the Nonoperative Management of Ulnar Collateral Ligament Injuries in Professional Baseball Pitchers.

PubMed

Frangiamore, Salvatore J; Lynch, T Sean; Vaughn, Michael D; Soloff, Lonnie; Forney, Michael; Styron, Joseph F; Schickendantz, Mark S

2017-07-01

A medial ulnar collateral ligament (UCL) injury of the elbow is an increasingly common injury in professional baseball pitchers. Predictors of success and failure are not well defined for the nonoperative management of these injuries. To evaluate the efficacy of objective measures to predict failure of the nonoperative management of UCL injuries. Case-control study; Level of evidence, 3. Thirty-two professional pitchers (82%) met inclusion criteria and underwent an initial trial of nonoperative treatment for UCL tears based on clinical and radiological findings. Age, preseason physical examination results, magnetic resonance imaging (MRI) characteristics, and performance metrics were analyzed for these pitchers. Successful nonoperative management was defined as a return to the same level of play or higher for >1 year. Failure was defined as recurrent pain or weakness requiring a surgical intervention after a minimum of 3 months' rest when attempting a return to a throwing rehabilitation program. Thirty-two pitchers (mean age, 22.3 years) who underwent initial nonoperative treatment of UCL injuries were evaluated. Thirty-four percent (11/32) failed and required subsequent ligament reconstruction. Sixty-six percent (21/32) successfully returned to the same level of play for 1 year without a surgical intervention. There was no significant difference seen in physical examination findings or performance metrics between these patients. When comparing MRI findings between the groups, 82% (9/11) ( P < .001) who failed nonoperative management had distal tears, and 81% (17/21) who did not fail had proximal tears ( P < .001). When adjusting for age, location, and evidence of chronic changes on MRI, the likelihood of failing nonoperative management was 12.40 times greater ( P = .020) with a distal tear. No other variable alone or in combination reached significance. When combining the parameters of a high-grade tear and distal location, 88% (7/8) failed nonoperative management. In professional pitchers, distal UCL tears showed significantly higher odds of failure with nonoperative management compared with proximal tears. Thus, tear location should be considered when deciding between operative and nonoperative management.

The influence of sex and trauma impact on the rupture site of the ulnar collateral ligament of the thumb.

PubMed

Boesmueller, Sandra; Huf, Wolfgang; Rettl, Gregor; Dahm, Falko; Meznik, Alexander; Muschitz, Gabriela; Kitzinger, Hugo; Bukaty, Adam; Fialka, Christian; Vierhapper, Martin

2017-01-01

Although sex- and gender-specific analyses have been gaining more attention during the last years they have rarely been performed in orthopaedic literature. The primary purpose of this study was to investigate whether for injuries of the UCL the specific location of the rupture is influenced by sex. A secondary study question addressed the sex-independent effect of trauma intensity on the rupture site of the UCL. This study is a retrospective analysis of all patients with either a proximal or distal bony avulsion or with a mid-substance tear or ligament avulsion of the UCL treated surgically between 1992 and 2015 at two level-I trauma centres. Trauma mechanisms leading to the UCL injury were classified into the following categories: (1) blunt trauma (i.e., strains), (2) low-velocity injuries (e.g., fall from standing height, assaults), and (3) high-velocity injuries (e.g., sports injuries, motor vehicle accidents). After reviewing the surgical records, patients were divided into three groups, depending upon the ligament rupture site: (1) mid-substance tears, (2) proximal ligament or bony avulsions and (3) distal ligament or bony avulsions. Dependencies between the specific rupture site and the explanatory variables (sex, age, and trauma intensity) were evaluated using χ2 test and logistic regression analysis. In total, 1582 patients (1094 males, 488 females) met the inclusion criteria. Mean age was 41 years (range: 9-90 years). Taking into account the effects of sex on trauma intensity (p<0.001) and of trauma intensity on rupture site (p<0.001), mid-substance tears occurred more frequently in women, whereas men were more prone to distal ligament or bony avulsions (p<0.001). In other words, sex and rupture site correlated due to the effects of sex on trauma intensity and of trauma intensity on rupture site, but taking into account those effects there still was a significant effect of sex on rupture site. The results of this study demonstrate that with regression analysis both sex and trauma intensity allow to predict rupture site in UCL injuries.

The influence of sex and trauma impact on the rupture site of the ulnar collateral ligament of the thumb

PubMed Central

Huf, Wolfgang; Rettl, Gregor; Dahm, Falko; Meznik, Alexander; Muschitz, Gabriela; Kitzinger, Hugo; Bukaty, Adam; Fialka, Christian; Vierhapper, Martin

2017-01-01

Purpose and hypothesis Although sex- and gender-specific analyses have been gaining more attention during the last years they have rarely been performed in orthopaedic literature. The primary purpose of this study was to investigate whether for injuries of the UCL the specific location of the rupture is influenced by sex. A secondary study question addressed the sex-independent effect of trauma intensity on the rupture site of the UCL. Methods This study is a retrospective analysis of all patients with either a proximal or distal bony avulsion or with a mid-substance tear or ligament avulsion of the UCL treated surgically between 1992 and 2015 at two level-I trauma centres. Trauma mechanisms leading to the UCL injury were classified into the following categories: (1) blunt trauma (i.e., strains), (2) low-velocity injuries (e.g., fall from standing height, assaults), and (3) high-velocity injuries (e.g., sports injuries, motor vehicle accidents). After reviewing the surgical records, patients were divided into three groups, depending upon the ligament rupture site: (1) mid-substance tears, (2) proximal ligament or bony avulsions and (3) distal ligament or bony avulsions. Dependencies between the specific rupture site and the explanatory variables (sex, age, and trauma intensity) were evaluated using χ2 test and logistic regression analysis. Results In total, 1582 patients (1094 males, 488 females) met the inclusion criteria. Mean age was 41 years (range: 9–90 years). Taking into account the effects of sex on trauma intensity (p<0.001) and of trauma intensity on rupture site (p<0.001), mid-substance tears occurred more frequently in women, whereas men were more prone to distal ligament or bony avulsions (p<0.001). In other words, sex and rupture site correlated due to the effects of sex on trauma intensity and of trauma intensity on rupture site, but taking into account those effects there still was a significant effect of sex on rupture site. Conclusions The results of this study demonstrate that with regression analysis both sex and trauma intensity allow to predict rupture site in UCL injuries. PMID:28738083

Guilty as charged: unmeasured urinary anions in a case of pyroglutamic acidosis.

PubMed

Rolleman, E J; Hoorn, E J; Didden, P; Zietse, R

2008-09-01

A patient developed an unexplained metabolic acidosis with the characteristics of renal tubular acidosis. By correcting the serum anion gap for hypoalbuminaemia and analysing the urinary anions and cations, the presence of unmeasured anions was revealed. The diagnosis of pyroglutamic acidosis, caused by a combination of flucloxacillin and acetaminophen, was established. Strategies for solving complex cases of metabolic acidosis are discussed.

Pyrrole- and Naphthobipyrrole-Strapped Calix[4]pyrroles as Azide Anion Receptors.

PubMed

Kim, Seung Hyeon; Lee, Juhoon; Vargas-Zúñiga, Gabriela I; Lynch, Vincent M; Hay, Benjamin P; Sessler, Jonathan L; Kim, Sung Kuk

2018-03-02

The binding interactions between the azide anion (N 3 - ) and the strapped calix[4]pyrroles 2 and 3 bearing auxiliary hydrogen bonding donors on the bridging moieties, as well as of normal calix[4]pyrrole 1, were investigated via 1 H NMR spectroscopic and isothermal titration calorimetry analyses. The resulting data revealed that receptors 2 and 3 have significantly higher affinities for the azide anion in organic media as compared with the unfunctionalized calix[4]pyrrole 1 and other azide receptors reported to date. Single crystal X-ray diffraction analyses and calculations using density functional theory revealed that receptor 2 binds CsN 3 in two distinct structural forms. As judged from the metric parameters, in the resulting complexes one limiting azide anion resonance contributor is favored over the other, with the specifics depending on the binding mode. In contrast to what is seen for 2, receptor 3 forms a CsN 3 complex in 20% CD 3 OD in CDCl 3 , wherein the azide anion is bound only vertically to the NH protons of the calix[4]pyrrole and the cesium cation is complexed within the cone shaped-calix[4]pyrrole bowl. The bound cesium cation is also in close proximity to a naphthobipyrrole subunit present in a different molecule, forming an apparent cation-π complex.

Reduction of paraquat-induced renal cytotoxicity by manganese and copper complexes of EGTA and EHPG.

PubMed

Samai, Mohamed; Hague, Theresa; Naughton, Declan P; Gard, Paul R; Chatterjee, Prabal K

2008-02-15

Superoxide anion generation plays an important role in the development of paraquat toxicity. Although superoxide dismutase mimetics (SODm) have provided protection against organ injury involving generation of superoxide anions, they often suffer problems, e.g., regarding their bioavailability or potential pro-oxidant activity. The aim here was to investigate and compare the therapeutic potential of two novel SODm, manganese(II) and copper(II) complexes of the calcium chelator ethylenebis(oxyethylenenitrilo)tetraacetic acid (EGTA) and of the contrast agent ethylenebis(hydroxyphenylglycine) (EHPG), against paraquat-induced renal toxicity in vitro. Incubation of renal NRK-52E cells with paraquat (1 mM) for 24 h produced submaximal, yet significant, reduction in cellular viability and cell death and produced significant increases in superoxide anion and hydroxyl radical generation. Manganese and copper complexes of EGTA (10-100 microM) and EHPG (30-100 microM) reduced paraquat-induced renal cell toxicity and reduced superoxide anion and hydroxyl radical generation significantly. Manganese complexes displayed greater efficacy than copper complexes and, at equivalent concentrations, manganese complexed with EHPG provided the greatest protection. Furthermore, these metal complexes did not interfere with the uptake of [methyl-(14)C]paraquat into NRK-52E cells, suggesting that they provided protection against paraquat cytotoxicity via intracellular mechanisms. These complexes did not display cytotoxicity at the concentrations examined. Together, these results suggest that manganese and copper complexes of EGTA and EHPG, and especially the manganese-EHPG complex, could provide benefit against paraquat nephrotoxicity.

Fluorine-18-labeled Gd3+/Yb3+/Er3+ co-doped NaYF4 nanophosphors for multimodality PET/MR/UCL imaging.

PubMed

Zhou, Jing; Yu, Mengxiao; Sun, Yun; Zhang, Xianzhong; Zhu, Xingjun; Wu, Zhanhong; Wu, Dongmei; Li, Fuyou

2011-02-01

Molecular imaging modalities provide a wealth of information that is highly complementary and rarely redundant. To combine the advantages of molecular imaging techniques, (18)F-labeled Gd(3+)/Yb(3+)/Er(3+) co-doped NaYF(4) nanophosphors (NPs) simultaneously possessing with radioactivity, magnetic, and upconversion luminescent properties have been fabricated for multimodality positron emission tomography (PET), magnetic resonance imaging (MRI), and laser scanning upconversion luminescence (UCL) imaging. Hydrophilic citrate-capped NaY(0.2)Gd(0.6)Yb(0.18)Er(0.02)F(4) nanophosphors (cit-NPs) were obtained from hydrophobic oleic acid (OA)-coated nanoparticles (OA-NPs) through a process of ligand exchange of OA with citrate, and were found to be monodisperse with an average size of 22 × 19 nm. The obtained hexagonal cit-NPs show intense UCL emission in the visible region and paramagnetic longitudinal relaxivity (r(1) = 0.405 s(-1)·(mM)(-1)). Through a facile inorganic reaction based on the strong binding between Y(3+) and F(-), (18)F-labeled NPs have been fabricated in high yield. The use of cit-NPs as a multimodal probe has been further explored for T(1)-weighted MR and PET imaging in vivo and UCL imaging of living cells and tissue slides. The results indicate that (18)F-labeled NaY(0.2)Gd(0.6)Yb(0.18)Er(0.02) is a potential candidate as a multimodal nanoprobe for ultra-sensitive molecular imaging from the cellular scale to whole-body evaluation. Copyright © 2010 Elsevier Ltd. All rights reserved.

Red-light-controllable liquid-crystal soft actuators via low-power excited upconversion based on triplet-triplet annihilation.

PubMed

Jiang, Zhen; Xu, Ming; Li, Fuyou; Yu, Yanlei

2013-11-06

A red-light-controllable soft actuator has been achieved, driven by low-power excited triplet-triplet annihilation-based upconversion luminescence (TTA-UCL). First, a red-to-blue TTA-based upconversion system with a high absolute quantum yield of 9.3 ± 0.5% was prepared by utilizing platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP) as the sensitizer and 9,10-bis(diphenylphosphoryl)anthracene (BDPPA) as the annihilator. In order to be employed as a highly effective phototrigger of photodeformable cross-linked liquid-crystal polymers (CLCPs), the PtTPBP&BDPPA system was incorporated into a rubbery polyurethane film and then assembled with an azotolane-containing CLCP film. The generating assembly film bent toward the light source when irradiated with a 635 nm laser at low power density of 200 mW cm(-2) because the TTA-UCL was effectively utilized by the azotolane moieties in the CLCP film, inducing their trans-cis photoisomerization and an alignment change of the mesogens via an emission-reabsorption process. It is the first example of a soft actuator in which the TTA-UCL is trapped and utilized to create photomechanical effect. Such advantages of using this novel red-light-controllable soft actuator in potential biological applications have also been demonstrated as negligible thermal effect and its excellent penetration ability into tissues. This work not only provides a novel photomanipulated soft actuation material system based on the TTA-UCL technology but also introduces a new technological application of the TTA-based upconversion system in photonic devices.

Accurate, precise, and efficient theoretical methods to calculate anion-π interaction energies in model structures.

PubMed

Mezei, Pál D; Csonka, Gábor I; Ruzsinszky, Adrienn; Sun, Jianwei

2015-01-13

A correct description of the anion-π interaction is essential for the design of selective anion receptors and channels and important for advances in the field of supramolecular chemistry. However, it is challenging to do accurate, precise, and efficient calculations of this interaction, which are lacking in the literature. In this article, by testing sets of 20 binary anion-π complexes of fluoride, chloride, bromide, nitrate, or carbonate ions with hexafluorobenzene, 1,3,5-trifluorobenzene, 2,4,6-trifluoro-1,3,5-triazine, or 1,3,5-triazine and 30 ternary π-anion-π' sandwich complexes composed from the same monomers, we suggest domain-based local-pair natural orbital coupled cluster energies extrapolated to the complete basis-set limit as reference values. We give a detailed explanation of the origin of anion-π interactions, using the permanent quadrupole moments, static dipole polarizabilities, and electrostatic potential maps. We use symmetry-adapted perturbation theory (SAPT) to calculate the components of the anion-π interaction energies. We examine the performance of the direct random phase approximation (dRPA), the second-order screened exchange (SOSEX), local-pair natural-orbital (LPNO) coupled electron pair approximation (CEPA), and several dispersion-corrected density functionals (including generalized gradient approximation (GGA), meta-GGA, and double hybrid density functional). The LPNO-CEPA/1 results show the best agreement with the reference results. The dRPA method is only slightly less accurate and precise than the LPNO-CEPA/1, but it is considerably more efficient (6-17 times faster) for the binary complexes studied in this paper. For 30 ternary π-anion-π' sandwich complexes, we give dRPA interaction energies as reference values. The double hybrid functionals are much more efficient but less accurate and precise than dRPA. The dispersion-corrected double hybrid PWPB95-D3(BJ) and B2PLYP-D3(BJ) functionals perform better than the GGA and meta-GGA functionals for the present test set.

Modifications in structure and interaction of nanoparticle-protein-surfactant complexes in electrolyte solution

NASA Astrophysics Data System (ADS)

Mehan, Sumit; Kumar, S.; Aswal, V. K.; Schweins, R.

2016-05-01

SANS experiments of three-component system of anionic silica nanoparticles, anionic BSA protein and anionic SDS surfactants have been carried out without and with electrolyte in aqueous solution. In both the cases, the interaction of surfactant with protein results in formation of bead-necklace structure of protein-surfactant complexes in solution. These protein-surfactant complexes interact very differently with nanoparticles in absence and presence of electrolyte. In absence of electrolyte, nanoparticles remain in dispersed phase in solution, whereas with the addition of electrolyte the nanoparticles fractal aggregates are formed. SANS describes the phase behavior to be governed by competition of electrostatic and depletion interactions among the components solution.

Early-lanthanide(III) acetonitrile–solvento adducts with iodide and noncoordinating anions

DOE PAGES

Brown, Jessie L.; Davis, Benjamin L.; Scott, Brian L.; ...

2015-12-25

Dissolution of LnI 3 (Ln = La, Ce) in acetonitrile (MeCN) results in the highly soluble solvates LnI 3(MeCN) 5 [Ln = La (1), Ce (2)] in good yield. The ionic complex [La(MeCN) 9][LaI 6] (4), containing a rare homoleptic La 3+ cation and anion, was also isolated as a minor product. Extending this chemistry to NdI 3 results in the consistent formation of the complex ionic structure [Nd(MeCN) 9] 2[NdI 5(MeCN)][NdI 6][I] (3), which contains an unprecedented pentaiodide lanthanoid anion. Also described is the synthesis, isolation, and structural characterization of several homoleptic early-lanthanide MeCN solvates with noncoordinating anions, namely,more » [Ln(MeCN) 9][AlCl 4] 3 [Ln = La (5), Ce (6), Nd (7)]. Notably, complex 6 is the first homoleptic cerium MeCN solvate reported to date. All reported complexes were structurally characterized by X-ray crystallography, as well as by IR spectroscopy and CHN elemental analysis. Furthermore, complexes 1–3 were also characterized by thermogravimetric analysis coupled with mass spectrometry to further elucidate their bulk composition in the solid-state.« less

Method of separating thorium from plutonium

DOEpatents

Clifton, David G.; Blum, Thomas W.

1984-01-01

A method of chemically separating plutonium from thorium. Plutonium and thorium to be separated are dissolved in an aqueous feed solution, preferably as the nitrate salts. The feed solution is acidified and sodium nitrite is added to the solution to adjust the valence of the plutonium to the +4 state. A chloride salt, preferably sodium chloride, is then added to the solution to induce formation of an anionic plutonium chloride complex. The anionic plutonium chloride complex and the thorium in solution are then separated by ion exchange on a strong base anion exchange column.

Method of separating thorium from plutonium

DOEpatents

Clifton, D.G.; Blum, T.W.

A method of chemically separating plutonium from thorium is claimed. Plutonium and thorium to be separated are dissolved in an aqueous feed solution, preferably as the nitrate salts. The feed solution is acidified and sodium nitrite is added to the solution to adjust the valence of the plutonium to the +4 state. A chloride salt, preferably sodium chloride, is then added to the solution to induce formation of an anionic plutonium chloride complex. The anionic plutonium chloride complex and the thorium in solution are then separated by ion exchange on a strong base anion exchange column.

Method of separating thorium from plutonium

DOEpatents

Clifton, D.G.; Blum, T.W.

1984-07-10

A method is described for chemically separating plutonium from thorium. Plutonium and thorium to be separated are dissolved in an aqueous feed solution, preferably as the nitrate salts. The feed solution is acidified and sodium nitrite is added to the solution to adjust the valence of the plutonium to the +4 state. A chloride salt, preferably sodium chloride, is then added to the solution to induce formation of an anionic plutonium chloride complex. The anionic plutonium chloride complex and the thorium in solution are then separated by ion exchange on a strong base anion exchange column.

Outer-sphere interaction of aluminum and gallium solvates with competitive anions in 1,2-propanediol solutions

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

Petrosyants, S.P.; Buslaeva, E.R.

1986-04-01

The interaction of aluminum and gallium solvates with ..pi..-acid ligand in 1,2-propanediol solutions has been investigated. The formation of associates of hexacoordinate aluminum solvates depends on the solvation of the anions in the bulk of the solution or on the faces of the solvento complexes. In the case of gallium the association of the solvates with the anions is determined by two factors: the existence of a configurational equilibrium for the solvento complexes and the preferential solvation of the competitive ..pi..-acid ligands.

Label-Free Pyrophosphate Recognition with Functionalized Asymmetric Nanopores.

PubMed

Ali, Mubarak; Ahmed, Ishtiaq; Ramirez, Patricio; Nasir, Saima; Niemeyer, Christof M; Mafe, Salvador; Ensinger, Wolfgang

2016-04-01

The label-free detection of pyrophosphate (PPi) anions with a nanofluidic sensing device based on asymmetric nanopores is demonstrated. The pore surface is functionalized with zinc complexes based on two di(2-picolyl)amine [bis(DPA)] moieties using carbodiimide coupling chemistry. The complexation of zinc (Zn(2+) ) ion is achieved by exposing the modified pore to a solution of zinc chloride to form bis(Zn(2+) -DPA) complexes. The chemical functionalization is demonstrated by recording the changes in the observed current-voltage (I-V) curves before and after pore modification. The bis(Zn(2+) -DPA) complexes on the pore walls serve as recognition sites for pyrophosphate anion. The experimental results show that the proposed nanofluidic sensor has the ability to sense picomolar concentrations of PPi anion in the surrounding environment. On the contrary, it does not respond to other phosphate anions, including monohydrogen phosphate, dihydrogen phosphate, adenosine monophosphate, adenosine diphosphate, and adenosine triphosphate. The experimental results are described theoretically by using a model based on the Poisson-Nernst-Planck equations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bidentate urea derivatives of p-tert-butyldihomooxacalix[4]arene: neutral receptors for anion complexation.

PubMed

Marcos, Paula M; Teixeira, Filipa A; Segurado, Manuel A P; Ascenso, José R; Bernardino, Raul J; Michel, Sylvia; Hubscher-Bruder, Véronique

2014-01-17

Three new bidentate ureidodihomooxacalix[4]arene derivatives (phenyl 5a, n-propyl 5b, and tert-butyl 5c) were synthesized in four steps from the parent compound p-tert-butyldihomooxacalix[4]arene and obtained in the cone conformation, as shown by NMR studies. The binding ability of these neutral receptors toward spherical, linear, trigonal planar, and tetrahedrical anions was assessed by (1)H NMR and UV-vis titrations. The structures and complexation energies of some complexes were also studied by DFT methods. The data showed that the association constants are strongly dependent on the nature of the substituent (aryl/alkyl) at the urea moiety. In general, for all the receptors, the association constants decrease with decrease of anion basicity. Ph-urea 5a is the best anion receptor, showing the strongest complexation for F(-) (log K(assoc) = 3.10 in CDCl3) and also high binding affinity for the carboxylates AcO(-) and BzO(-). Similar results were obtained by UV-vis studies and were also corroborated by DFT calculations.

Novel fragmentation pathways of anionic adducts of steroids formed by electrospray anion attachment involving regioselective attachment, regiospecific decompositions, charge-induced pathways, and ion-dipole complex intermediates.

PubMed

Rannulu, Nalaka S; Cole, Richard B

2012-09-01

The analysis of several bifunctional neutral steroids, 5-α-pregnane diol (5-α-pregnane-3α-20βdiol), estradiol (3,17α-dihydroxy-1,3,5(10)-estratriene), progesterone (4-pregnene-3,20-dione), lupeol (3β-hydroxy-20(29)-lupene), pregnenolone (5-pregnen-3β-ol-20-one), and pregnenolone acetate (5-pregnen-3β-ol-20-one acetate) was accomplished by negative ion electrospray mass spectrometry (ESI-MS) employing adduct formation with various anions: fluoride, bicarbonate, acetate, and chloride. Fluoride yielded higher abundances of anionic adducts and more substantial abundances of deprotonated molecules compared with other investigated anions. Collision-induced dissociation (CID) of precursor [M + anion](-) adducts of these steroids revealed that fluoride adduct [M + F](-) precursors first lose HF to produce [M - H](-) and then undergo consecutive decompositions to yield higher abundances of structurally-informative product ions than the other tested anions. In addition to charge-remote fragmentations, the majority of CID pathways of estradiol are deduced to occur via charge-induced fragmentation. Most interestingly, certain anions exhibit preferential attachment to a specific site on these bifunctional steroid molecules, which we are calling "regioselective anion attachment." Regioselective anion attachment is evidenced by subsequent regiospecific decomposition. Regioselective attachment of fluoride (and acetate) anions to low (and moderate) acidity functional groups of pregnenolone, respectively, is demonstrated using deuterated compounds. Moreover, the formation of unique intermediate ion-dipole complexes leading to novel fragmentation pathways of fluoride adducts of pregnenolone acetate, and bicarbonate adducts of d(4)-pregnenolone, are also discussed.

Novel Fragmentation Pathways of Anionic Adducts of Steroids Formed by Electrospray Anion Attachment Involving Regioselective Attachment, Regiospecific Decompositions, Charge-Induced Pathways, and Ion-Dipole Complex Intermediates

NASA Astrophysics Data System (ADS)

Rannulu, Nalaka S.; Cole, Richard B.

2012-09-01

The analysis of several bifunctional neutral steroids, 5-α-pregnane diol (5-α-pregnane-3α-20βdiol), estradiol (3,17α-dihydroxy-1,3,5(10)-estratriene), progesterone (4-pregnene-3,20-dione), lupeol (3β-hydroxy-20(29)-lupene), pregnenolone (5-pregnen-3β-ol-20-one), and pregnenolone acetate (5-pregnen-3β-ol-20-one acetate) was accomplished by negative ion electrospray mass spectrometry (ESI-MS) employing adduct formation with various anions: fluoride, bicarbonate, acetate, and chloride. Fluoride yielded higher abundances of anionic adducts and more substantial abundances of deprotonated molecules compared with other investigated anions. Collision-induced dissociation (CID) of precursor [M + anion]- adducts of these steroids revealed that fluoride adduct [M + F]- precursors first lose HF to produce [M - H]- and then undergo consecutive decompositions to yield higher abundances of structurally-informative product ions than the other tested anions. In addition to charge-remote fragmentations, the majority of CID pathways of estradiol are deduced to occur via charge-induced fragmentation. Most interestingly, certain anions exhibit preferential attachment to a specific site on these bifunctional steroid molecules, which we are calling "regioselective anion attachment." Regioselective anion attachment is evidenced by subsequent regiospecific decomposition. Regioselective attachment of fluoride (and acetate) anions to low (and moderate) acidity functional groups of pregnenolone, respectively, is demonstrated using deuterated compounds. Moreover, the formation of unique intermediate ion-dipole complexes leading to novel fragmentation pathways of fluoride adducts of pregnenolone acetate, and bicarbonate adducts of d4-pregnenolone, are also discussed.

Synthesis of a new class of carbon-bonded anionic sigma complexes with 1,3-dimethyl-2,6-dioxo-5-(2,4,6-trinitrophenyl)-1,2,3,6-tetrahydropyrimidin-4-olate moiety as insensitive high energy density materials -- implications from impact sensitivity and thermal testings.

PubMed

Kulandaiya, Rajamani; Doraisamyraja, Kalaivani

2015-01-01

Poly nitro aromatic compounds are high energy density materials. Carbon-bonded anionic sigma complexes derived from them have remarkable thermal stability. At present there is a strong requirement for thermally stable insensitive high energy density materials (IHEDMs) in the energetic field which necessitates the present investigation. Three new carbon-bonded anionic sigma complexes were synthesized from 2-chloro-1,3,5-trinitrobenzene, 1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione (1,3-dimethylbarbituric acid) and bases such as triethanolamine, pyridine and N,N-diethylaniline, characterized by UV-VIS, IR, (1)H NMR, (13)C NMR and elemental analysis data. Their molecular structures were further ascertained through single crystal X-ray diffraction studies. TGA/DTA testings were undertaken at four different heating rates (5, 10, 20 and 40 K/min) and energy of activation was determined employing Ozawa and Kissinger plots. The reported carbon-bonded anionic sigma complexes were prepared through single pot synthesis in good yield with high purity. These complexes are molecular salts comprise of cation and anion moieties. Because of the salt-like nature, they are highly stable upto 300°C and decompose in two stages on further heating. They are stable towards impact of 2 kg mass hammer upto height limit (160 cm) of the instrument. The delocalization of the negative charge and various hydrogen bonds noticed in their crystals are the added factors of their thermal stability. The new insensitive high energy density materials of the present findings may receive attention in the field of energetics in future. Graphical AbstractA new class of carbon-bonded anionic sigma complexes as insensitive high energy density materials.

Mixed cerium-platinum oxides: Electronic structure of [CeO]Pt{sub n} (n = 1, 2) and [CeO{sub 2}]Pt complex anions and neutrals

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

Ray, Manisha; Kafader, Jared O.; Topolski, Josey E.

The electronic structures of several small Ce–Pt oxide complexes were explored using a combination of anion photoelectron (PE) spectroscopy and density functional theory calculations. Pt and Pt{sub 2} both accept electron density from CeO diatomic molecules, in which the cerium atom is in a lower-than-bulk oxidation state (+2 versus bulk +4). Neutral [CeO]Pt and [CeO]Pt{sub 2} complexes are therefore ionic, with electronic structures described qualitatively as [CeO{sup +2}]Pt{sup −2} and [CeO{sup +}]Pt{sub 2}{sup −}, respectively. The associated anions are described qualitatively as [CeO{sup +}]Pt{sup −2} and [CeO{sup +}]Pt{sub 2}{sup −2}, respectively. In both neutrals and anions, the most stable molecularmore » structures determined by calculations feature a distinct CeO moiety, with the positively charged Ce center pointing toward the electron rich Pt or Pt{sub 2} moiety. Spectral simulations based on calculated spectroscopic parameters are in fair agreement with the spectra, validating the computationally determined structures. In contrast, when Pt is coupled with CeO{sub 2}, which has no Ce-localized electrons that can readily be donated to Pt, the anion is described as [CeO{sub 2}]Pt{sup −}. The molecular structure predicted computationally suggests that it is governed by charge-dipole interactions. The neutral [CeO{sub 2}]Pt complex lacks charge-dipole stabilizing interactions, and is predicted to be structurally very different from the anion, featuring a single Pt–O–Ce bridge bond. The PE spectra of several of the complexes exhibit evidence of photodissociation with Pt{sup −} daughter ion formation. The electronic structures of these complexes are related to local interactions in Pt-ceria catalyst-support systems.« less

Making the invisible visible: improved electrospray ion formation of metalloporphyrins/-phthalocyanines by attachment of the formate anion (HCOO(-)).

PubMed

Hitzenberger, Jakob Felix; Dammann, Claudia; Lang, Nina; Lungerich, Dominik; García-Iglesias, Miguel; Bottari, Giovanni; Torres, Tomás; Jux, Norbert; Drewello, Thomas

2016-02-21

A protocol is developed for the coordination of the formate anion (HCOO(-)) to neutral metalloporphyrins (Pors) and -phthalocyanines (Pcs) containing divalent metals as a means to improve their ion formation in electrospray ionization (ESI). This method is particularly useful when the oxidation of the neutral metallomacrocycle fails. While focusing on Zn(II)Pors and Zn(II)Pcs, we show that formate is also readily attached to Mn(II), Mg(II) and Co(II)Pcs. However, for the Co(II)Pc secondary reactions can be observed. Upon collision-induced dissociation (CID), Zn(II)Por/Pc·formate supramolecular complexes can undergo the loss of CO2 in combination with transfer of a hydride anion (H(-)) to the zinc metal center. Further dissociation leads to electron transfer and hydrogen atom loss, generating a route to the radical anion of the Zn(II)Por/Pc without the need for electrochemical reduction, although the Zn(II)Por/Pc may have a too low electron affinity to allow electron transfer directly from the formate anion. In addition to single Por molecules, multi Por arrays were successfully analyzed by this method. In this case, multiple addition of formate occurs, giving rise to multiply charged species. In these multi Por arrays, complexation of the formate anion occurs by two surrounding Por units (sandwich). Therefore, the maximum attainment of formate anions in these arrays corresponds to the number of such sandwich complexes rather than the number of porphyrin moieties. The same bonding motif leads to dimers of the composition [(Zn(II)Por/Pc)2·HCOO](-). In these, the formate anion can act as a structural probe, allowing the distinction of isomeric ions with the formate bridging two macrocycles or being attached to a dimer of directly connected macrocycles.

PROCESS FOR THE PURIFICATION OF URANIUM

DOEpatents

Rosenfeld, S.

1959-01-20

A proccss is described for reclaiming uranium values from aqueous solutions containing U, Fe, Ni, Cu, and Cr comprising treating the solution with NH/sub 3/ to precipitate the: U, Fc, and Cr and leaving Cu and Ni in solution as ammonia complex ions. The precipitate is chlorinated with CCl/sub 4/ at an elevated temperature to convert the U, Tc, and Cr into their chlorides. The more volatile FeCl/sub 3/ and CrCl/sub 3/ are separated from the UCl/sub 4/. The process is used when U is treated in a calutron, and composite solutions are produccd which contain dissolved products of stainless steel.

A pyrophosphate-responsive gadolinium(III) MRI contrast agent.

PubMed

Surman, Andrew J; Bonnet, Célia S; Lowe, Mark P; Kenny, Gavin D; Bell, Jimmy D; Tóth, Eva; Vilar, Ramon

2011-01-03

This study shows that the relaxivity and optical properties of functionalised lanthanide-DTPA-bis-amide complexes (lanthanide=Gd(3+) and Eu(3+) , DTPA=diethylene triamine pentaacetic acid) can be successfully modulated by addition of specific anions, without direct Ln(3+) /anion coordination. Zinc(II)-dipicolylamine moieties, which are known to bind strongly to phosphates, were introduced in the amide "arms" of these ligands, and the interaction of the resulting Gd-Zn(2) complexes with a range of anions was screened by using indicator displacement assays (IDAs). Considerable selectivity for polyphosphorylated species (such as pyrophosphate and adenosine-5'-triphosphate (ATP)) over a range of other anions (including monophosphorylated anions) was apparent. In addition, we show that pyrophosphate modulates the relaxivity of the gadolinium(III) complex, this modulation being sufficiently large to be observed in imaging experiments. To establish the binding mode of the pyrophosphate and gain insight into the origin of the relaxometric modulation, a series of studies including UV/Vis and emission spectroscopy, luminescence lifetime measurements in H(2) O and D(2) O, (17) O and (31) P NMR spectroscopy and nuclear magnetic resonance dispersion (NMRD) studies were carried out. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite

NASA Technical Reports Server (NTRS)

West, William C.; Whitacre, Jay F.; Leifer, Nicole; Greenbaum, Steve; Smart, Marshall; Bugga, Ratnakumar; Blanco, Mario; Narayanan, S. R.

2007-01-01

We have demonstrated a route to reversibly intercalate fluoride-anion receptor complexes in graphite via a nonaqueous electrochemical process. This approach may find application for a rechargeable lithium-fluoride dual-ion intercalating battery with high specific energy. The cell chemistry presented here uses graphite cathodes with LiF dissolved in a nonaqueous solvent through the aid of anion receptors. Cells have been demonstrated with reversible cathode specific capacity of approximately 80 mAh/g at discharge plateaus of upward of 4.8 V, with graphite staging of the intercalant observed via in situ synchrotron X-ray diffraction during charging. Electrochemical impedance spectroscopy and B-11 nuclear magnetic resonance studies suggest that cointercalation of the anion receptor with the fluoride occurs during charging, which likely limits the cathode specific capacity. The anion receptor type dictates the extent of graphite fluorination, and must be further optimized to realize high theoretical fluorination levels. To find these optimal anion receptors, we have designed an ab initio calculations-based scheme aimed at identifying receptors with favorable fluoride binding and release properties.

Photoelectron spectroscopic and computational study of (M-CO2)- anions, M = Cu, Ag, Au

NASA Astrophysics Data System (ADS)

Zhang, Xinxing; Lim, Eunhak; Kim, Seong K.; Bowen, Kit H.

2015-11-01

In a combined photoelectron spectroscopic and computational study of (M-CO2)-, M = Au, Ag, Cu, anionic complexes, we show that (Au-CO2)- forms both the chemisorbed and physisorbed isomers, AuCO 2- and Au-(CO2), respectively; that (Ag-CO2)- forms only the physisorbed isomer, Ag-(CO2); and that (Cu-CO2)- forms only the chemisorbed isomer, CuCO 2- . The two chemisorbed complexes, AuCO 2- and CuCO 2- , are covalently bound, formate-like anions, in which their CO2 moieties are significantly reduced. These two species are examples of electron-induced CO2 activation. The two physisorbed complexes, Au-(CO2) and Ag-(CO2), are electrostatically and thus weakly bound.

Copper complexes of anionic nitrogen ligands in the amidation and imidation of aryl halides.

PubMed

Tye, Jesse W; Weng, Zhiqiang; Johns, Adam M; Incarvito, Christopher D; Hartwig, John F

2008-07-30

Copper(I) imidate and amidate complexes of chelating N,N-donor ligands, which are proposed intermediates in copper-catalyzed amidations of aryl halides, have been synthesized and characterized by X-ray diffraction and detailed solution-phase methods. In some cases, the complexes adopt neutral, three-coordinate trigonal planar structures in the solid state, but in other cases they adopt an ionic form consisting of an L 2Cu (+) cation and a CuX 2 (-) anion. A tetraalkylammonium salt of the CuX 2 (-) anion in which X = phthalimidate was also isolated. Conductivity measurements and (1)H NMR spectra of mixtures of two complexes all indicate that the complexes exist predominantly in the ionic form in DMSO and DMF solutions. One complex was sufficiently soluble for conductance measurements in less polar solvents and was shown to adopt some degree of the ionic form in THF and predominantly the neutral form in benzene. The complexes containing dative nitrogen ligands reacted with iodoarenes and bromoarenes to form products from C-N coupling, but the ammonium salt of [Cu(phth) 2] (-) did not. Similar selectivities for stoichiometric and catalytic reactions with two different iodoarenes and faster rates for the stoichiometric reactions implied that the isolated amidate and imidate complexes are intermediates in the reactions of amides and imides with haloarenes catalyzed by copper complexes containing dative N,N ligands. These amidates and imidates reacted much more slowly with chloroarenes, including chloroarenes that possess more favorable reduction potentials than some bromoarenes and that are known to undergo fast dissociation of chloride from the chloroarene radical anion. The reaction of o-(allyloxy)iodobenzene with [(phen) 2Cu][Cu(pyrr) 2] results in formation of the C-N coupled product in high yield and no detectable amount of the 3-methyl-2,3-dihydrobenzofuran or 3-methylene-2,3-dihydrobenzofuran products that would be expected from a reaction that generated free radicals. These data and computed reaction barriers argue against mechanisms in which the haloarene reacts with a two-coordinate anionic copper species and mechanisms that start with electron transfer to generate a free iodoarene radical anion. Instead, these data are more consistent with mechanisms involving cleavage of the carbon-halogen bond within the coordination sphere of the metal.

Anion capture and sensing with cationic boranes: on the synergy of Coulombic effects and onium ion-centred Lewis acidity.

PubMed

Zhao, Haiyan; Leamer, Lauren A; Gabbaï, François P

2013-06-21

Stimulated by the growing importance and recognized toxicity of anions such as fluoride, cyanide and azides, we have, in the past few years, developed a family of Lewis acidic triarylboranes that can be used for the complexation of these anions in organic and protic solvents, including water. A central aspect of our approach lies in the decoration of the boranes with peripheral ammonium, phosphonium, sulfonium stibonium or telluronium groups. The presence of these cationic groups provides a Coulombic drive for the capture of the anion, leading to boranes that can be used in aqueous solutions where anion hydration and/or protonation are usually competitive. The anion affinity of these boranes can be markedly enhanced by narrowing the separation between the anion binding site (i.e. the boron atom) and the onium ion. In such systems, the latent Lewis acidity of the onium ion also plays a role as manifested by the formation of B-X→E (E = P, S, Sb, or Te; X = F, CN or N3) chelate motifs that provide additional stability to the resulting complexes. These effects, which are maximum in stibonium and telluronium boranes, show that the Lewis acidity of heavy onium ions can be exploited for anion coordination and capture. The significance of these advances is illustrated by the development of applications in anion sensing, fluorination chemistry and (18)F radiolabeling for positron emission tomography.

Isolation of (CO)1- and (CO2)1- radical complexes of rare earths via Ln(NR2)3/K reduction and [K2(18-crown-6)2]2+ oligomerization.

PubMed

Fang, Ming; Farnaby, Joy H; Ziller, Joseph W; Bates, Jefferson E; Furche, Filipp; Evans, William J

2012-04-11

Deep-blue solutions of Y(2+) formed from Y(NR(2))(3) (R = SiMe(3)) and excess potassium in the presence of 18-crown-6 at -45 °C under vacuum in diethyl ether react with CO at -78 °C to form colorless crystals of the (CO)(1-) radical complex, {[(R(2)N)(3)Y(μ-CO)(2)][K(2)(18-crown-6)(2)]}(n), 1. The polymeric structure contains trigonal bipyramidal [(R(2)N)(3)Y(μ-CO)(2)](2-) units with axial (CO)(1-) ligands linked by [K(2)(18-crown-6)(2)](2+) dications. Byproducts such as the ynediolate, [(R(2)N)(3)Y](2)(μ-OC≡CO){[K(18-crown-6)](2)(18-crown-6)}, 2, in which two (CO)(1-) anions are coupled to form (OC≡CO)(2-), and the insertion/rearrangement product, {(R(2)N)(2)Y[OC(═CH(2))Si(Me(2))NSiMe(3)]}[K(18-crown-6)], 3, are common in these reactions that give variable results depending on the specific reaction conditions. The CO reduction in the presence of THF forms a solvated variant of 2, the ynediolate [(R(2)N)(3)Y](2)(μ-OC≡CO)[K(18-crown-6)(THF)(2)](2), 2a. CO(2) reacts analogously with Y(2+) to form the (CO(2))(1-) radical complex, {[(R(2)N)(3)Y(μ-CO(2))(2)][K(2)(18-crown-6)(2)]}(n), 4, that has a structure similar to that of 1. Analogous (CO)(1-) and (OC≡CO)(2-) complexes of lutetium were isolated using Lu(NR(2))(3)/K/18-crown-6: {[(R(2)N)(3)Lu(μ-CO)(2)][K(2)(18-crown-6)(2)]}(n), 5, [(R(2)N)(3)Lu](2)(μ-OC≡CO){[K(18-crown-6)](2)(18-crown-6)}, 6, and [(R(2)N)(3)Lu](2)(μ-OC≡CO)[K(18-crown-6)(Et(2)O)(2)](2), 6a. © 2012 American Chemical Society

Using AFM to probe the complexation of DNA with anionic lipids mediated by Ca(2+): the role of surface pressure.

PubMed

Luque-Caballero, Germán; Martín-Molina, Alberto; Sánchez-Treviño, Alda Yadira; Rodríguez-Valverde, Miguel A; Cabrerizo-Vílchez, Miguel A; Maldonado-Valderrama, Julia

2014-04-28

Complexation of DNA with lipids is currently being developed as an alternative to classical vectors based on viruses. Most of the research to date focuses on cationic lipids owing to their spontaneous complexation with DNA. Nonetheless, recent investigations have revealed that cationic lipids induce a large number of adverse effects on DNA delivery. Precisely, the lower cytotoxicity of anionic lipids accounts for their use as a promising alternative. However, the complexation of DNA with anionic lipids (mediated by cations) is still in early stages and is not yet well understood. In order to explore the molecular mechanisms underlying the complexation of anionic lipids and DNA we proposed a combined methodology based on the surface pressure-area isotherms, Gibbs elasticity and Atomic Force Microscopy (AFM). These techniques allow elucidation of the role of the surface pressure in the complexation and visualization of the interfacial aggregates for the first time. We demonstrate that the DNA complexes with negatively charged model monolayers (DPPC/DPPS 4 : 1) only in the presence of Ca(2+), but is expelled at very high surface pressures. Also, according to the Gibbs elasticity plot, the complexation of lipids and DNA implies a whole fluidisation of the monolayer and a completely different phase transition map in the presence of DNA and Ca(2+). AFM imaging allows identification for the first time of specific morphologies associated with different packing densities. At low surface coverage, a branched net like structure is observed whereas at high surface pressure fibers formed of interfacial aggregates appear. In summary, Ca(2+) mediates the interaction between DNA and negatively charged lipids and also the conformation of the ternary system depends on the surface pressure. Such observations are important new generic features of the interaction between DNA and anionic lipids.

Metabolomic profiling of anionic metabolites by capillary electrophoresis mass spectrometry.

PubMed

Soga, Tomoyoshi; Igarashi, Kaori; Ito, Chiharu; Mizobuchi, Katsuo; Zimmermann, Hans-Peter; Tomita, Masaru

2009-08-01

We describe a sheath flow capillary electrophoresis time-of-flight mass spectrometry (CE-TOFMS) method in the negative mode using a platinum electrospray ionization (ESI) spray needle, which allows the comprehensive analysis of anionic metabolites. The material of the spray needle had significant effect on the measurement of anions. A stainless steel spray needle was oxidized and corroded at the anodic electrode due to electrolysis. The precipitation of iron oxides (rust) plugged the capillary outlet, resulting in shortened capillary lifetime. Many anionic metabolites also formed complexes with the iron oxides or migrating nickel ion, which was also generated by electrolysis and moved toward the cathode (the capillary inlet). The metal-anion complex formation significantly reduced detection sensitivity of the anionic compounds. The use of a platinum ESI needle prevented both oxidation of the metals and needle corrosion. Sensitivity using the platinum needle increased from several- to 63-fold, with the largest improvements for anions exhibiting high metal chelating properties such as carboxylic acids, nucleotides, and coenzyme A compounds. The detection limits for most anions were between 0.03 and 0.87 micromol/L (0.8 and 24 fmol) at a signal-to-noise ratio of 3. This method is quantitative, sensitive, and robust, and its utility was demonstrated by the analysis of the metabolites in the central metabolic pathways extracted from mouse liver.

Dehydroacetic Acid Derivatives Bearing Amide or Urea Moieties as Effective Anion Receptors.

PubMed

Bregović, Nikola; Cindro, Nikola; Bertoša, Branimir; Barišić, Dajana; Frkanec, Leo; Užarević, Krunoslav; Tomišić, Vladislav

2017-08-01

Derivatives of dehydroacetic acid comprising amide or urea subunits have been synthesized and their anion-binding properties investigated. Among a series of halides and oxyanions, the studied compounds selectively bind acetate and dihydrogen phosphate in acetonitrile and dimethyl sulfoxide. The corresponding complexation processes were characterized by means of 1 H NMR titrations, which revealed a 1:1 complex stoichiometry in most cases, with the exception of dihydrogen phosphate, which formed 2:1 (anion/ligand) complexes in acetonitrile. The complex stability constants were determined and are discussed with respect to the structural properties of the receptors, the hydrogen-bond-forming potential of the anions, and the characteristics of the solvents used. Based on the spectroscopic data and results of Monte Carlo simulations, the amide or urea groups were affirmed as the primary binding sites in all cases. The results of the computational methods indicate that an array of both inter- and intramolecular hydrogen bonds can form in the studied systems, and these were shown to play an important role in defining the overall stability of the complexes. Solubility measurements were carried out in both solvents and the thermodynamics of transfer from acetonitrile to dimethyl sulfoxide were characterized on a quantitative level. This has afforded a detailed insight into the impact of the medium on the complexation reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural study of surfactant-dependent interaction with protein

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

Mehan, Sumit; Aswal, Vinod K., E-mail: vkaswal@barc.gov.in; Kohlbrecher, Joachim

2015-06-24

Small-angle neutron scattering (SANS) has been used to study the complex structure of anionic BSA protein with three different (cationic DTAB, anionic SDS and non-ionic C12E10) surfactants. These systems form very different surfactant-dependent complexes. We show that the structure of protein-surfactant complex is initiated by the site-specific electrostatic interaction between the components, followed by the hydrophobic interaction at high surfactant concentrations. It is also found that hydrophobic interaction is preferred over the electrostatic interaction in deciding the resultant structure of protein-surfactant complexes.

Structural study of surfactant-dependent interaction with protein

NASA Astrophysics Data System (ADS)

Mehan, Sumit; Aswal, Vinod K.; Kohlbrecher, Joachim

2015-06-01

Small-angle neutron scattering (SANS) has been used to study the complex structure of anionic BSA protein with three different (cationic DTAB, anionic SDS and non-ionic C12E10) surfactants. These systems form very different surfactant-dependent complexes. We show that the structure of protein-surfactant complex is initiated by the site-specific electrostatic interaction between the components, followed by the hydrophobic interaction at high surfactant concentrations. It is also found that hydrophobic interaction is preferred over the electrostatic interaction in deciding the resultant structure of protein-surfactant complexes.

Loss of benzene to generate an enolate anion by a site-specific double-hydrogen transfer during CID fragmentation of o-alkyl ethers of ortho-hydroxybenzoic acids.

PubMed

Attygalle, Athula B; Bialecki, Jason B; Nishshanka, Upul; Weisbecker, Carl S; Ruzicka, Josef

2008-09-01

Collision-induced dissociation of anions derived from ortho-alkyloxybenzoic acids provides a facile way of producing gaseous enolate anions. The alkyloxyphenyl anion produced after an initial loss of CO(2) undergoes elimination of a benzene molecule by a double-hydrogen transfer mechanism, unique to the ortho isomer, to form an enolate anion. Deuterium labeling studies confirmed that the two hydrogen atoms transferred in the benzene loss originate from positions 1 and 2 of the alkyl chain. An initial transfer of a hydrogen atom from the C-1 position forms a phenyl anion and a carbonyl compound, both of which remain closely associated as an ion/neutral complex. The complex breaks either directly to give the phenyl anion by eliminating the neutral carbonyl compound, or to form an enolate anion by transferring a hydrogen atom from the C-2 position and eliminating a benzene molecule in the process. The pronounced primary kinetic isotope effect observed when a deuterium atom is transferred from the C-1 position, compared to the weak effect seen for the transfer from the C-2 position, indicates that the first transfer is the rate determining step. Quantum mechanical calculations showed that the neutral loss of benzene is a thermodynamically favorable process. Under the conditions used, only the spectra from ortho isomers showed peaks at m/z 77 for the phenyl anion and m/z 93 for the phenoxyl anion, in addition to that for the ortho-specific enolate anion. Under high collision energy, the ortho isomers also produce a peak at m/z 137 for an alkene loss. The spectra of meta and para compounds show a peak at m/z 92 for the distonic anion produced by the homolysis of the O-C bond. Moreover, a small peak at m/z 136 for a distonic anion originating from an alkyl radical loss allows the differentiation of para compounds from meta isomers.

Dipotassium tetra­kis­(thio­cyanato-κS)palladate(II)–(2,2′-bipyrimidine-κ2 N 1,N 1′)bis­(thio­cyanato-κS)palladium(II) (1/2)

PubMed Central

Ha, Kwang

2012-01-01

The asymmetric unit of the title compound, K2[Pd(NCS)4]·2[Pd(NCS)2(C8H6N4)], contains two crystallographically independent half-mol­ecules of the anionic PdII complex, two K+ cations and two independent neutral PdII complexes; an inversion centre is located at the centroid of each anionic complex. In the anionic complexes, each PdII ion is four-coordinated in an almost regular square-planar environment by four S atoms from four SCN− anions, and the PdS4 unit is exactly planar. In the neutral complexes, the PdII ion has a slightly distorted square-planar coordination environment defined by two pyrimidine N atoms derived from a chelating 2,2′-bipyrimidine ligand and two mutually cis S atoms from two SCN− anions. Both 2,2′-bipyrimidine ligands are almost planar [dihedral angle between the rings = 3.98 (16) and 4.57 (17)°] and also chelate to a potassium ion from their other two N atoms. In the crystal, the K+ ions inter­act with various S and N atoms of the ligands, forming a three-dimensional polymeric network, in which the shortest K⋯K contacts between the KN7S polyhedra are 4.4389 (17) and 4.4966 (18) Å. Intra- and inter­molecular C—H⋯S and C—H⋯N hydrogen bonds are also observed. PMID:22590117

The Effect of Sulphate Anions on the Ultrafine Titania Nucleation

NASA Astrophysics Data System (ADS)

Kotsyubynsky, Volodymyr O.; Myronyuk, Ivan F.; Chelyadyn, Volodymyr L.; Hrubiak, Andriy B.; Moklyak, Volodymyr V.; Fedorchenko, Sofia V.

2017-05-01

The phenomenological model of sulphate anions effect on the nanodispersed titania synthesis during hydrolysis of titanium tetrachloride was studied. It was proposed that both chelating and bridging bidentate complexes formation between sulphate anions and octahedrally coordinated [Ti(OH)h(OH2)6-h](4-h)+ mononers is the determinative factor for anatase phase nucleation.

Self-organizing layers from complex molecular anions

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

Warneke, Jonas; McBriarty, Martin E.; Riechers, Shawn L.

Ions are promising building blocks for tunable self-organizing materials with advanced technological applications. However, because of strong Coulomb attraction with counterions, the intrinsic properties of ions are difficult to exploit for preparation of bulk materials. Here, we report the precisely-controlled preparation of macroscopic surface layers by soft landing of mass selected complex anions which determine the self organization of the layers with their molecular properties. The family of halogenated dodecaborates [B12X12]2- (X = F, Cl, Br, I), in which the internal charge distribution between core and shell regions of the molecular ions systematically vary, was deposited on different self assembledmore » monolayer surfaces (SAMs) on gold at high coverage. Layers of anions were found to be stabilized by accumulation of neutral molecules. Different phases, self-organization mechanisms and optical properties were observed to depend upon the internal charge distribution of the deposited anions, the underlying surface and the coadsorbed molecules. This demonstrates rational control of the properties of anion based layers.« less

Dramatically stabilizing multiprotein complex structure in the absence of bulk water using tuned Hofmeister salts.

PubMed

Han, Linjie; Hyung, Suk-Joon; Ruotolo, Brandon T

2013-01-01

The role that water plays in the salt-based stabilization of proteins is central to our understanding of protein biophysics. Ion hydration and the ability of ions to alter water surface tension are typically invoked, along with direct ion-protein binding, to describe Hofmeister stabilization phenomena observed for proteins experimentally, but the relative influence of these forces has been extraordinarily difficult to measure directly. Recently, we have used gas-phase measurements of proteins and large multiprotein complexes, using a combination of innovative ion mobility (IM) and mass spectrometry (MS) techniques, to assess the ability of bound cations and anions to stabilize protein ions in the absence of the solvation forces described above. Our previous work has studied a broad set of 12 anions bound to a range of proteins and protein complexes, and while primarily motivated by the analytical challenges surrounding the gas-phase measurement of solution-phase relevant protein structures, our work has also lead to a detailed physical mechanism of anion-protein complex stabilization in the absence of bulk solvent. Our more-recent work has screened a similarly-broad set of cations for their ability to stabilize gas-phase protein structure, and we have discovered surprising differences between the operative mechanisms for cations and anions in gas-phase protein stabilization. In both cases, cations and anions affect protein stabilization in the absence of solvent in a manner that is generally reversed relative to their ability to stabilize the same proteins in solution. In addition, our evidence suggests that the relative solution-phase binding affinity of the anions and cations studied here is preserved in our gas-phase measurements, allowing us to study the influence of such interactions in detail. In this report, we collect and summarize such gas-phase measurements to distill a generalized picture of salt-based protein stabilization in the absence of bulk water. Further, we communicate our most recent efforts to study the combined effects of stabilizing cations and anions on gas-phase proteins, and identify those salts that bear anion/cation pairs having the strongest stabilizing influence on protein structures

Predictions of diagenetic reactions in the presence of organic acids

NASA Astrophysics Data System (ADS)

Harrison, Wendy J.; Thyne, Geoffrey D.

1992-02-01

Stability constants have been estimated for cation complexes with anions of monofunctional and difunctional acids (combinations of Ca, Mg, Fe, Al, Sr, Mn, U, Th, Pb, Cu, Zn with formate, acetate, propionate, oxalate, malonate, succinate, and salicylate) between 0 and 200°C. Difunctional acid anions form much more stable complexes than monofunctional acid anions with aluminum; the importance of the aluminum-acetate complex is relatively minor in comparison to aluminum oxalate and malonate complexes. Divalent metal cations such as Mg, Ca, and Fe form more stable complexes with acetate than with difunctional acid anions. Aluminum-oxalate can dominate the species distribution of aluminum under acidic pH conditions, whereas the divalent cation-acetate and oxalate complexes rarely account for more than 60% of the total dissolved cation, and then only in more alkaline waters. Mineral thermodynamic affinities were calculated using the reaction path model EQ3/6 for waters having variable organic acid anion (OAA) contents under conditions representative of those found during normal burial diagenesis. The following scenarios are possible: 1) K-feldspar and albite are stable, anorthite dissolves 2) All feldpars are stable 3) Carbonates can be very unstable to slightly unstable, but never increase in stability. Organic acid anions are ineffective at neutral to alkaline pH in modifying stabilities of aluminosilicate minerals whereas the anions are variably effective under a wide range of pH in modifying carbonate mineral stabilities. Reaction path calculations demonstrate that the sequence of mineral reactions occurring in an arkosic sandstone-fluid system is only slightly modified by the presence of OAA. A spectrum of possible sandstone alteration mineralogies can be obtained depending on the selected boundary conditions: EQ3/6 predictions include quartz overgrowth, calcite replacement of plagioclase, albitization of plagioclase, and the formation of porosity-occluding calcite cement, smectite, and illite, all of which are commonly documented in rocks. Under some circumstances, OAA-bearing waters are less effective at producing porosity in an arkosic sandstone than are OAA-free waters. In the scenarios modeled in this study the role of OAA in fluid-rock interactions is to contribute to the total alteration assemblage but not necessarily to dominate it, except under exceptional circumstances that might include, for example, hydrocarbon contaminant plumes in aquifers, wetland environments, and within hydrocarbon source-rocks.

Method for the production of uranium chloride salt

DOEpatents

Westphal, Brian R.; Mariani, Robert D.

2013-07-02

A method for the production of UCl.sub.3 salt without the use of hazardous chemicals or multiple apparatuses for synthesis and purification is provided. Uranium metal is combined in a reaction vessel with a metal chloride and a eutectic salt- and heated to a first temperature under vacuum conditions to promote reaction of the uranium metal with the metal chloride for the production of a UCl.sub.3 salt. After the reaction has run substantially to completion, the furnace is heated to a second temperature under vacuum conditions. The second temperature is sufficiently high to selectively vaporize the chloride salts and distill them into a condenser region.

Low-temperature synthesis of actinide tetraborides by solid-state metathesis reactions

DOEpatents

Lupinetti, Anthony J [Los Alamos, NM; Garcia, Eduardo [Los Alamos, NM; Abney, Kent D [Los Alamos, NM

2004-12-14

The synthesis of actinide tetraborides including uranium tetraboride (UB.sub.4), plutonium tetraboride (PuB.sub.4) and thorium tetraboride (ThB.sub.4) by a solid-state metathesis reaction are demonstrated. The present method significantly lowers the temperature required to .ltoreq.850.degree. C. As an example, when UCl.sub.4 is reacted with an excess of MgB.sub.2, at 850.degree. C., crystalline UB.sub.4 is formed. Powder X-ray diffraction and ICP-AES data support the reduction of UCl.sub.3 as the initial step in the reaction. The UB.sub.4 product is purified by washing water and drying.

Effects of temperature, concentration, and uranium chloride mixture on zirconium electrochemical studies in LiClsbnd KCl eutectic salt

NASA Astrophysics Data System (ADS)

Hoover, Robert O.; Yoon, Dalsung; Phongikaroon, Supathorn

2016-08-01

Experimental studies were performed to provide measurement and analysis of zirconium (Zr) electrochemistry in LiClsbnd KCl eutectic salt at different temperatures and concentrations using cyclic voltammetry (CV). An additional experimental set with uranium chloride added into the system forming UCl3sbnd ZrCl4sbnd LiClsbnd KCl was performed to explore the general behavior of these two species together. Results of CV experiments with ZrCl4 show complicated cathodic and anodic peaks, which were identified along with the Zr reactions. The CV results reveal that diffusion coefficients (D) of ZrCl4 and ZrCl2 as the function of temperature can be expressed as DZr(IV) = 0.00046exp(-3716/T) and DZr(II) = 0.027exp(-5617/T), respectively. The standard rate constants and apparent standard potentials of ZrCl4 at different temperatures were calculated. Furthermore, the results from the mixture of UCl3 and ZrCl4 indicate that high concentrations of UCl3 hide the features of the smaller concentration of ZrCl4 while Zr peaks become prominent as the concentration of ZrCl4 increases.

Using a statistical process control chart during the quality assessment of cancer registry data.

PubMed

Myles, Zachary M; German, Robert R; Wilson, Reda J; Wu, Manxia

2011-01-01

Statistical process control (SPC) charts may be used to detect acute variations in the data while simultaneously evaluating unforeseen aberrations that may warrant further investigation by the data user. Using cancer stage data captured by the Summary Stage 2000 (SS2000) variable, we sought to present a brief report highlighting the utility of the SPC chart during the quality assessment of cancer registry data. Using a county-level caseload for the diagnosis period of 2001-2004 (n=25,648), we found the overall variation of the SS2000 variable to be in control during diagnosis years of 2001 and 2002, exceeded the lower control limit (LCL) in 2003, and exceeded the upper control limit (UCL) in 2004; in situ/localized stages were in control throughout the diagnosis period, regional stage exceeded UCL in 2004, and distant stage exceeded the LCL in 2001 and the UCL in 2004. Our application of the SPC chart with cancer registry data illustrates that the SPC chart may serve as a readily available and timely tool for identifying areas of concern during the data collection and quality assessment of central cancer registry data.

Covalent Polymers Containing Discrete Heterocyclic Anion Receptors

PubMed Central

Rambo, Brett M.; Silver, Eric S.; Bielawski, Christopher W.; Sessler, Jonathan L.

2010-01-01

This chapter covers recent advances in the development of polymeric materials containing discrete heterocyclic anion receptors, and focuses on advances in anion binding and chemosensor chemistry. The development of polymers specific for anionic species is a relatively new and flourishing area of materials chemistry. The incorporation of heterocyclic receptors capable of complexing anions through non-covalent interactions (e.g., hydrogen bonding and electrostatic interactions) provides a route to not only sensitive but also selective polymer materials. Furthermore, these systems have been utilized in the development of polymers capable of extracting anionic species from aqueous environments. These latter materials may lead to advances in water purification and treatment of diseases resulting from surplus ions. PMID:20871791

Amplification of anion sensing by disulfide functionalized ferrocene and ferrocene-calixarene receptors adsorbed onto gold surfaces.

PubMed

Cormode, David P; Evans, Andrew J; Davis, Jason J; Beer, Paul D

2010-07-28

A disulfide functionalized bis-ferrocene urea acyclic receptor and disulfide functionalized mono- and bis-ferrocene amide and urea appended upper rim calix[4]arene receptors were prepared for the fabrication of SAM redox-active anion sensors. 1H NMR and diffusive voltammetric anion recognition investigations revealed each receptor to be capable of complexing and electrochemically sensing anions via cathodic perturbations of the respective receptor's ferrocene/ferrocenium redox couple. SAMs of a ferrocene urea receptor 3 and ferrocene urea calixarene receptor 17 exhibited significant enhanced magnitudes of cathodic response upon anion addition as compared to observed diffusive perturbations. SAMs of 17 were demonstrated to sense the perrhenate anion in aqueous solutions.

Aza-Bambusurils En Route to Anion Transporters.

PubMed

Singh, Mandeep; Solel, Ephrath; Keinan, Ehud; Reany, Ofer

2016-06-20

Previous calculations of anion binding with various bambusuril analogs predicted that the replacement of oxygen by nitrogen atoms to produce semiaza-bambus[6]urils would award these new cavitands with multiple anion binding properties. This study validates the hypothesis by efficient synthesis, crystallography, thermogravimetric analysis and calorimetry. These unique host molecules are easily accessible from the corresponding semithio-bambusurils in a one-pot reaction, which converts a single anion receptor into a potential anion channel. Solid-state structures exhibit simultaneous accommodation of three anions, linearly positioned within the cavity along the main symmetry axis. The ability to hold anions at a short distance of about 4 Å is reminiscent of natural chloride channels in E. coli, which exhibit similar distances between their adjacent anion binding sites. The calculated transition-state energy for double-anion movement through the channel suggests that although these host-guest complexes are thermodynamically stable they enjoy high kinetic flexibility to render them efficient anion channels. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

N-acetylglyoxylic amide bearing a nitrophenyl group as anion receptors: NMR and X-ray investigations on anion binding and selectivity

NASA Astrophysics Data System (ADS)

Suryanti, Venty; Bhadbhade, Mohan; Black, David StC; Kumar, Naresh

2017-10-01

N-Nitrophenylglyoxylic amides 1 and 2 in presence of tetrabutylammonium cation (TBA) act as receptors for anions HSO4-, Cl-, Br- and NO3- as investigated by NMR studies. The receptors formed 1:1 host-guest complexes in solution. X-ray structure of 1 along with TBA that bind a chloride anion is reported. Molecule 1 showed the highest selectivity for HSO4- anion over others measured. X-ray structure of the bound Cl- revealed a pocket containing the anion making strong (Nsbnd H⋯Cl) and weak hydrogen bonds (Csbnd H⋯Cl) that contribute to the recognition of the chloride anion. Nsbnd H and Csbnd H hydrogen bonds resulted in a relatively strong binding for chloride ions.

Anion-induced reconstitution of a self-assembling system to express a chloride-binding Co10L15 pentagonal prism.

PubMed

Riddell, Imogen A; Smulders, Maarten M J; Clegg, Jack K; Hristova, Yana R; Breiner, Boris; Thoburn, John D; Nitschke, Jonathan R

2012-09-01

Biochemical systems are adaptable, capable of reconstitution at all levels to achieve the functions associated with life. Synthetic chemical systems are more limited in their ability to reorganize to achieve new functions; they can reconfigure to bind an added substrate (template effect) or one binding event may modulate a receptor's affinity for a second substrate (allosteric effect). Here we describe a synthetic chemical system that is capable of structural reconstitution on receipt of one anionic signal (perchlorate) to create a tight binding pocket for another anion (chloride). The complex, barrel-like structure of the chloride receptor is templated by five perchlorate anions. This second-order templation phenomenon allows chemical networks to be envisaged that express more complex responses to chemical signals than is currently feasible.

The 2:2 complex of pyridine betaine with squaric acid studied by X-ray diffraction, FTIR, NMR and DTG methods

NASA Astrophysics Data System (ADS)

Dega-Szafran, Z.; Dutkiewicz, G.; Kosturkiewicz, Z.

2012-12-01

The 2:2 ionic crystals of pyridine betaine (PyB) with squaric acid (H2SQ) belong to monoclinic space group C2/c. Supramolecular structure of the crystals investigated is formed by the loss of one proton from every two squaric acid molecules. Pyridine betaines form a homoconjugated cation, [(PyB)2H]+, through a short, symmetric COO⋯H⋯OOC hydrogen bond of 2.463(2) Å. The hydrogen squarate anions are linked into a homoconjugated anion, [(HSQ)2H]-, by a short symmetric, non-linear O⋯H⋯O hydrogen bond of 2.453(1) Å, with the H-atom located on the twofold axis. The bis(hydrogen squarate)hydrogen anions are linked into a centrosymmetric cyclic dimer by two identical asymmetric Osbnd H⋯O hydrogen bonds of 2.536(2) Å. The (PyB)2H cation and cyclic dimer of hydrogen squarate anions are placed around two different systems of inversion centers in the unit cell. The FTIR spectrum is consistent with the X-ray results. The 13C chemical shift of the Cdbnd O atom confirms the presence of the hydrogen squarate anion in the complex studied. The complex decomposed in three thermal stages.

Carbon Chain Anions and the Growth of Complex Organic Molecules in Titan’s Ionosphere

NASA Astrophysics Data System (ADS)

Desai, R. T.; Coates, A. J.; Wellbrock, A.; Vuitton, V.; Crary, F. J.; González-Caniulef, D.; Shebanits, O.; Jones, G. H.; Lewis, G. R.; Waite, J. H.; Cordiner, M.; Taylor, S. A.; Kataria, D. O.; Wahlund, J.-E.; Edberg, N. J. T.; Sittler, E. C.

2017-08-01

Cassini discovered a plethora of neutral and ionized molecules in Titan’s ionosphere including, surprisingly, anions and negatively charged molecules extending up to 13,800 u q-1. In this Letter, we forward model the Cassini electron spectrometer response function to this unexpected ionospheric component to achieve an increased mass resolving capability for negatively charged species observed at Titan altitudes of 950-1300 km. We report on detections consistently centered between 25.8 and 26.0 u q-1 and between 49.0-50.1 u q-1 which are identified as belonging to the carbon chain anions, CN-/C3N- and/or C2H-/C4H-, in agreement with chemical model predictions. At higher ionospheric altitudes, detections at 73-74 u q-1 could be attributed to the further carbon chain anions C5N-/C6H- but at lower altitudes and during further encounters extend over a higher mass/charge range. This, as well as further intermediary anions detected at >100 u, provide the first evidence for efficient anion chemistry in space involving structures other than linear chains. Furthermore, at altitudes below <1100 km, the low-mass anions (<150 u q-1) were found to deplete at a rate proportional to the growth of the larger molecules, a correlation that indicates the anions are tightly coupled to the growth process. This study adds Titan to an increasing list of astrophysical environments where chain anions have been observed and shows that anion chemistry plays a role in the formation of complex organics within a planetary atmosphere as well as in the interstellar medium.

Cytochrome b5 reductase is the component from neuronal synaptic plasma membrane vesicles that generates superoxide anion upon stimulation by cytochrome c.

PubMed

Samhan-Arias, Alejandro K; Fortalezas, Sofia; Cordas, Cristina M; Moura, Isabel; Moura, José J G; Gutierrez-Merino, Carlos

2018-05-01

In this work, we measured the effect of cytochrome c on the NADH-dependent superoxide anion production by synaptic plasma membrane vesicles from rat brain. In these membranes, the cytochrome c stimulated NADH-dependent superoxide anion production was inhibited by antibodies against cytochrome b 5 reductase linking the production to this enzyme. Measurement of the superoxide anion radical generated by purified recombinant soluble and membrane cytochrome b 5 reductase corroborates the production of the radical by different enzyme isoforms. In the presence of cytochrome c, a burst of superoxide anion as well as the reduction of cytochrome c by cytochrome b 5 reductase was measured. Complex formation between both proteins suggests that cytochrome b 5 reductase is one of the major partners of cytochrome c upon its release from mitochondria to the cytosol during apoptosis. Superoxide anion production and cytochrome c reduction are the consequences of the stimulated NADH consumption by cytochrome b 5 reductase upon complex formation with cytochrome c and suggest a major role of this enzyme as an anti-apoptotic protein during cell death. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Steric Effects on the Binding of Phosphate and Polyphosphate Anions by Zinc(II) and Copper(II) Dinuclear Complexes of m-Xylyl-bis-cyclen.

PubMed

Esteves, Catarina V; Esteban-Gómez, David; Platas-Iglesias, Carlos; Tripier, Raphaël; Delgado, Rita

2018-05-11

The triethylbenzene-bis-cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) compound (tbmce) was designed with an imposed structural rigidity at the m-xylyl spacer to be compared to a less restrained and known parent compound (bmce). The framework of both compounds differs only in the substituents of the m-xylyl spacer. The study was centered in the differences observed in the acid-base reactions of both compounds, their copper(II) and zinc(II) complexation behaviors, as well as in the uptake of phosphate and polyphosphate anions (HPPi 3- , ATP 4- , ADP 3- , AMP 2- , PhPO 4 2- , and HPO 4 2- ). On the one hand, the acid-base reactions showed lower values for the third and fourth protonation constants of tbmce than for bmce, suggesting that the ethyl groups of the spacer in tbmce force the two cyclen units to more conformational restricted positions. On the other hand, the stability constant values for copper(II) and zinc(II) complexes revealed that bmce is a better chelator than tbmce pointing out to additional conformational restraints imposed by the triethylbenzene spacer. The binding studies of phosphates by the dinuclear copper(II) and zinc(II) complexes showed much smaller effective association constants for the dicopper complexes. Single-crystal X-ray and computational (density functional theory) studies suggest that anion binding promotes the formation of tetranuclear entities in which anions are bridging the metal centers. Our studies also revealed the dinuclear zinc(II) complex of bmce as a promising receptor for phosphate anions, with the largest effective association constant of 5.94 log units being observed for the formation of [Zn 2 bmce(HPPi)] + . Accordingly, a colorimetric study via an indicator displacement assay to detect phosphates in aqueous solution found that the [Zn 2 bmce] 4+ complex acts as the best receptor for pyrophosphate displaying a detection limit of 2.5 nM by changes visible to naked eye.

Anionic tantalum dihydride complexes: heterobimetallic coupling reactions and reactivity toward small-molecule activation.

PubMed

Ostapowicz, Thomas G; Fryzuk, Michael D

2015-03-02

The anionic dihydride complex [Cp2TaH2](-) was synthesized as a well-defined molecular species by deprotonation of Cp2TaH3 while different solubilizing agents, such as [2.2.2]cryptand and 18-crown-6, were applied to encapsulate the alkali-metal counterion. The ion pairs were characterized by multiple spectroscopic methods as well as X-ray crystallography, revealing varying degrees of interaction between the hydride ligands of the anion and the respective countercation in solution and in the solid state. The [Cp2TaH2](-) complex anion shows slow exchange of the hydride ligands when kept under a D2 atmosphere, but a very fast reaction is observed when [Cp2TaH2](-) is reacted with CO2, from which Cp2TaH(CO) is obtained as the tantalum-containing reaction product, along with inorganic salts. Furthermore, [Cp2TaH2](-) can act as a synthon in heterobimetallic coupling reactions with transition-metal halide complexes. Thus, the heterobimetallic complexes Cp2Ta(μ-H)2Rh(dippp) and Cp2Ta(μ-H)2Ru(H)(CO)(P(i)Pr3)2 were synthesized and characterized by various spectroscopies and via single-crystal X-ray diffraction. The new hydride bridged tantalum-rhodium heterobimetallic complex is cleaved under a CO atmosphere to yield mononuclear species and slowly exchanges protons and hydride ligands when exposed to D2 gas.

Synthesis, characterization, and reactivity of the first uranium metallocene 1,2 bis(diphenylphosphino)acetylene complexes.

DOE PAGES

Pagano, Justin Kane; Scott, Brian Lindley; Kiplinger, Jaqueline Loetsch

2018-06-09

Two new uranium metallacyclopropenes, (C 5Me 4R) 2U(η 2-Ph 2PC=CPPh 2) (R = Me, Et) were prepared by reducing the corresponding (C 5Me 4R) 2UCl 2 complexes with KC 8 in the presence of 1,2-bis(diphenylphosphino)acetylene (Ph 2P–C≡C–PPh 2). Both compounds were fully characterized by a combination of elemental analysis and multinuclear NMR, UV–visible–NIR, and IR spectroscopies. Differences in the electronic spectra of these novel compounds and the known (C 5Me 5) 2U(η 2-Me 3SiC=CSiMe 3) are discussed. Finally, also presented is the solid-state structure of (C 5Me 4Et) 2U(η 2-Ph 2PC=CPPh 2), which reveals significant distortions of the coordinated 1,2-bis(diphenylphosphino)acetylenemore » (Ph 2P–C≡C–PPh 2) ligand.« less

Synthesis, characterization, and reactivity of the first uranium metallocene 1,2 bis(diphenylphosphino)acetylene complexes.

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

Pagano, Justin Kane; Scott, Brian Lindley; Kiplinger, Jaqueline Loetsch

Two new uranium metallacyclopropenes, (C 5Me 4R) 2U(η 2-Ph 2PC=CPPh 2) (R = Me, Et) were prepared by reducing the corresponding (C 5Me 4R) 2UCl 2 complexes with KC 8 in the presence of 1,2-bis(diphenylphosphino)acetylene (Ph 2P–C≡C–PPh 2). Both compounds were fully characterized by a combination of elemental analysis and multinuclear NMR, UV–visible–NIR, and IR spectroscopies. Differences in the electronic spectra of these novel compounds and the known (C 5Me 5) 2U(η 2-Me 3SiC=CSiMe 3) are discussed. Finally, also presented is the solid-state structure of (C 5Me 4Et) 2U(η 2-Ph 2PC=CPPh 2), which reveals significant distortions of the coordinated 1,2-bis(diphenylphosphino)acetylenemore » (Ph 2P–C≡C–PPh 2) ligand.« less

Evidence of Multiple Sorption Modes in Layered Double Hydroxides Using Mo As Structural Probe.

PubMed

Ma, Bin; Fernandez-Martinez, Alejandro; Grangeon, Sylvain; Tournassat, Christophe; Findling, Nathaniel; Claret, Francis; Koishi, Ayumi; Marty, Nicolas C M; Tisserand, Delphine; Bureau, Sarah; Salas-Colera, Eduardo; Elkaïm, Erik; Marini, Carlo; Charlet, Laurent

2017-05-16

Layered double hydroxides (LDHs) have been considered as effective phases for the remediation of aquatic environments, to remove anionic contaminants mainly through anion exchange mechanisms. Here, a combination of batch isotherm experiments and X-ray techniques was used to examine molybdate (MoO 4 2- ) sorption mechanisms on CaAl LDHs with increasing loadings of molybdate. Advanced modeling of aqueous data shows that the sorption isotherm can be interpreted by three retention mechanisms, including two types of edge sites complexes, interlayer anion exchange, and CaMoO 4 precipitation. Meanwhile, Mo geometry evolves from tetrahedral to octahedral on the edge, and back to tetrahedral coordination at higher Mo loadings, indicated by Mo K-edge X-ray absorption spectra. Moreover, an anion exchange process on both CaAl LDHs was followed by in situ time-resolved synchrotron-based X-ray diffraction, remarkably agreeing with the sorption isotherm. This detailed molecular view shows that different uptake mechanisms-edge sorption, interfacial dissolution-reprecipitation-are at play and control anion uptake under environmentally relevant conditions, which is contrast to the classical view of anion exchange as the primary retention mechanism. This work puts all these mechanisms in perspective, offering a new insight into the complex interplay of anion uptake mechanisms by LDH phases, by using changes in Mo geometry as powerful molecular-scale probe.

Synthesis of thin film containing 4-amino-1,2,4-triazole iron(II) complexes

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

Onggo, Djulia, E-mail: djulia@Chem.itb.ac.id

The Iron(II) complex with 4-amino-1,2,4 triazole (NH{sub 2}-trz) ligand has potential applications as smart material since the compounds show a distinct color change from lilac at low temperature to colorless at high temperature. The lilac color of the complex represent the diamagnetic low spin state while the colorless correspond to the paramagnetic high spin state of iron(II). The transition between the two states could be tuned by changing the anionic group. Generally, the complex was synthesized directly from aqueous solution of iron(II) salt with considerable amounts of NH{sub 2}-trz solution produced solid powder compound. For application as an electronic molecularmore » device, the complex should be obtained as a thin film. The transparent [Fe(NH{sub 2}trz){sub 3}]-Nafion film has been successfully obtained, however, no anion variation can be produced since the nafion is an anionic resin. In this work, the [Fe(NH{sub 2}trz){sub 3}]-complexes with several anions have been synthesized inside nata de coco membrane that commonly used as a medium for deposition metal nano-particles. After drying the membrane containing the complex became a thin film. At room temperature, the film containing iron(II) complexes of sulphate and nitrate salts show lilac color, similar to that of the original complexes in the powder form. On heating, the color of the complex film changed to colorless and this color change was observed reversibly. In contrast, the films containing perchlorate and tetrafluoroborate iron(II) complexes are colorless at room temperature and changed to lilac on cooling. The significant color changing of the iron(II)complexes in the nata de coco film can be used for demonstration thermo chromic effect of smart materials with relatively small amount of the compounds.« less

p-Dimethylaminobenzamide as an ICT dual fluorescent neutral receptor for anions under proton coupled electron transfer sensing mechanism

NASA Astrophysics Data System (ADS)

Wu, Fang-Ying; Jiang, Yun-Bao

2002-04-01

The intramolecular charge transfer (ICT) dual fluorescence of p-dimethylaminobenzamide (DMABA) in acetonitrile was found to show highly sensitive response to HSO 4- over several other anions such as H 2PO 4-,AcO - and ClO 4-. In the presence of bisulfate anion the dual fluorescence intensity ratio and the total intensity of DMABA decreased while the dual emission band positions remained unchanged. Absorption titration indicated that a 1:1 hydrogen bonding complex was formed between bisulfate anion and DMABA, which gave a binding constant of 2.02×10 4 mol-1 l that is two orders of magnitude higher than those for other anions. The obvious isotopic effect observed in the fluorescence quenching [ K SV( HSO4-)/K SV( DSO4-)=1.63 ] suggests that the hydrogen atom moving is an important reaction coordinate. It was assumed that the dual fluorescence response was due to proton coupled electron transfer mediated by hydrogen bonds within the 1:1 HSO 4--DMABA hydrogen-bonding complex.

Chemical mechanism of the Gram stain and synthesis of a new electron-opaque marker for electron microscopy which replaces the iodine mordant of the stain.

PubMed Central

Davies, J A; Anderson, G K; Beveridge, T J; Clark, H C

1983-01-01

Crystal violet (hexamethyl-para-rosaniline chloride) interacts with aqueous KI-I2 during the Gram stain via a simple metathetical anion exchange to produce a chemical precipitate. There is an apparent 1:1 stoichiometry between anion (I-) and cation (hexamethyl-para-rosaniline+) during the reaction and, since the small chloride anion is replaced by the bulkier iodide, the complex formed becomes insoluble in water. It is this same precipitate which forms in the cellular substance of bacteria (both gram-positive and gram-negative types) and which initiates the Gram reaction. Potassium trichloro(eta 2-ethylene)-platinum(II), as an electronopaque marker for electron microscopy, was chemically synthesized, and it produced an anion in aqueous solution which was compatible with crystal violet for the Gram stain. It interacted with crystal violet in a similar manner as iodide to produce an insoluble complex which was chemically and physically analogous to the dye-iodide precipitate. This platinum anion therefore allows the Gram staining mechanism to be followed by electron microscopy. Images PMID:6195147

Silver(i) complexes with 1'-(diphenylphosphino)-1-cyanoferrocene: the art of improvisation in coordination.

PubMed

Škoch, Karel; Uhlík, Filip; Císařová, Ivana; Štěpnička, Petr

2016-06-28

1'-(Diphenylphosphino)-1-cyanoferrocene () reacts with silver(i) halides at a 1 : 1 metal-to-ligand ratio to afford the heterocubane complexes [Ag(μ3-X)(-κP)]4, where X = Cl (), Br (), and I (). In addition, the reaction with AgCl with 2 equiv. of leads to chloride-bridged dimer [(μ-Cl)2{Ag(-κP)2}2] () and, presumably, also to [(μ(P,N)-){AgCl(-κP)}]2 (). While similar reactions with AgCN furnished only the insoluble coordination polymer [(-κP)2Ag(NC)Ag(CN)]n (), those with AgSCN afforded the heterocubane [Ag(-κP)(μ-SCN-S,S,N)]4 () and the thiocyanato-bridged disilver(i) complex [Ag(-κP)2(μ-SCN-S,N)]2 (), thereby resembling reactions in the AgCl- system. Attempted reactions with AgF led to ill-defined products, among which [Ag(-κP)2(μ-HF2)]2 () and [(μ-SiF6){Ag(-κP)2}2] () could be identified. The latter compound was prepared also from Ag2[SiF6] and . Reactions between and AgClO4 or Ag[BF4] afforded disilver complexes [(μ(P,N)-)Ag(ClO4-κO)]2 () and [(μ(P,N)-)Ag(BF4-κF)]2 () featuring pseudolinear Ag(i) centers that are weakly coordinated by the counter anions. A similar reaction with Ag[SbF6] followed by crystallization from ethyl acetate produced an analogous complex, albeit with coordinated solvent, [(μ(P,N)-)Ag(AcOEt-κO)]2[SbF6]2 (). Ultimately, a compound devoid of any additional ligands at the Ag(i) centers, [(μ(P,N)-)Ag]2[B(C6H3(CF3)2-3,5)4]2 (), was obtained from the reaction of with silver(i) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The reaction of Ag[BF4] with two equivalents of produced unique coordination polymer [Ag(-κP)(μ(P,N)-)]n[BF4]n (), the structure of which contained one of the phosphinoferrocene ligands coordinated as a P,N-chelate and the other forming a bridge to an adjacent Ag(i) center. All of these compounds were structurally characterized by single-crystal X-ray crystallography, revealing that the lengths of the bonds between silver and its anionic ligand(s) typically exceed the sum of the respective covalent radii, which is in line with the results of theoretical calculations at the density-functional theory (DFT) level, suggesting that standard covalent dative bonds are formed between silver and phosphorus (soft acid/soft base interactions) while the interactions between silver and the ligand's nitrile group (if coordinated) or the supporting anion are of predominantly electrostatic nature.

Antimicrobial Activity of ε-Poly-l-lysine after Forming a Water-Insoluble Complex with an Anionic Surfactant.

PubMed

Ushimaru, Kazunori; Hamano, Yoshimitsu; Katano, Hajime

2017-04-10

ε-Poly-l-lysine (ε-PL) is one of the few homopoly(amino-acid)s occurring in nature. ε-PL, which possesses multiple amino groups, is highly soluble in water, where it forms the antimicrobial polycationic chain (PL n+ ). Although the high water-solubility is advantageous for the use of ε-PL as a food preservative, it has limited the applicability of ε-PL as a biopolymer plastic. Here, we report on the preparation and availability of a water-insoluble complex formed with PL n+ and an anionic surfactant, bis(2-ethylhexyl) sulfosuccinate (BEHS - , is also commercialized as AOT) anion. The PL n+ /BEHS - -complex, which is soluble in organic solvents, was successfully used as a coating material for a cellulose acetate membrane to create a water-resistant antimicrobial membrane. In addition, the thermoplastic PL n+ /BEHS - -complex was able to be uniformly mixed with polypropylene by heating, resulting in materials exhibiting antimicrobial activities.

Phosphorus dendrimers and photodynamic therapy. Spectroscopic studies on two dendrimer-photosensitizer complexes: Cationic phosphorus dendrimer with rose bengal and anionic phosphorus dendrimer with methylene blue.

PubMed

Dabrzalska, Monika; Zablocka, Maria; Mignani, Serge; Majoral, Jean Pierre; Klajnert-Maculewicz, Barbara

2015-08-15

Dendrimers due to their unique architecture may play an important role in drug delivery systems including chemotherapy, gene therapy and recently, photodynamic therapy as well. We investigated two dendrimer-photosensitizer systems in context of potential use of these systems in photodynamic therapy. The mixtures of an anionic phosphorus dendrimer of the second generation and methylene blue were studied by UV-vis spectroscopy while that of a cationic phosphorus dendrimer (third generation) and rose bengal were investigated by spectrofluorimetric methods. Spectroscopic analysis of these two systems revealed the formation of dendrimer-photosensitizer complexes via electrostatic interactions as well as π stacking. The stoichiometry of the rose bengal-cationic dendrimer complex was estimated to be 7:1 and 9:1 for the methylene blue-anionic dendrimer complex. The results suggest that these polyanionic or polycationic phosphorus dendrimers can be promising candidates as carriers in photodynamic therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

Complexes of carboxyl-containing polymer and monosubstituted bipyridinium salts

NASA Astrophysics Data System (ADS)

Merekalova, N. D.; Bondarenko, G. N.; Krylsky, D. W.; Zakirov, M. I.; Talroze, R. V.

2013-09-01

Semi-empirical PM3 method for the quantum calculations of molecular electronic structure based on NDDO integral approximation is used to investigate the complex formation of monosubstituted 4,4‧-bipyridinium salts BpyR (Hal) containing a halide anion interacting with the quaternary nitrogen atom and carboxylic group of the two-units construct. Significant effect of the BpyR (Hal) electronic structure is unveiled that contributes in two different structures of these salts, namely, partial charge transfer complex and ion pair structure, both having stable energy minima. We demonstrate that (i) the structure of the N-substituent modulates the energy and electronic characteristics of monosubstituted salts BpyR with chlorine and bromine anions and (ii) the coulomb interactions between quaternary N-atom, halogen anion, and the proton of carboxylic group stimulate the transformation of the charge transfer complex into the ion pair structure. Results of calculations are compared with the experimental FTIR spectra of blends of BpyR(Hal) with Eudragit copolymer.

Unusual Complex Formation and Chemical Reaction of Haloacetate Anion on the Exterior Surface of Cucurbit[6]uril in the Gas Phase

NASA Astrophysics Data System (ADS)

Choi, Tae Su; Ko, Jae Yoon; Heo, Sung Woo; Ko, Young Ho; Kim, Kimoon; Kim, Hugh I.

2012-10-01

Noncovalent interactions of cucurbit[6]uril (CB[6]) with haloacetate and halide anions are investigated in the gas phase using electrospray ionization ion mobility mass spectrometry. Strong noncovalent interactions of monoiodoacetate, monobromoacetate, monochloroacetate, dichloroacetate, and trichloroacetate on the exterior surface of CB[6] are observed in the negative mode electrospray ionization mass spectra. The strong binding energy of the complex allows intramolecular SN2 reaction of haloacetate, which yields externally bound CB[6]-halide complex, by collisional activation. Utilizing ion mobility technique, structures of exteriorly bound CB[6] complexes of haloacetate and halide anions are confirmed. Theoretically determined low energy structures using density functional theory (DFT) further support results from ion mobility studies. The DFT calculation reveals that the binding energy and conformation of haloacetate on the CB[6] surface affect the efficiency of the intramolecular SN2 reaction of haloacetate, which correlate well with the experimental observation.

Complexing Methylene Blue with Phosphorus Dendrimers to Increase Photodynamic Activity.

PubMed

Dabrzalska, Monika; Janaszewska, Anna; Zablocka, Maria; Mignani, Serge; Majoral, Jean Pierre; Klajnert-Maculewicz, Barbara

2017-02-23

The efficiency of photodynamic therapy is limited mainly due to low selectivity, unfavorable biodistribution of photosensitizers, and long-lasting skin sensitivity to light. However, drug delivery systems based on nanoparticles may overcome the limitations mentioned above. Among others, dendrimers are particularly attractive as carriers, because of their globular architecture and high loading capacity. The goal of the study was to check whether an anionic phosphorus dendrimer is suitable as a carrier of a photosensitizer-methylene blue (MB). As a biological model, basal cell carcinoma cell lines were used. We checked the influence of the MB complexation on its singlet oxygen production ability using a commercial fluorescence probe. Next, cellular uptake, phototoxicity, reactive oxygen species (ROS) generation, and cell death were investigated. The MB-anionic dendrimer complex (MB-1an) was found to generate less singlet oxygen; however, the complex showed higher cellular uptake and phototoxicity against basal cell carcinoma cell lines, which was accompanied with enhanced ROS production. Owing to the obtained results, we conclude that the photodynamic activity of MB complexed with an anionic dendrimer is higher than free MB against basal cell carcinoma cell lines.

Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

USGS Publications Warehouse

Balistrieri, L.S.; Chao, T.T.

1990-01-01

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density. ?? 1990.

Water-stable NaLuF4-based upconversion nanophosphors with long-term validity for multimodal lymphatic imaging.

PubMed

Zhou, Jing; Zhu, Xingjun; Chen, Min; Sun, Yun; Li, Fuyou

2012-09-01

Multimodal imaging is rapidly becoming an important tool for biomedical applications because it can compensate for the deficiencies of individual imaging modalities. Herein, multifunctional NaLuF(4)-based upconversion nanoparticles (Lu-UCNPs) were synthesized though a facile one-step microemulsion method under ambient condition. The doping of lanthanide ions (Gd(3+), Yb(3+) and Er(3+)/Tm(3+)) endows the Lu-UCNPs with high T(1)-enhancement, bright upconversion luminescence (UCL) emissions, and excellent X-ray absorption coefficient. Moreover, the as-prepared Lu-UCNPs are stable in water for more than six months, due to the protection of sodium glutamate and diethylene triamine pentacetate acid (DTPA) coordinating ligands on the surface. Lu-UCNPs have been successfully applied to the trimodal CT/MR/UCL lymphatic imaging on the modal of small animals. It is worth noting that Lu-UCNPs could be used for imaging even after preserving for over six months. In vitro transmission electron microscope (TEM), methyl thiazolyl tetrazolium (MTT) assay and histological analysis demonstrated that Lu-UCNPs exhibited low toxicity on living systems. Therefore, Lu-UCNPs could be multimodal agents for CT/MR/UCL imaging, and the concept can be served as a platform technology for the next-generation of probes for multimodal imaging. Copyright © 2012 Elsevier Ltd. All rights reserved.

Role of Anions Associated with the Formation and Properties of Silver Clusters.

PubMed

Wang, Quan-Ming; Lin, Yu-Mei; Liu, Kuan-Guan

2015-06-16

Metal clusters have been very attractive due to their aesthetic structures and fascinating properties. Different from nanoparticles, each cluster of a macroscopic sample has a well-defined structure with identical composition, size, and shape. As the disadvantages of polydispersity are ruled out, informative structure-property relationships of metal clusters can be established. The formation of a high-nuclearity metal cluster involves the organization of metal ions into a complex entity in an ordered way. To achieve controllable preparation of metal clusters, it is helpful to introduce a directing agent in the formation process of a cluster. To this end, anion templates have been used to direct the formation of high nuclearity clusters. In this Account, the role of anions played in the formation of a variety of silver clusters has been reviewed. Silver ions are positively charged, so anionic species could be utilized to control the formation of silver clusters on the basis of electrostatic interactions, and the size and shape of the resulted clusters can be dictated by the templating anions. In addition, since the anion is an integral component in the silver clusters described, the physical properties of the clusters can be modulated by functional anions. The templating effects of simple inorganic anions and polyoxometales are shown in silver alkynyl clusters and silver thiolate clusters. Intercluster compounds are also described regarding the importance of anions in determining the packing of the ion pairs and making contribution to electron communications between the positive and negative counterparts. The role of the anions is threefold: (a) an anion is advantageous in stabilizing a cluster via balancing local positive charges of the metal cations; (b) an anion template could help control the size and shape of a cluster product; (c) an anion can be a key factor in influencing the function of a cluster through bringing in its intrinsic properties. Properties including electron communication, luminescent thermochromism, single-molecule magnet, and intercluster charge transfer associated with anion-directed silver clusters have been discussed. We intend to attract chemists' attention to the role that anions could play in determining the structures and properties of metal complexes, especially clusters. We hope that this Account will stimulate more efforts in exploiting new role of anions in various metal cluster systems. Anions can do much more than counterions for charge balance, and they should be considered in the design and synthesis of cluster-based functional materials.

Strapped Calix[4]pyrroles Bearing an 1,3-Indanedione at a β-Pyrrolic Position: Chemodosimeters for the Cyanide Anion

PubMed Central

Kim, Sook-Hee; Hong, Seong-Jin; Yoo, Jaeduk; Kim, Sung Kuk; Sessler, Janathan L.; Lee, Chang-Hee

2014-01-01

A strapped calix[4]pyrrole bearing an 1,3-indanedione group at a β-pyrrolic position has been synthesized and studied as a ratiometric cyanide selective chemosensor. A concentration-dependent bleaching of the initial yellow color was observed upon addition of the cyanide anion. The bleaching, which was observed exclusively with the cyanide anion, occurred even in the presence of other anions. Spectroscopic studies provides support for a mechanistic interpretation wherein the cyanide anion forms a complex with the receptor (K = 2.78 × 104 M-1) through a fast equilibrium, which is followed by slow nucleophilic addition to the β-position of the 1,3-indanedione group. A minimum inhibitory effect from other anions was observed, a feature that could be beneficial in the selective sensing of the cyanide anion. PMID:19639968

Comparisons of auditory brainstem response and sound level tolerance in tinnitus ears and non-tinnitus ears in unilateral tinnitus patients with normal audiograms.

PubMed

Shim, Hyun Joon; An, Yong-Hwi; Kim, Dong Hyun; Yoon, Ji Eun; Yoon, Ji Hyang

2017-01-01

Recently, "hidden hearing loss" with cochlear synaptopathy has been suggested as a potential pathophysiology of tinnitus in individuals with a normal hearing threshold. Several studies have demonstrated that subjects with tinnitus and normal audiograms show significantly reduced auditory brainstem response (ABR) wave I amplitudes compared with control subjects, but normal wave V amplitudes, suggesting increased central auditory gain. We aimed to reconfirm the "hidden hearing loss" theory through a within-subject comparison of wave I and wave V amplitudes and uncomfortable loudness level (UCL), which might be decreased with increased central gain, in tinnitus ears (TEs) and non-tinnitus ears (NTEs). Human subjects included 43 unilateral tinnitus patients (19 males, 24 females) with normal and symmetric hearing thresholds and 18 control subjects with normal audiograms. The amplitudes of wave I and V from the peak to the following trough were measured twice at 90 dB nHL and we separately assessed UCLs at 500 Hz and 3000 Hz pure tones in each TE and NTE. The within-subject comparison between TEs and NTEs showed no significant differences in wave I and wave V amplitude, or wave V/I ratio in both the male and female groups. Individual data revealed increased V/I amplitude ratios > mean + 2 SD in 3 TEs, but not in any control ears. We found no significant differences in UCL at 500 Hz or 3000 Hz between the TEs and NTEs, but the UCLs of both TEs and NTEs were lower than those of the control ears. Our ABR data do not represent meaningful evidence supporting the hypothesis of cochlear synaptopathy with increased central gain in tinnitus subjects with normal audiograms. However, reduced sound level tolerance in both TEs and NTEs might reflect increased central gain consequent on hidden synaptopathy that was subsequently balanced between the ears by lateral olivocochlear efferents.

Comparisons of auditory brainstem response and sound level tolerance in tinnitus ears and non-tinnitus ears in unilateral tinnitus patients with normal audiograms

PubMed Central

An, Yong-Hwi; Kim, Dong Hyun; Yoon, Ji Eun; Yoon, Ji Hyang

2017-01-01

Objective Recently, “hidden hearing loss” with cochlear synaptopathy has been suggested as a potential pathophysiology of tinnitus in individuals with a normal hearing threshold. Several studies have demonstrated that subjects with tinnitus and normal audiograms show significantly reduced auditory brainstem response (ABR) wave I amplitudes compared with control subjects, but normal wave V amplitudes, suggesting increased central auditory gain. We aimed to reconfirm the “hidden hearing loss” theory through a within-subject comparison of wave I and wave V amplitudes and uncomfortable loudness level (UCL), which might be decreased with increased central gain, in tinnitus ears (TEs) and non-tinnitus ears (NTEs). Subjects and methods Human subjects included 43 unilateral tinnitus patients (19 males, 24 females) with normal and symmetric hearing thresholds and 18 control subjects with normal audiograms. The amplitudes of wave I and V from the peak to the following trough were measured twice at 90 dB nHL and we separately assessed UCLs at 500 Hz and 3000 Hz pure tones in each TE and NTE. Results The within-subject comparison between TEs and NTEs showed no significant differences in wave I and wave V amplitude, or wave V/I ratio in both the male and female groups. Individual data revealed increased V/I amplitude ratios > mean + 2 SD in 3 TEs, but not in any control ears. We found no significant differences in UCL at 500 Hz or 3000 Hz between the TEs and NTEs, but the UCLs of both TEs and NTEs were lower than those of the control ears. Conclusions Our ABR data do not represent meaningful evidence supporting the hypothesis of cochlear synaptopathy with increased central gain in tinnitus subjects with normal audiograms. However, reduced sound level tolerance in both TEs and NTEs might reflect increased central gain consequent on hidden synaptopathy that was subsequently balanced between the ears by lateral olivocochlear efferents. PMID:29253030

Ulnar collateral ligament reconstruction using bisuspensory fixation: a biomechanical comparison with the docking technique.

PubMed

Jackson, Timothy J; Adamson, Gregory J; Peterson, Alexander; Patton, John; McGarry, Michelle H; Lee, Thay Q

2013-05-01

Many ulnar collateral ligament (UCL) reconstruction techniques have been created and biomechanically tested. Single-bundle reconstructions aim to re-create the important anterior bundle of the UCL. To date, no technique has utilized suspensory fixation on the ulnar and humeral sides to create a single-bundle reconstruction. The bisuspensory technique will restore valgus laxity to its native state, with comparable load-to-failure characteristics to the docking technique. Controlled laboratory study. Six matched pairs of fresh-frozen cadaveric elbows were randomized to undergo UCL reconstruction using either the docking technique or a novel single-bundle bisuspensory technique. Valgus laxity and rotation measurements were quantified using a MicroScribe 3DLX digitizer at various flexion angles for the native ligament, transected ligament, and 1 of the 2 tested reconstructed ligaments. Laxity testing was performed from maximum extension to 120° of flexion. Each reconstruction was then tested to failure, and the method of failure was recorded. Valgus laxity was restored to the intact state at all degrees of elbow flexion for both the docking and bisuspensory techniques. In load-to-failure testing, there was no significant difference with regard to stiffness, ultimate torque, ultimate torque angle, energy absorbed, and applied moment to reach 10° of valgus. Yield torques for the bisuspensory and docking reconstructions were 18.7 ± 7.8 N·m and 18.6 ± 4.4 N·m, respectively (P = .95). The ultimate torque for the bisuspensory technique measured 26.5 ± 9.2 N·m and for the docking technique measured 25.1 ± 7.1 N·m (P = .78). The bisuspensory fixation technique, a reproducible single-bundle reconstruction, was able to restore valgus laxity to the native state, with similar load-to-failure characteristics as the docking technique. This reconstruction technique could be considered in a clinical setting as a primary method of UCL reconstruction or as a backup fixation method should intraoperative complications occur.

Squarylium-based chromogenic anion sensors

NASA Astrophysics Data System (ADS)

Lee, Eun-Mi; Gwon, Seon-Yeong; Son, Young-A.; Kim, Sung-Hoon

2012-09-01

A squarylium (SQ) dye was synthesized by the reaction between squaric acid and 2,3,3-trimethylindolenine and its anion sensing properties were investigated using absorption and emission spectroscopy. This chemosensor exhibited high selectivity for CN- as compared with F-, CHCO2-, Br-, HPO4-, Cl-, and NO3- in acetonitrile, which was attributed to the formation of a 1:1 squarylium:CN- coordination complex, the formation of which was supported by the calculated geometry of the complex.

Structural basis of control of inward rectifier Kir2 channel gating by bulk anionic phospholipids

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

Lee, Sun-Joo; Ren, Feifei; Zangerl-Plessl, Eva-Maria

2016-08-15

Inward rectifier potassium (Kir) channel activity is controlled by plasma membrane lipids. Phosphatidylinositol-4,5-bisphosphate (PIP 2) binding to a primary site is required for opening of classic inward rectifier Kir2.1 and Kir2.2 channels, but interaction of bulk anionic phospholipid (PL -) with a distinct second site is required for high PIP 2sensitivity. Here we show that introduction of a lipid-partitioning tryptophan at the second site (K62W) generates high PIP 2sensitivity, even in the absence of PL -. Furthermore, high-resolution x-ray crystal structures of Kir2.2[K62W], with or without added PIP 2(2.8- and 2.0-Å resolution, respectively), reveal tight tethering of the C-terminal domainmore » (CTD) to the transmembrane domain (TMD) in each condition. Our results suggest a refined model for phospholipid gating in which PL -binding at the second site pulls the CTD toward the membrane, inducing the formation of the high-affinity primary PIP 2site and explaining the positive allostery between PL -binding and PIP 2sensitivity.« less

Structural basis of control of inward rectifier Kir2 channel gating by bulk anionic phospholipids.

PubMed

Lee, Sun-Joo; Ren, Feifei; Zangerl-Plessl, Eva-Maria; Heyman, Sarah; Stary-Weinzinger, Anna; Yuan, Peng; Nichols, Colin G

2016-09-01

Inward rectifier potassium (Kir) channel activity is controlled by plasma membrane lipids. Phosphatidylinositol-4,5-bisphosphate (PIP2) binding to a primary site is required for opening of classic inward rectifier Kir2.1 and Kir2.2 channels, but interaction of bulk anionic phospholipid (PL(-)) with a distinct second site is required for high PIP2 sensitivity. Here we show that introduction of a lipid-partitioning tryptophan at the second site (K62W) generates high PIP2 sensitivity, even in the absence of PL(-) Furthermore, high-resolution x-ray crystal structures of Kir2.2[K62W], with or without added PIP2 (2.8- and 2.0-Å resolution, respectively), reveal tight tethering of the C-terminal domain (CTD) to the transmembrane domain (TMD) in each condition. Our results suggest a refined model for phospholipid gating in which PL(-) binding at the second site pulls the CTD toward the membrane, inducing the formation of the high-affinity primary PIP2 site and explaining the positive allostery between PL(-) binding and PIP2 sensitivity. © 2016 Lee et al.

Syntheses, crystal structures and magnetic properties of complexes based on [Ni(L-L)3]2+ complex cations with dimethylderivatives of 2,2‧-bipyridine and TCNQ

NASA Astrophysics Data System (ADS)

Černák, Juraj; Hegedüs, Michal; Váhovská, Lucia; Kuchár, Juraj; Šoltésová, Daniela; Čižmár, Erik; Feher, Alexander; Falvello, L. R.

2018-03-01

From the aqueous-methanolic systems Ni(NO3)2 - LiTCNQ - 5,5‧-dmbpy and Ni(NO3)2 - LiTCNQ - 4,4‧-dmbpy three novel complexes [Ni(5,5‧-dmbpy)3](TCNQ)2 (1), [Ni(4,4‧-dmbpy)3](TCNQ)2 (2) and [Ni(4,4‧-dmbpy)3]2(TCNQ-TCNQ)(TCNQ)2•0.60H2O (3), were isolated in single crystal form. The new compounds were identified using chemical analyses and IR spectroscopy. Single crystal studies of all samples corroborated their compositions and have shown that their ionic structures contain the complex cations [Ni(5,5‧-dmbpy)]2+ (1) or [Ni(4,4‧-dmbpy)]2+ (2 and 3). The anionic parts of the respective crystal structures 1-3 are formed by TCNQṡ- anion-radicals and in 3 also by a σ-dimerized dianion (TCNQ-TCNQ)2- with a C-C distance of 1.663(5) Å. The supramolecular structures are governed by weak hydrogen bonding interactions. The variable-temperature (2-300 K) magnetic studies of 1 and 3 confirmed the presence of magnetically active Ni(II) atoms with S = 1 and TCNQṡ- anion-radicals with S = 1/2 while the (TCNQ-TCNQ)2- dianion is magnetically silent. The magnetic behavior was described by a complex magnetic model assuming strong antiferromagnetic interactions between some TCNQṡ- anion-radicals.

Unusual saccharin-N,O (carbonyl) coordination in mixed-ligand copper(II) complexes: Synthesis, X-ray crystallography and biological activity

NASA Astrophysics Data System (ADS)

Mokhtaruddin, Nur Shuhada Mohd; Yusof, Enis Nadia Md; Ravoof, Thahira B. S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhi; Tahir, Mohamed Ibrahim Mohamed

2017-07-01

Three tridentate Schiff bases containing N and S donor atoms were synthesized via the condensation reaction between S-2-methylbenzyldithiocarbazate with 2-acetyl-4-methylpyridine (S2APH); 4-methyl-3-thiosemicarbazide with 2-acetylpyridine (MT2APH) and 4-ethyl-3-thiosemicarbazide with 2-acetylpyridine (ET2APH). Three new, binuclear and mixed-ligand copper(II) complexes with the general formula, [Cu(sac)(L)]2 (sac = saccharinate anion; L = anion of the Schiff base) were then synthesized, and subsequently characterized by IR and UV/Vis spectroscopy as well as by molar conductivity and magnetic susceptibility measurements. The Schiff bases were also spectroscopically characterized using NMR and MS to further confirm their structures. The spectroscopic data indicated that the Schiff bases behaved as a tridentate NNS donor ligands coordinating via the pyridyl-nitrogen, azomethine-nitrogen and thiolate-sulphur atoms. Magnetic data indicated a square pyramidal environment for the complexes and the conductivity values showed that the complexes were essentially non-electrolytes in DMSO. The X-ray crystallographic analysis of one complex, [Cu(sac)(S2AP)]2 showed that the Cu(II) atom was coordinated to the thiolate-S, azomethine-N and pyridyl-N donors of the S2AP Schiff base and to the saccharinate-N from one anion, as well as to the carbonyl-O atom from a symmetry related saccharinate anion yielding a centrosymmetric binuclear complex with a penta-coordinate, square pyramidal geometry. All the copper(II) saccharinate complexes were found to display strong cytotoxic activity against the MCF-7 and MDA-MB-231 human breast cancer cell lines.

Carbon Chain Anions and the Growth of Complex Organic Molecules in Titan’s Ionosphere

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

Desai, R. T.; Coates, A. J.; Wellbrock, A.

Cassini discovered a plethora of neutral and ionized molecules in Titan’s ionosphere including, surprisingly, anions and negatively charged molecules extending up to 13,800 u q{sup −1}. In this Letter, we forward model the Cassini electron spectrometer response function to this unexpected ionospheric component to achieve an increased mass resolving capability for negatively charged species observed at Titan altitudes of 950–1300 km. We report on detections consistently centered between 25.8 and 26.0 u q{sup −1} and between 49.0–50.1 u q{sup −1} which are identified as belonging to the carbon chain anions, CN{sup −}/C{sub 3}N{sup −} and/or C{sub 2}H{sup −}/C{sub 4}H{sup −},more » in agreement with chemical model predictions. At higher ionospheric altitudes, detections at 73–74 u q{sup −1} could be attributed to the further carbon chain anions C{sub 5}N{sup −}/C{sub 6}H{sup −} but at lower altitudes and during further encounters extend over a higher mass/charge range. This, as well as further intermediary anions detected at >100 u, provide the first evidence for efficient anion chemistry in space involving structures other than linear chains. Furthermore, at altitudes below <1100 km, the low-mass anions (<150 u q{sup −1}) were found to deplete at a rate proportional to the growth of the larger molecules, a correlation that indicates the anions are tightly coupled to the growth process. This study adds Titan to an increasing list of astrophysical environments where chain anions have been observed and shows that anion chemistry plays a role in the formation of complex organics within a planetary atmosphere as well as in the interstellar medium.« less

Real-time analysis of multiple anion mixtures in aqueous media using a single receptor.

PubMed

Havel, Vaclav; Yawer, Mirza Arfan; Sindelar, Vladimir

2015-03-18

Bambusuril-based receptors have been used in conjunction with (1)H NMR spectroscopy to recognize mixtures of inorganic anions in aqueous solutions. This was achieved by examining complexation-induced changes in the receptors' (1)H NMR fingerprints. This approach enables the simultaneous identification of up to 9 anions and the quantification of up to 5 anions using a single receptor in DMSO-d6 containing 5% D2O. Toxic perchlorate was recognized and quantified at 0.1 μM (1.8 ppb, mol mol(-1)) concentration in pure water.

Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes

DOE PAGES

Berg, John M.; Gaunt, Andrew J.; May, Iain; ...

2015-04-22

A-type tri-lacunary heteropolyoxotungstate anions (e.g., [PW 9O 34] 9-, [AsW 9O 34] 9-, [SiW 9O 34] 10- and [GeW 9O 34] 10-) are multi-dentate oxygen donor ligands that readily form sandwich complexes with actinyl cations ({UO 2} 2+, {NpO 2} +, {NpO 2} 2+ & {PuO 2} 2+) in near neutral/slightly alkaline aqueous solutions. Two or three actinyl cations are sandwiched between two trilacunary anions, with additional cations (Na +, K + or NH 4 +) also often held within the cluster. Studies thus far have indicated that it is these additional +I cations, rather than the specific actinylmore » cation, that direct the structural variation in the complexes formed. We now report the structural characterization of the neptunyl (VI) cluster complex (NH 4) 13 [Na(NpO 2) 2(A-α- PW 9O 34) 2]·12H 2O. The anion in this complex, [Na(NpO 2) 2(PW 9O 34) 2] 13-, contains one Na + cation and two {NpO 2} 2+ cations held between two [PW 9O 34] 9- anions – with an additional partial occupancy NH 4 + or {NpO 2} 2+ cation also present. In the analogous uranium (VI) system, under similar reaction conditions that includes an excess of NH 4Cl in the parent solution, it was previously shown that [(NH 4) 2(U VIO 2) 2(A-PW 9O 34) 2] 12- is the dominant species in both solution and the crystallized salt. Spectroscopic studies provide further proof of differences in the observed chemistry for the {NpO 2} 2+/[PW 9O 34] 9- and {UO 2} 2+/[PW 9O 34] 9- systems, both in solution and in solid state complexes crystallized from comparable salt solutions. The work revealed that varying the actinide element (Np vs. U) can indeed measurably impact structure and complex stability in the cluster chemistry of actinyl (VI) cations with A-type tri-lacunary heteropolyoxotungstate anions.« less

Mechanistic Significance of the Si–O–Pd Bond in the Palladium-Catalyzed Cross-Coupling Reactions of Arylsilanolates

PubMed Central

2016-01-01

Through the combination of reaction kinetics (both stoichiometric and catalytic), solution- and solid-state characterization of arylpalladium(II) arylsilanolates, and computational analysis, the intermediacy of covalent adducts containing Si–O–Pd linkages in the cross-coupling reactions of arylsilanolates has been unambiguously established. Two mechanistically distinct pathways have been demonstrated: (1) transmetalation via a neutral 8-Si-4 intermediate that dominates in the absence of free silanolate (i.e., stoichiometric reactions of arylpalladium(II) arylsilanolate complexes), and (2) transmetalation via an anionic 10-Si-5 intermediate that dominates in the cross-coupling under catalytic conditions (i.e., in the presence of free silanolate). Arylpalladium(II) arylsilanolate complexes bearing various phosphine ligands have been isolated, fully characterized, and evaluated for their kinetic competence under thermal (stoichiometric) and anionic (catalytic) conditions. Comparison of the rates for thermal and anionic activation suggested, but did not prove, that intermediates containing the Si–O–Pd linkage were involved in the cross-coupling process. The isolation of a coordinatively unsaturated, T-shaped arylpalladium(II) arylsilanolate complex ligated with t-Bu3P allowed the unambiguous demonstration of the operation of both pathways involving 8-Si-4 and 10-Si-5 intermediates. Three kinetic regimes were identified: (1) with 0.5–1.0 equiv of added silanolate (with respect to arylpalladium bromide), thermal transmetalation via a neutral 8-Si-4 intermediate; (2) with 1.0–5.0 equiv of added silanolate, activated transmetalation via an anionic 10-Si-5 intermediate; and (3) with >5.0 equiv of added silanolate, concentration-independent (saturation) activated transmetalation via an anionic 10-Si-5 intermediate. Transition states for the intramolecular transmetalation of neutral (8-Si-4) and anionic (10-Si-5) intermediates have been located computationally, and the anionic pathway is favored by 1.8 kcal/mol. The energies of all intermediates and transition states are highly dependent on the configuration around the palladium atom. PMID:25945516

Quantum chemical calculations of anion complex [B12Hx(CF3)12-x]2-, x = 9 - 12

NASA Astrophysics Data System (ADS)

Koblova, Elena A.; Saldin, Vitaly I.; Ustinov, Alexander Yu.

2016-12-01

The geometric, energetic, spectral and electronic properties of the most stable isomers of B12Hx(CF3)12-X2- anion complex with x = 9 - 12 have been studied using Density Functional Theory (B3LYP/6-311++G**). It was shown that these isomers are characterized by the preference to form the most symmetric structures with uniformly distributed charge densities. However, when replacing a hydrogen atom with fluoromethyl group, an inductive effect occurs. Blue shifts in the IR spectrum compared to the vibrations of the free CF3 molecule are in the range of 2 - 69 cm-1 and points to the stability of B12Hx(CF3)12-x2- anions.

Anion binding in the C3v-symmetric cavity of a protonated tripodal amine receptor: potentiometric and single crystal X-ray studies.

PubMed

Bose, Purnandhu; Ravikumar, I; Ghosh, Pradyut

2011-11-07

Tris(2-aminoethyl)amine (tren) based pentafluorophenyl-substituted tripodal L, tris[[(2,3,4,5,6-pentafluorobenzyl)amino]ethyl]amine receptor is synthesized in good yield and characterized by single crystal X-ray diffraction analysis. Detailed structural aspects of binding of different anionic guests toward L in its triprotonated form are examined thoroughly. Crystallographic results show binding of fluoride in the C(3v)-symmetric cavity of [H(3)L](3+) where spherical anion fluoride is in tricoordinated geometry via (N-H)(+)···F interaction in the complex [H(3)L(F)]·[F](2)·2H(2)O, (3). In the case of complexes [H(3)L(OTs)]·[OTs](2), (4) and [H(3)L(OTs)]·[NO(3)]·[OTs], (5), tetrahedral p-toluenesulphonate ion is engulfed in the cavity of [H(3)L](3+) via (N-H)(+)···O interactions. Interestingly, complex [(H(3)L)(2)(SiF(6))]·[BF(4)](4)·CH(3)OH·H(2)O, (6) shows encapsulation of octahedral hexafluorosilicate in the dimeric capsular assembly of two [H(3)L](3+) units, via a number of (N-H)(+)···F interactions. The kinetic parameters of L upon binding with different anions are evaluated using a potentiometric study in solution state. The potentiometric titration experiments in a polar protic methanol/water (1:1 v/v) binary solvent system show high affinity of the receptor toward more basic fluoride and acetate anions, with a lesser affinity for other inorganic anions (e.g., chloride, bromide, nitrate, sulfate, dihydrogenphosphate, and p-toluenesulphonate). © 2011 American Chemical Society

Time-resolved radiation chemistry: Dynamics of electron attachment to uracil following UV excitation of iodide-uracil complexes

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

King, Sarah B.; Yandell, Margaret A.; Stephansen, Anne B.

Electron attachment to uracil was investigated by applying time-resolved photoelectron imaging to iodide-uracil (I{sup –}U) complexes. In these studies, an ultraviolet pump pulse initiated charge transfer from the iodide to the uracil, and the resulting dynamics of the uracil temporary negative ion were probed. Five different excitation energies were used, 4.00 eV, 4.07 eV, 4.14 eV, 4.21 eV, and 4.66 eV. At the four lowest excitation energies, which lie near the vertical detachment energy of the I{sup –}U complex (4.11 eV), signatures of both the dipole bound (DB) as well as the valence bound (VB) anion of uracil were observed.more » In contrast, only the VB anion was observed at 4.66 eV, in agreement with previous experiments in this higher energy range. The early-time dynamics of both states were highly excitation energy dependent. The rise time of the DB anion signal was ∼250 fs at 4.00 eV and 4.07 eV, ∼120 fs at 4.14 eV and cross-correlation limited at 4.21 eV. The VB anion rise time also changed with excitation energy, ranging from 200 to 300 fs for excitation energies 4.00–4.21 eV, to a cross-correlation limited time at 4.66 eV. The results suggest that the DB state acts as a “doorway” state to the VB anion at 4.00–4.21 eV, while direct attachment to the VB anion occurs at 4.66 eV.« less

Development of (99m)Tc-labeled asymmetric urea derivatives that target prostate-specific membrane antigen for single-photon emission computed tomography imaging.

PubMed

Kimura, Hiroyuki; Sampei, Sotaro; Matsuoka, Daiko; Harada, Naoya; Watanabe, Hiroyuki; Arimitsu, Kenji; Ono, Masahiro; Saji, Hideo

2016-05-15

Prostate-specific membrane antigen (PSMA) is expressed strongly in prostate cancers and is, therefore, an attractive diagnostic and radioimmunotherapeutic target. In contrast to previous reports of PMSA-targeting (99m)Tc-tricarbonyl complexes that are cationic or lack a charge, no anionic (99m)Tc-tricarbonyl complexes have been reported. Notably, the hydrophilicity conferred by both cationic and anionic charges leads to rapid hepatobiliary clearance, whereas an anionic charge might better enhance renal clearance relative to a cationic charge. Therefore, an improvement in rapid clearance would be expected with either cationic or anionic charges, particularly anionic charges. In this study, we designed and synthesized a novel anionic (99m)Tc-tricarbonyl complex ([(99m)Tc]TMCE) and evaluated its use as a single-photon emission computed tomography (SPECT) imaging probe for PSMA detection. Direct synthesis of [(99m)Tc]TMCE from dimethyl iminodiacetate, which contains both the asymmetric urea and succinimidyl moiety important for PSMA binding, was performed using our microwave-assisted one-pot procedure. The chelate formation was successfully achieved even though the precursor included a complicated bioactive moiety. The radiochemical yield of [(99m)Tc]TMCE was 12-17%, with a radiochemical purity greater than 98% after HPLC purification. [(99m)Tc]TMCE showed high affinity in vitro, with high accumulation in LNCaP tumors and low hepatic retention in biodistribution and SPECT/CT studies. These findings warrant further evaluation of [(99m)Tc]TMCE as an imaging agent and support the benefit of this strategy for the design of other PSMA imaging probes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Selective detection of pyrophosphate anion by a simple Cd(II) based terpyridine complex

NASA Astrophysics Data System (ADS)

Purohit, Aditya Kumar; Ghosh, Biswa Nath; Kar, Pravin Kumar

2018-01-01

A simple ratiometric terpyridine-Cd(ll) complex was synthesized by the treatment of CdCl2 with terpyridine ligand 4‧-(4-N,N‧-dimethylaminophenyl)-2,2‧:6‧,2″-terpyridine. The synthesized complex was found to act as a selective fluorescent chemosensor for pyrophosphate P2O74 - (PPi) over other anions like F-, Cl-, Br-, CO32 -, SO32 -, AcO-, NO2-, and H2PO4-. Furthermore, the receptor probe was also successfully employed in HeLa cell for PPi detection, which indicates this can be used as a chemosensor for cells.

Fluoride ion recognition by chelating and cationic boranes.

PubMed

Hudnall, Todd W; Chiu, Ching-Wen; Gabbaï, François P

2009-02-17

Because of the ubiquity of fluoride ions and their potential toxicity at high doses, researchers would like to design receptors that selectively detect this anion. Fluoride is found in drinking water, toothpaste, and osteoporosis drugs. In addition, fluoride ions also can be detected as an indicator of uranium enrichment (via hydrolysis of UF(6)) or of the chemical warfare agent sarin, which releases the ion upon hydrolysis. However, because of its high hydration enthalpy, the fluoride anion is one of the most challenging targets for anion recognition. Among the various recognition strategies that are available, researchers have focused a great deal of attention on Lewis acidic boron compounds. These molecules typically interact with fluoride anions to form the corresponding fluoroborate species. In the case of simple triarylboranes, the fluoroborates are formed in organic solvents but not in water. To overcome this limitation, this Account examines various methods we have pursued to increase the fluoride-binding properties of boron-based receptors. We first considered the use of bifunctional boranes, which chelate the fluoride anion, such as 1,8-diborylnaphthalenes or heteronuclear 1-boryl-8-mercurio-naphthalenes. In these molecules, the neighboring Lewis acidic atoms can cooperatively interact with the anionic guest. Although the fluoride binding constants of the bifunctional compounds exceed those of neutral monofunctional boranes by several orders of magnitude, the incompatibility of these systems with aqueous media limits their utility. More recently, we have examined simple triarylboranes whose ligands are decorated by cationic ammonium or phosphonium groups. These cationic groups increase the electrophilic character of these boranes, and unlike their neutral analogs, they are able to complex fluoride in aqueous media. We have also considered cationic boranes, which form chelate complexes with fluoride anions. Our work demonstrates that Coulombic and chelate effects are additive and can be combined to boost the anion affinity of Lewis acidic hosts. The boron compounds that we have investigated present a set of photophysical and electrochemical properties that can serve to signal the fluoride-binding event. We can also apply this approach to cyanide complexation and are continuing our investigations in that area.

Anion-π aromatic neutral tweezers complexes: are they stable in polar solvents?

PubMed

Sánchez-Lozano, Marta; Otero, Nicolás; Hermida-Ramón, Jose M; Estévez, Carlos M; Mandado, Marcos

2011-03-17

The impact of the solvent environment on the stabilization of the complexes formed by fluorine (T-F) and cyanide (T-CN) substituted tweezers with halide anions has been investigated theoretically. The study was carried out using computational methodologies based on density functional theory (DFT) and symmetry adapted perturbation theory (SAPT). Interaction energies were obtained at the M05-2X/6-31+G* level. The obtained results show a large stability of the complexes in solvents with large dielectric constant and prove the suitability of these molecular tweezers as potential hosts for anion recognition in solution. A detailed analysis of the effects of the solvent on the electron withdrawing ability of the substituents and its influence on the complex stability has been performed. In particular, the interaction energy in solution was split up into intermonomer and solvent-complex terms. In turn, the intermonomer interaction energy was partitioned into electrostatic, exchange, and polarization terms. Polar resonance structures in T-CN complexes are favored by polar solvents, giving rise to a stabilization of the intermonomer interaction, the opposite is found for T-F complexes. The solvent-complex energy increases with the polarity of the solvent in T-CN complexes, nonetheless the energy reaches a maximum and then decreases slowly in T-F complexes. An electron density analysis was also performed before and after complexation, providing an explanation to the trends followed by the interaction energies and their different components in solution.

Analysis of the difference in color development in the dye-binding method due to the kind of buffer solution.

PubMed

Suzuki, Yuji

2006-06-01

In a dye-binding method using a pH indicator, color development has reportedly been affected by the kind of buffer solution used in the color reagent. This phenomenon was analyzed by using a calculation based on the assumption that the anion of the buffer solution also reacts with protein. Color development decreases with increases in the anion concentration of the buffer solution and in the equilibrium constant of the reaction between the anion and protein. The differences in color development due to the kind of buffer solution can be attributed to differences in the equilibrium constant of the reaction forming the anion-protein complex and to the concentration of the anion between the buffer solutions.

Competing supramolecular interactions give a new twist to terpyridyl chemistry: anion- and solvent-induced formation of spiral arrays in silver(I) complexes of a simple terpyridine.

PubMed

Hannon, Michael J; Painting, Claire L; Plummer, Edward A; Childs, Laura J; Alcock, Nathaniel W

2002-05-17

Multiple competing molecular interactions (metal-ligand, pi-stacking and hydrogen-bonding) in the silver(I) complexes of 4'-thiomethyl-2,2':6',2"-terpyridine give rise to a range of different molecular architectures, in which the metal-ligand coordination requirements are satisfied in quite different ways. Polynuclear supramolecular spirals, aggregated mononuclear and aggregated dinuclear units are all structurally characterised. The metallo-supramolecular architecture obtained displays a remarkable dependence both on the choice of non-coordinated anion and the type of solvent used (coordinating or non-coordinating). The anion dependence is particularly surprising, since the anions are not integrated into the centre of the supramolecular structure. The solution behaviour is also solvent and anion dependent, with aggregation of planar mononuclear cations observed in acetonitrile, but oligonuclear spiral species implicated in nitromethane. The extraordinarily variable geometries of these systems suggest that they provide a novel example of the "frustration" principle, in which opposing tendencies cannot simultaneously be satisfied and identify an alternative approach to the design of metallo-supramolecular systems whose structure is responsive to external agents.

Towards Rational Design of Functional Fluoride and Oxyfluoride Materials from First Principles

NASA Astrophysics Data System (ADS)

Charles, Nenian

Complex transition metal compounds (TMCs) research has produced functional materials with a range of properties, including ferroelectricity, colossal magnetoresistance, nonlinear optical activity and high-temperature superconductivity. Conventional routes to tune properties in transition metal oxides, for example, have relied primarily on cation chemical substitution and interfacial effects in thin film heterostructures. In heteroanionic TMCs, exhibiting two chemically distinct anions coordinating the same or different cations, engineering of the anion sub-lattice for property control is a promising alternative approach. The presence of multiple anions provides additional design variables, such as anion order, that are absent in homoanionic counterparts. The more complex structural and chemical phase space of heteroanionic materials provides a unique opportunity to realize enhanced or unanticipated electronic, optical, and magnetic responses. Although there is growing interest in heteroanionic materials, and synthetic and characterization advances are occurring for these materials, the crystal-chemistry principles for realizing structural and property control are only slowing emerging. This dissertation employs anion engineering to investigate phenomena in transition metal fluorides and oxyfluorides compounds using first principles density functional theory calculations. Oxyfluorides are particularly intriguing owing their tendency to stabilize highly ordered anion sublattices as well as the potential to combine the advantageous properties of transition metal oxides and fluorides. This work 1) addresses the challenges of studying fluorides and oxyfluorides using first principles calculations; 2) evaluates the feasibility of using external stimuli, such as epitaxial strain and hydrostatic pressure, to control properties of fluorides and oxyfluorides; and 3) formulates a computational workflow based on multiple levels of theory and computation to elucidate structure-property relationships and anion-order descriptors. The insights gained in this work advance the understanding of oxide-fluoride anion engineered materials and we anticipate that it will motivate novel experimental efforts and materials by design in the future.

Experiments on planetary ices at UCL

NASA Astrophysics Data System (ADS)

Grindrod, P. M.; Fortes, A. D.; Wood, I. G.; Dobson, D.; Sammonds, P. R.; Stone-Drake, L.; Vocadlo, L.

2007-08-01

Using a suite of techniques and equipment, we conduct several different types of experiments on planetary ices at UCL. Samples are prepared in the Ice Physics Laboratory, which consists of a 5 chamber complex of inter-connected cold rooms, controllable from +30 to -30 deg C. Within this laboratory we have a functioning triaxial deformation cell operating at low temperature (down to -90 deg C) and high pressures (300 MPa), an Automatic Ice Fabric Analyser (AIFA) and a low-temperature microscope with CCD output. Polycrystalline samples, 40mm diameter by 100mm long, are compressed in the triaxial rig with a confining pressure; single crystal specimens are compressed in a separate uniaxial creep rig which operates at zero confining pressure for surface studies. A cold stage is also available for study of ice microstructural studies on our new Jeol JSM-6480LV SEM, which also allows tensile, compression and/or bending tests, with load ranges from less than 2N to 5000N. Finally, we also use a cold stage on a new PANalytical, X'pert PRO MPD, high resolution powder diffractometer to study the structure and phase behaviour of icy materials. Recent highlights of our work include: (1) derivation of a manufacturing process for methane clathrate at low temperatures, analysed in the X-Ray Diffraction Laboratory, for future rheological experiments, (2) analysed the growth behaviour of MS11, (3) refurbished and commenced calibration tests on the triaxial deformation cell using ice Ih, and (4) performed creep tests on gypsum and epsomite using the single crystal deformation cell. Further experiments will build on these preliminary results.

Anion-exchange high-performance liquid chromatography of water-soluble chromium (VI) and chromium (III) complexes in biological materials.

PubMed

Suzuki, Y

1987-04-10

A high-performance anion-exchange liquid chromatograph coupled to visible-range (370 nm) and UV (280 nm) detectors and an atomic-absorption spectrometer allowed the rapid determination of CrVI and/or complexes of CrIII in rat plasma, erythrocyte lysate and liver supernatant treated with CrVI or CrIII in vitro. CrVI in the eluates was determined using both the visible-range detector and atomic-absorption spectrometer (AAS). The detection limits of CrVI in standard solutions using these methods were 2 and 5 ng (signal-to-noise ratio = 2), respectively. Separations of the biological components and of CrIII complexes were monitored by UV and AAS analyses, respectively. Time-related decreases of CrVI accompanied by increases in CrIII complexes were observed, indicating the reduction of CrVI by some of the biological components. The reduction rates were considerably higher in the liver supernatant and erythrocyte lysate than in the plasma. These results indicate that the anion-exchange high-performance liquid chromatographic system is useful for simultaneous determination of CrVI and CrIII complexes in biological materials.

Anion Photoelectron Spectroscopic Studies of NbCr(CO)_n- (n = 2,3) Heterobimetallic Carbonyl Complexes

NASA Astrophysics Data System (ADS)

Baudhuin, Melissa A.; Boopalachandran, Praveenkumar; Leopold, Doreen

2015-06-01

Anion photoelectron spectra and density functional calculations are reported for NbCr(CO)2- and NbCr(CO)3- complexes prepared by addition of Cr(CO)6 vapor to a flow tube equipped with a niobium cathode discharge source. Electron affinities (± 0.007 eV) are measured to be 1.668 eV for NbCr(CO)2 and 1.162 eV for NbCr(CO)3, values which exceed the 0.793 eV electron affinity previously measured for ligand-free NbCr. The vibrationally-resolved 488 nm photoelectron spectra are compared with Franck-Condon spectra predicted for various possible isomers and spin states of the anionic and neutral metal carbonyl complexes. Results are also compared with photoelectron spectra of the corresponding chromium carbonyl complexes and of NbCr and NbCr-, which have formal bond orders of 5.5 (2Δ) and 6 (1σ+), respectively. These comparisons help to elucidate the effects of sequential carbonylation on this multiple metal-metal bond, and of the formation of this bond on the chromium-carbonyl interactions.

Anion responsive Europium (III) complexes for Optical Sensing and PARACEST MRI

NASA Astrophysics Data System (ADS)

Buttarazzi, Leandro Alfredo

The Eu(III) complexes of 1-(acetyl-7-Methyl-4-(trifluoromethyl) quinolin-2(1H)-one)4,7,10 tris(2-hydroxypropyl)-1,4,7,10-tetraazacycladodecane (Eu(S-THPC)3+ ) and 1-(acetyl-dioctadecylamine)4,7,10 tris(hydroxypropyl)-1,4,7,10-tetraazacycladodecane (Eu(S-THMC)3+) were studied in order to develop complexes that are both optical sensors and MRI contrast agents that respond to biologically relevant anions. Both complexes are related to Eu(S-THP) where S-THP = (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane. Eu(III) excitation, emission and time resolved luminescence spectroscopy experiments were used to study binding of the anions. One complex, Eu(THPC)3+ has an appended carbostyril dye for sensitization of Eu(III) luminescence. Luminescence experiments were done on this complex in order to quantify the effectiveness of the energy transfer from the dye to the lanthanide and to obtain binding constants of the anions from the Eu(III) emission peaks. Emission spectra were obtained by exciting the chromophore at 340 nm. Our results suggest that phosphate binds with a dissociation constant (Kd) of 4.2mM and citrate binds with a Kd of 228 uM. The quantum yield for the complex was low compared to other reported complexes in literature. Eu(S-THMC) 3+, and Eu(S-THMAC)3+ containing long carbon chains for incorporation into liposomes were explored as an approach to develop complexes with increased sensitivity as CEST agents. CEST experiments with the complex incorporated into a liposome and as a micelle were carried out. Liposome formation was achieved but no CEST effect was observed with two different lanthanide complexes. Eu(S-THMC)3+ gave the most promising results by showing CEST in acetonitrile and 50/50 acetonitrile/H 2O. However further experiments with this complex in buffered aqueous solution failed. Yb(S-THMAC)3+ solubility was poor in both acetonitrile and in water and this likely prevented the observation of CEST spectra.

Regulation of superoxide anion production by NADPH oxidase in monocytes/macrophages: contributions to atherosclerosis.

PubMed

Cathcart, Martha K

2004-01-01

Monocyte extravasation into the vessel wall has been shown to be a critical step in the development of atherosclerosis. Upon activation, monocytes produce a burst of superoxide anion due to activation of the NADPH oxidase enzyme complex. Monocyte-derived superoxide anion contributes to oxidant stress in inflammatory sites, is required for monocyte-mediated LDL oxidation, and alters basic cell functions such as adhesion and proliferation. We hypothesize that monocyte-derived superoxide anion production contributes to atherosclerotic lesion formation. In this brief review, we summarize our current understanding of the signal transduction pathways regulating NADPH oxidase activation and related superoxide anion production in activated human monocytes. Novel pathways are identified that may serve as future targets for therapeutic intervention in this pathogenic process. The contributions of superoxide anion and NADPH oxidase to atherogenesis are discussed. Future experiments are needed to clarify the exact role of NADPH oxidase-derived superoxide anion in atherogenesis, particularly that derived from monocytes.

Anion sensing with a Lewis acidic BODIPY-antimony(v) derivative.

PubMed

Christianson, Anna M; Gabbaï, François P

2017-02-21

We describe the synthesis of a BODIPY dye substituted with a Lewis acidic antimony(v) moiety. This compound, which has been fully characterized, shows a high affinity for small anions including fluoride and cyanide, the complexation of which elicits a fluorescence turn-on response.

Medial ulnar collateral ligament reconstruction of the elbow in major league baseball players: Where do we stand?

PubMed Central

Erickson, Brandon J; Bach Jr, Bernard R; Bush-Joseph, Charles A; Verma, Nikhil N; Romeo, Anthony A

2016-01-01

The ulnar collateral ligament (UCL) is a vital structure to the overhead athlete, especially the baseball pitcher. For reasons not completely understood, UCL injuries have become increasingly more common in major league baseball (MLB) pitchers over the past 10 years. UCL reconstruction (UCLR) is the current gold standard of treatment for these injuries in MLB pitchers who wish to return to sport (RTS) at a high level and who have failed a course of non-operative treatment. Results following UCLR in MLB pitchers have been encouraging, with multiple RTS rates now cited at greater than 80%. Unfortunately, with the rising number of UCLR, there has also been a spike in the number of revision UCLR in MLB pitchers. Similar to primary UCLR, the etiology of the increase in revision UCLR, aside from an increase in the number of pitchers who have undergone a primary UCLR, remains elusive. The current literature has attempted to address several questions including those surrounding surgical technique (method of exposure, graft choice, management of the ulnar nerve, concomitant elbow arthroscopy, etc.), post-operative rehabilitation strategies, and timing of RTS following UCLR. While some questions have been answered, many remain unknown. The literature surrounding UCLR in MLB pitchers will be reviewed, and future directions regarding this injury in these high level athletes will be discussed. PMID:27335810

Corrosion Behavior of Yttria-Stabilized Zirconia-Coated 9Cr-1Mo Steel in Molten UCl3-LiCl-KCl Salt

NASA Astrophysics Data System (ADS)

Jagadeeswara Rao, Ch.; Venkatesh, P.; Prabhakara Reddy, B.; Ningshen, S.; Mallika, C.; Kamachi Mudali, U.

2017-02-01

For the electrorefining step in the pyrochemical reprocessing of spent metallic fuels of future sodium cooled fast breeder reactors, 9Cr-1Mo steel has been proposed as the container material. The electrorefining process is carried out using 5-6 wt.% UCl3 in LiCl-KCl molten salt as the electrolyte at 500 °C under argon atmosphere. In the present study, to protect the container vessel from hot corrosion by the molten salt, 8-9% yttria-stabilized zirconia (YSZ) ceramic coating was deposited on 9Cr-1Mo steel by atmospheric plasma spray process. The hot corrosion behavior of YSZ-coated 9Cr-1Mo steel specimen was investigated in molten UCl3-LiCl-KCl salt at 600 °C for 100-, 500-, 1000- and 2000-h duration. The results revealed that the weight change in the YSZ-coated specimen was insignificant even after exposure to molten salt for 2000 h, and delamination of coating did not occur. SEM examination showed the lamellar morphology of the YSZ coating after the corrosion test with occluded molten salt. The XRD analysis confirmed the presence of tetragonal and cubic phases of ZrO2, without any phase change. Formation of UO2 in some regions of the samples was evident from XRD results.

Multifunctional NaYF4:Yb, Er@mSiO2@Fe3O4-PEG nanoparticles for UCL/MR bioimaging and magnetically targeted drug delivery.

PubMed

Liu, Bei; Li, Chunxia; Ma, Ping'an; Chen, Yinyin; Zhang, Yuanxin; Hou, Zhiyao; Huang, Shanshan; Lin, Jun

2015-02-07

A low toxic multifunctional nanoplatform, integrating both mutimodal diagnosis methods and antitumor therapy, is highly desirable to assure its antitumor efficiency. In this work, we show a convenient and adjustable synthesis of multifunctional nanoparticles NaYF4:Yb, Er@mSiO2@Fe3O4-PEG (MFNPs) based on different sizes of up-conversion nanoparticles (UCNPs). With strong up-conversion fluorescence offered by UCNPs, superparamagnetism properties attributed to Fe3O4 nanoparticles and porous structure coming from the mesoporous SiO2 shell, the as-obtained MFNPs can be utilized not only as a contrast agent for dual modal up-conversion luminescence (UCL)/magnetic resonance (MR) bio-imaging, but can also achieve an effective magnetically targeted antitumor chemotherapy both in vitro and in vivo. Furthermore, the UCL intensity of UCNPs and the magnetic properties of Fe3O4 in the MFNPs were carefully balanced. Silica coating and further PEG modifying can improve the hydrophilicity and biocompatibility of the as-synthesized MFNPs, which was confirmed by the in vitro/in vivo biocompatibility and in vivo long-time bio-distributions tests. Those results revealed that the UCNPs based magnetically targeted drug carrier system we synthesized has great promise in the future for multimodal bio-imaging and targeted cancer therapy.

Anion complexation and the Hofmeister effect.

PubMed

Carnegie, Ryan S; Gibb, Corinne L D; Gibb, Bruce C

2014-10-20

The (1)H NMR spectroscopic analysis of the binding of the ClO4(-) anion to the hydrophobic, concave binding site of a deep-cavity cavitand is presented. The strength of association between the host and the ClO4(-) anion is controlled by both the nature and concentration of co-salts in a manner that follows the Hofmeister series. A model that partitions this trend into the competitive binding of the co-salt anion to the hydrophobic pocket of the host and counterion binding to its external carboxylate groups successfully accounts for the observed changes in ClO4(-) affinity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stabilization of oxidovanadium(IV) by organic radicals.

PubMed

Kundu, Suman; Maity, Suvendu; Maity, Amarendra Nath; Ke, Shyue-Chu; Ghosh, Prasanta

2013-04-07

o-Imino-p-R'-benzosemiquinone anion radical (L(R')(IS)(˙-)) complexes of oxidovanadium(IV) of type [(L(1)(R-))(VO(2+))(L(R')(IS)(˙-))] (R = H, R' = H, 1; R = H, R' = -CMe(3), 2; R = -CMe(3), R' = H, 3 and R = -CMe(3), R' = -CMe(3), 4) incorporating the redox-innocent tridentate NNO-donor L(1)(R-) ligands (L(1)(R)H = 2,4-di-R-6-{(2-(pyridin-2-yl)hydrazono)methyl}phenol) were isolated and substantiated by elemental analyses, IR, mass, NMR and UV-vis spectra including the single crystal X-ray structure determinations. The V-O(phenolato) (cis to the V=O) lengths spanning 1.905(3)-1.9355(15) Å in 1-4 are consistent with the coordination to the [VO](2+) state. The V-O(IS) (trans to the V=O) lengths, 2.1505(17)-2.1869(15) Å, in 1-4 are longer due to the trans influence of the V=O bond. The V-N(IS) lengths, 1.906(3)-1.924(2) Å, in 1-4 are comparatively shorter due to the higher affinity of the paramagnetic [VO](2+) ion towards the L(R')(IS)(˙-) anion radicals. Density functional theory (DFT) calculations using B3LYP, B3PW91 and PBE1PBE functionals on 1 and 2 authenticated that the closed shell singlet (CSS) solutions (dianionic o-amido-p-R'-phenolates (L(R')(AP)(2-)) coordinated to VO(3+), Type I) of 1-4 are unstable with respect to the open shell singlet (OSS) perturbations. Broken symmetry, BS (1,1) M(s) = 0 (L(R')(IS)(˙-) coordinated to the VO(2+) ion, Type III) solutions of 1-4 are stable and reproduce the experimental bond parameters. Frozen glasses EPR spectra of [1-4](+) ions (e.g. g(||) = 1.948, g(⊥) = 1.978, A(||) = 184 (22 G), A(⊥) = 62(15 G) for [2](+)) and unrestricted DFT calculations on [1](+), [2](+), [1](-) and [2](-) ions using doublet spin state elucidated that the reversible anodic waves at [0.15-0.31] V of 1-4 complexes are due to the oxidation of L(R')(IS)(˙-) generating [(L(1)(R-))(VO(2+))(L(R')(IQ))]+ complexes (L(R')(IQ) = o-imino-p-R'-benzoquinone) coordinated to the [VO](2+) ion (Type V) while the irreversible cathodic waves at -[1.08-1.49] V are due to the formation of unstable [(L(1)(R-))(VO(2+))(L(R')(AP)(2-))](-) complexes (Type II). The second anodic waves at [0.76-0.89] V are assigned to a [VO](3+)-[VO](2+) couple affording diamagnetic [(L(1)(R-))(VO(3+))(L(R')(IQ))](2+), [1-4](2+) complexes (Type VI) which are identified by UV-vis spectra, DFT and time dependent (TD) DFT calculations. Spectro-electrochemical measurements and TD DFT calculations on 1 and 2 disclosed that lower energy electronic absorption bands of 1-4 are due to the LMCT and CSS-OSS perturbation which disappear in [1-4](+) ions. [1-4](+) absorb at 600-650 nm due to d-d transitions and MLCT which are absent in VO(3+) complexes, [1-4](2+).

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

Mazurkiewicz, Kamil; Haranczyk, Maciej; Gutowski, Maciej S.

The electron affinity and the propensity to electron-induced proton transfer (PT) of hydrogen-bonded complexes between the Watson–Crick adenine–thymine pair (AT) and simple organic acid (HX), attached to adenine in the Hoogsteen-type configuration, were studied at the B3LYP/6-31+G** level. Although the carboxyl group is deprotonated at physiological pH, its neutral form, COOH, resembles the peptide bond or the amide fragment in the side chain of asparagine (Asn) or glutamine (Gln). Thus, these complexes mimic the interaction between the DNA environment (e.g., proteins) and nucleobase pairs incorporated in the biopolymer. Electron attachment is thermodynamically feasible and adiabatic electron affinities range from 0.41more » to 1.28 eV, while the vertical detachment energies of the resulting anions span the range of 0.39 –2.88 eV. Low-energy activation barriers separate the anionic minima: aHX(AT) from the more stable single-PT anionic geometry, aHX(AT)-SPT, and aHX(AT)-SPT from the double-PT anionic geometry, aHX(AT)-DPT. Interaction between the adenine of the Watson–Crick AT base pair with an acidic proton donor probably counterbalances the larger EA of isolated thymine, as SOMO is almost evenly delocalized over both types of nucleic bases in the aHX(AT) anions. Moreover, as a result of PT the excess electron localizes entirely on adenine. Thus, in DNA interacting with its physiological environment, damage induced by low-energy electrons could begin, contrary to the current view, with the formation of purine anions, which are not formed in isolated DNA because of the greater stability of anionic pyrimidines.« less

Infrared spectra and crystal chemistry of scapolites: implications for Martian mineralogy

USGS Publications Warehouse

Swayze, G.A.; Clark, R.N.

1990-01-01

Near-infrared and midinfrared spectra of a wide range of scapolite compositions were studied to determine the cause of the 2.36-??m features that have been correlated with similar features in the near-IR spectrum of Mars. We attribute the 2.36-??m features to vibrations caused by HCO-3 and HSO-4 in the anion sites of scapolite. The 2.36-??m absorption complex consists of four overlapping bands. The relative intensities of all four bands vary according to the HCO-3/HSO-4 ratio and disordered anion site occupancy. The positional disorder of HCO-3 and HSO4 in the low-symmetry anion site of scapolite gives the 2.36-??m band complex a unique spectral signature not likely to be duplicated in any other mineral. -from Authors

Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple

DOE PAGES

Ellis, Ross J.; Bera, Mrinal K.; Reinhart, Benjamin; ...

2016-11-07

Redox-driven ion transfer between phases underpins many biological and technological processes, including industrial separation of ions. Here we investigate the electrochemical transfer of nitrate anions between oil and water phases, driven by the reduction and oxidation of cerium coordination complexes in oil phases. We find that the coordination environment around the cerium cation has a pronounced impact on the overall redox potential, particularly with regard to the number of coordinated nitrate anions. Our results suggest a new fundamental mechanism for tuning ion transfer between phases; by 'trapping' the migrating ion inside the coordination sphere of a redox-active complex. Here, thismore » presents a new route for controlling anion transfer in electrochemically-driven separation applications.« less

Redox chemistry of nickel(II) complexes supported by a series of noninnocent β-diketiminate ligands.

PubMed

Takaichi, June; Morimoto, Yuma; Ohkubo, Kei; Shimokawa, Chizu; Hojo, Takayuki; Mori, Seiji; Asahara, Haruyasu; Sugimoto, Hideki; Fujieda, Nobutaka; Nishiwaki, Nagatoshi; Fukuzumi, Shunichi; Itoh, Shinobu

2014-06-16

Nickel complexes of a series of β-diketiminate ligands ((R)L(-), deprotonated form of 2-substituted N-[3-(phenylamino)allylidene]aniline derivatives (R)LH, R = Me, H, Br, CN, and NO2) have been synthesized and structurally characterized. One-electron oxidation of the neutral complexes [Ni(II)((R)L(-))2] by AgSbF6 or [Ru(III)(bpy)3](PF6)3 (bpy = 2,2'-bipyridine) gave the corresponding metastable cationic complexes, which exhibit an EPR spectrum due to a doublet species (S = 1/2) and a characteristic absorption band in near IR region ascribable to a ligand-to-ligand intervalence charge-transfer (LLIVCT) transition. DFT calculations have indicated that the divalent oxidation state of nickel ion (Ni(II)) is retained, whereas one of the β-diketiminate ligands is oxidized to give formally a mixed-valence complex, [Ni(II)((R)L(-))((R)L(•))](+). Thus, the doublet spin state of the oxidized cationic complex can be explained by taking account of the antiferromagnetic interaction between the high-spin nickel(II) ion (S = 1) and the organic radical (S = 1/2) of supporting ligand. A single-crystal structure of one of the cationic complexes (R = H) has been successfully determined to show that both ligands in the cationic complex are structurally equivalent. On the basis of theoretical analysis of the LLIVCT band and DFT calculations as well as the crystal structure, the mixed-valence complexes have been assigned to Robin-Day class III species, where the radical spin is equally delocalized between the two ligands to give the cationic complex, which is best described as [Ni(II)((R)L(0.5•-))2](+). One-electron reduction of the neutral complexes with decamethylcobaltocene gave the anionic complexes when the ligand has the electron-withdrawing substituent (R = CN, NO2, Br). The generated anionic complexes exhibited EPR spectra due to a doublet species (S = 1/2) but showed no LLIVCT band in the near-IR region. Thus, the reduced complexes are best described as the d(9) nickel(I) complexes supported by two anionic β-diketiminate ligands, [Ni(I)((R)L(-))2](-). This conclusion was also supported by DFT calculations. Substituent effects on the electronic structures of the three oxidation states (neutral, cationic, and anionic) of the complexes are systematically evaluated on the basis of DFT calculations.

Anionic Palladium(0) and Palladium(II) Ate Complexes.

PubMed

Kolter, Marlene; Böck, Katharina; Karaghiosoff, Konstantin; Koszinowski, Konrad

2017-10-16

Palladium ate complexes are frequently invoked as important intermediates in Heck and cross-coupling reactions, but so far have largely eluded characterization at the molecular level. Here, we use electrospray-ionization mass spectrometry, electrical conductivity measurements, and NMR spectroscopy to show that the electron-poor catalyst [L 3 Pd] (L=tris[3,5-bis(trifluoromethyl)phenyl]phosphine) readily reacts with Br - ions to afford the anionic, zero-valent ate complex [L 3 PdBr] - . In contrast, more-electron-rich Pd catalysts display lower tendencies toward the formation of ate complexes. Combining [L 3 Pd] with LiI and an aryl iodide substrate (ArI) results in the observation of the Pd II ate complex [L 2 Pd(Ar)I 2 ] - . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of removing arsenic and other anionic contaminants from contaminated water using enhanced coagulation

DOEpatents

Teter, David M.; Brady, Patrick V.; Krumhansl, James L.; Khandaker, Nadim R.

2006-11-21

An improved water decontamination process comprising contacting water containing anionic contaminants with an enhanced coagulant to form an enhanced floc, which more efficiently binds anionic species (e.g., arsenate, arsenite, chromate, fluoride, selenate, and borate, and combinations thereof) predominantly through the formation of surface complexes. The enhanced coagulant comprises a trivalent metal cation coagulant (e.g., ferric chloride or aluminum sulfate) mixed with a divalent metal cation modifier (e.g., copper sulfate or zinc sulfate).

Ion/Ion Reactions with "Onium" Reagents: An Approach for the Gas-phase Transfer of Organic Cations to Multiply-Charged Anions

NASA Astrophysics Data System (ADS)

Gilbert, Joshua D.; Prentice, Boone M.; McLuckey, Scott A.

2015-05-01

The use of ion/ion reactions to effect gas-phase alkylation is demonstrated. Commonly used fixed-charge "onium" cations are well-suited for ion/ion reactions with multiply deprotonated analytes because of their tendency to form long-lived electrostatic complexes. Activation of these complexes results in an SN2 reaction that yields an alkylated anion with the loss of a neutral remnant of the reagent. This alkylation process forms the basis of a general method for alkylation of deprotonated analytes generated via electrospray, and is demonstrated on a variety of anionic sites. SN2 reactions of this nature are demonstrated empirically and characterized using density functional theory (DFT). This method for modification in the gas phase is extended to the transfer of larger and more complex R groups that can be used in later gas-phase synthesis steps. For example, N-cyclohexyl- N'-(2-morpholinoethyl)carbodiimide (CMC) is used to transfer a carbodiimide functionality to a peptide anion containing a carboxylic acid. Subsequent activation yields a selective reaction between the transferred carbodiimide group and a carboxylic acid, suggesting the carbodiimide functionality is retained through the transfer process. Many different R groups are transferable using this method, allowing for new possibilities for charge manipulation and derivatization in the gas phase.

Thumb Sprains

MedlinePlus

... Thumb Sprains Find a hand surgeon near you. Videos Figures Figure 1: The ulnar collateral ligament (UCL) ... or "in." Also, avoid using media types like "video," "article," and "picture." Tip 4: Your results can ...

Influence of ligand-bridged substitution on the exchange coupling constant of chromium-wheels host complexes: a density functional theory study

NASA Astrophysics Data System (ADS)

Sadeghi Googheri, Motahare; Abolhassani, Mohammad Reza; Mirzaei, Mahmoud

2018-05-01

Designing and introducing novel wheel-shaped supramolecular as host complexes with new magnetic properties is the theme of the day. So in this study, new eight binuclear chromium (III) complexes, as models of real chromium-wheel host complexes, were designed based on changing of bridged-ligands and exchange coupling constants (J) of them were calculated using the broken symmetry density functional theory approach. Substitution of fluorine ligand in fluoro-bridged model [Cr2F(tBuCO2)2(H2O)2(OH)4]-1 by halogen anions (Cl-, Br- and I- ) decreased the antiferromagnetic exchange coupling between Cr(III) centres such that by going from F- to I- the J values became more positive. In the case of hydroxo-bridged model [Cr2OH(tBuCO2)2(H2O)2(OH)4]-1, replacement of hydroxyl by methoxy anion (OMe-) strengthened the antiferromagnetic property of the complex but substitution by sulfanide (SH-) and amide (NH2-) anions weakened it and changed the nature of complexes to ferromagnetic. Because of their different magnetic properties, these new investigated complexes can be suggested as interesting synthetic targets. Also, the J value changes due to ligand substitution were evaluated and it was found that the Cr-X bond strength and partial charges of involved atoms were the most effective factors on it.

Structural diversity of silver (I) azine complexes - Effect of substituents and counter anions

NASA Astrophysics Data System (ADS)

Patra, Goutam Kumar; Mukherjee, Anindita; Mitra, Partha; Adarsh, N. N.

2011-08-01

Three new Ag(I) complexes, 1, 2, and 3 of two azine ligands diacetyl dihydrazone ( L1) and benzil dihydrazone ( L2) have been synthesized and characterized by single crystal X-ray diffraction studies (for 2 and 3), X-ray powder diffraction studies( 1 and 2), elemental analyses, IR and UV-VIS spectroscopy and TGA analysis. They represent one-dimensional polymeric assemblies and discrete dinuclear Ag(I) complex depending on functionality of the ligands and the counter anions. Tetrahedral as well as square pyramidal coordination motifs of the silver (I) ions have been observed in the supramolecular designing of such hybrid organic-inorganic materials.

Crystal structure of tetra-aqua-bis(3,5-di-amino-4H-1,2,4-triazol-1-ium)cobalt(II) bis-[bis-(pyridine-2,6-di-carboxyl-ato)cobaltate(II)] dihydrate.

PubMed

Johnson, Atim; Mbonu, Justina; Hussain, Zahid; Loh, Wan-Sin; Fun, Hoong-Kun

2015-06-01

The asymmetric unit of the title compound, [Co(C2H6N5)2(H2O)4][Co(C7H3NO4)2]2·2H2O, features 1.5 Co(II) ions (one anionic complex and one half cationic complex) and one water mol-ecule. In the cationic complex, the Co(II) atom is located on an inversion centre and is coordinated by two triazolium cations and four water mol-ecules, adopting an octa-hedral geometry where the N atoms of the two triazolium cations occupy the axial positions and the O atoms of the four water mol-ecules the equatorial positions. The two triazole ligands are parallel offset (with a distance of 1.38 Å between their planes). In the anionic complex, the Co(II) ion is six-coordinated by two N and four O atoms of the two pyridine-2,6-di-carboxyl-ate anions, exhibiting a slightly distorted octa-hedral coordination geometry in which the mean plane of the two pyridine-2,6-di-carboxyl-ate anions are almost perpendicular to each other, making a dihedral angle of 85.87 (2)°. In the crystal, mol-ecules are linked into a three-dimensional network via C-H⋯O, C-H⋯N, O-H⋯O and N-H⋯O hydrogen bonds.

Observations of the ground-attachment process in natural lightning in the absence of tall strike objects

NASA Astrophysics Data System (ADS)

Tran, M. D.; Rakov, V. A.

2017-12-01

Synchronized high-speed (124 or 210 kiloframes per second) video images and wideband electromagnetic field records of the attachment process were obtained for 4 negative strokes in natural lightning at the Lightning Observatory in Gainesville, Florida. The apparent strike objects were trees, whose heights were less than 30 m or so. Upward connecting leaders (UCLs) and multiple upward unconnected leaders were imaged in multiple frames. The majority of these upward positive leaders exhibited a pulsating behavior (brightening/fading cycles). UCLs, whose maximum extent ranged from 11 to 25 m, propagated at speeds ranging from 1.8×105 to 6.0×105 m/s with a mean of 3.4×105 m/s. Within about 100 m of the ground, the ratio of speeds of the downward negative leader and the corresponding UCL was about 3-4 for 2 events and 0.5 for 1 event. The breakthrough phase (BTP), corresponding to leader extensions inside the common streamer zone (CSZ), was imaged for 2 events. The initial length of CSZ was estimated to be about 30-40 m. For 2 events, estimated speeds of positive and negative leaders inside the CSZ were found to be between 2.4×106 and 3.7×106 m/s. For 1 event, opposite polarity leaders were observed to accelerate inside the CSZ. Further, in this same event, a space-leader-like formation, accompanied by significant intensification of UCL and apparently associated with the onset of BTP, was imaged. We speculate that the step-wise extension of the downward leader facilitated corona streamer bursts from both the downward negative and upward positive (UCL) leader tips, resulting in the establishment of CSZ. First speed profiles for colliding positive and negative leaders were obtained. In one event, the negative leader speed increased from 7.2 ×105 in virgin air to 2.5×106 (by a factor of 3.5), and then to 3.2×106 m/s just prior to the fast transition (FT) in the return-stroke field waveform. The positive leader accelerated from 1.8×105 (in virgin air) to 2.5×106 (by a factor of 14), and then to 3.2×106 m/s. Using integrated dB/dt waveforms, a transmission-line-type model, and peak current reported by the U.S. National Lightning Detection Network, we inferred the current increases during the BTP and FT to be on average 16 and 18 kA, respectively, indicating that these two processes contribute about equally to the overall current peak.

Spectral Fluorescence Properties of an Anionic Oxacarbocyanine Dye in Complexes with Human Serum Albumin

NASA Astrophysics Data System (ADS)

Pronkin, P. G.; Tatikolov, A. S.

2015-07-01

The spectral fluorescence properties of the anionic oxacarbocyanine dye 3,3'-di-(γ-sulfopropyl)-5,5'-diphenyl-9-ethyloxacarbocyanine betaine (OCC) were studied in solutions and in complexes with human serum albumin (HSA). Interaction with HSA leads to a significant increase in the fluorescence of the dye. We studied quenching of the fluorescence of OCC in a complex with HSA by ibuprofen and warfarin. Data on quenching of fluorescence by ibuprofen indicate binding of the dye to binding site II of subdomain IIIA in the HSA molecule. Synchronous fluorescence spectra of human serum albumin in the presence of OCC showed that complexation with OCC does not lead to appreciable rearrangement of the protein molecule at the binding site.

Bowl adamanzanes--bicyclic tetraamines: syntheses and crystal structures of complexes with cobalt(III) and chelating coordinated oxo-anions.

PubMed

Broge, Louise; Søtofte, Inger; Jensen, Kristian; Jensen, Nicolai; Pretzmann, Ulla; Springborg, Johan

2007-09-14

Seven cobalt(III) complexes of the macrobicyclic tetraamine ligand [2(4).3(1)]adamanzane ([2(4).3(1)]adz) are reported along with the crystal structure of six of these complexes. The solid state and solution structures are discussed, and a detailed assignment of the NMR spectra of the sulfato complex is provided. Four of the seven complexes contain a chelate coordinating oxo-anion (sulfate, formiate, nitrate, carbonate). Equilibration of these species with the corresponding diaqua complex is generally slow. The rates of equilibration in 5 mol dm(-3) perchloric acid at 25 degrees C have been measured, yielding half lives of 20 min, 10 min and 3 h for the sulfato, formiato and carbonato species respectively. The corresponding reaction for the nitrato complex occurs with a half life of less than 3 min. The concentration acid dissociation constant for the Co([2(4).3(1)]adz)(HCO(3))(2+) ion has been measured to K(a) = 0.33 mol dm(-3) [25 degrees C, I = 2 mol dm(-3)] and K(a) = 0.15 mol dm(-3) [25 degrees C, I = 5 mol dm(-3)]. The propensity for coordination of sulfate was found to be large enough for a quantitative conversion of the carbonato complex to the sulfato complex to occur in 3 mol dm(-3) triflic acid containing a small sulfate contamination. On this basis the decarboxylation in 5 mol dm(-3) triflic acid of the corresponding cobalt(III) carbonato complex of the larger macrobicyclic tetraamine ligand [3(5)]adz was reinvestigated and found to lead to the sulfato complex as well. The difference in exchange rate of the oxo-anion ligands for the cobalt(III) complexes of the two adamanzane ligands is discussed and attributed to fundamental differences in the molecular structure where an inverted configuration of the secondary non-bridged amine groups is seen for the complexes of the larger [3(5)]adz ligand. The high affinity for chelating coordination of oxo-anions for these two cobalt(iii)-adamanzane-moieties is rationalised on basis of the N-Co-N angles. N-Co-N angles are compared for a series of adamanzane complexes, and the structural consequences are discussed.

Return to football and long-term clinical outcomes after thumb ulnar collateral ligament suture anchor repair in collegiate athletes.

PubMed

Werner, Brian C; Hadeed, Michael M; Lyons, Matthew L; Gluck, Joshua S; Diduch, David R; Chhabra, A Bobby

2014-10-01

To evaluate return to play after complete thumb ulnar collateral ligament (UCL) injury treated with suture anchor repair for both skill position and non-skill position collegiate football athletes and report minimum 2-year clinical outcomes in this population. For this retrospective study, inclusion criteria were complete rupture of the thumb UCL and suture anchor repair in a collegiate football athlete performed by a single surgeon who used an identical technique for all patients. Data collection included chart review, determination of return to play, and Quick Disabilities of the Arm, Shoulder, and Hand (QuickDASH) outcomes. A total of 18 collegiate football athletes were identified, all of whom were evaluated for follow-up by telephone, e-mail, or regular mail at an average 6-year follow-up. Nine were skill position players; the remaining 9 played in nonskill positions. All players returned to at least the same level of play. The average QuickDASH score for the entire cohort was 1 out of 100; QuickDASH work score, 0 out of 100; and sport score, 1 out of 100. Average time to surgery for skill position players was 12 days compared with 43 for non-skill position players. Average return to play for skill position players was 7 weeks postoperatively compared with 4 weeks for non-skill position players. There was no difference in average QuickDASH overall scores or subgroup scores between cohorts. Collegiate football athletes treated for thumb UCL injuries with suture anchor repair had quick return to play, reliable return to the same level of activity, and excellent long-term clinical outcomes. Skill position players had surgery sooner after injury and returned to play later than non-skill position players, with no differences in final level of play or clinical outcomes. Management of thumb UCL injuries in collegiate football athletes can be safely and effectively tailored according to the demands of the player's football position. Therapeutic IV. Copyright © 2014 American Society for Surgery of the Hand. Published by Elsevier Inc. All rights reserved.

Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms for organometallic complexes

NASA Astrophysics Data System (ADS)

Our studies of reactions of metal carbonyl cations and anions have shown that metal carbonyl cations can catalyze CO exchange reactions on metal carbonyl anions. This result provides further evidence for a mechanism involving attack of the metal carbonyl anion on a carbon of the metal carbonyl cation in CO(exp 2+) transfer reactions. Reaction of metal carbonyl anions with metal carbonyl halides is a common approach to formation of metal-metal bonds. We have begun to use kinetic data and product analysis to understand the formation of homobimetallic versus heterobimetallic products in such reactions. Initial data indicate a nucleophilic attack, possibly through a ring-slippage mechanism.

Quantum chemical calculations of anion complex [B12Hx(NF2)12-x]2-, x = 9 - 12

NASA Astrophysics Data System (ADS)

Koblova, E. A.; Saldin, V. I.; Ustinov, A. Yu

2017-01-01

The geometric, energetic, spectral and electronic properties of various isomers of B12Hх(NF2)12-х 2- anion complex with x = 9 - 12 have been studied using Density Functional Theory (B3LYP/6-311++G**). It was shown that the most stable isomers are characterized by the preference to form the most symmetric structures with uniformly distributed charge densities. However, when replacing a hydrogen atom with difluoramino group, an inductive effect occurs. NF2 group pulls a part of electron density that leads to the polarization of the boron core. Blue shifts in the IR spectrum compared to the vibrations of the free radical NF2 ranging from 5 to 69 cm-1 for the most stable isomers with the minimum total energy are characteristic and points to the stability of B12Hх(NF2)12-х 2- anions. The obtained results broaden the idea of aromaticity of B12H12 2- anion and will be useful in synthesis of new B12H12 2- derivatives.

The interplay of ion crosslinking, free ion content, and polymer mobility in PEO-based single-ion conductors

NASA Astrophysics Data System (ADS)

Lin, Kan-Ju; Maranas, Janna

2010-03-01

We use molecular dynamics simulation to study ion clustering and dynamics in ion containing polymers. This PEO based single-ion conducting ionomer serves as a model system for understanding cation transport in solid state polymer electrolytes (SPEs). Although small-angle x-ray scattering does not show an ionomer peak, we observer various cation-anion complexes in the simulation, suggesting ionomer backbones are crosslinked through ion complexes. These crosslinks reduce the adjacent PEO mobility resulting in a symmetric mobility gradient along the PEO chain. We vary the cation-anion interaction in the simulation to observe the interplay of cation-anion association, polymer mobility and cation motion. Cation-anion association controls the number of free ions, which is important in ionic conductivity when these materials are used as SPEs. Polymer mobility controls how fast the free ions are able to move through the SPE. High conductivity requires both a high free ion content and fast polymer motion. To understand the connection between the two, we ``tune'' the force field in order to manipulate the free ion content and observe the influence on PEO dynamics.

Electron accommodation dynamics in the DNA base thymine

NASA Astrophysics Data System (ADS)

King, Sarah B.; Stephansen, Anne B.; Yokoi, Yuki; Yandell, Margaret A.; Kunin, Alice; Takayanagi, Toshiyuki; Neumark, Daniel M.

2015-07-01

The dynamics of electron attachment to the DNA base thymine are investigated using femtosecond time-resolved photoelectron imaging of the gas phase iodide-thymine (I-T) complex. An ultraviolet pump pulse ejects an electron from the iodide and prepares an iodine-thymine temporary negative ion that is photodetached with a near-IR probe pulse. The resulting photoelectrons are analyzed with velocity-map imaging. At excitation energies ranging from -120 meV to +90 meV with respect to the vertical detachment energy (VDE) of 4.05 eV for I-T, both the dipole-bound and valence-bound negative ions of thymine are observed. A slightly longer rise time for the valence-bound state than the dipole-bound state suggests that some of the dipole-bound anions convert to valence-bound species. No evidence is seen for a dipole-bound anion of thymine at higher excitation energies, in the range of 0.6 eV above the I-T VDE, which suggests that if the dipole-bound anion acts as a "doorway" to the valence-bound anion, it only does so at excitation energies near the VDE of the complex.

Electron accommodation dynamics in the DNA base thymine.

PubMed

King, Sarah B; Stephansen, Anne B; Yokoi, Yuki; Yandell, Margaret A; Kunin, Alice; Takayanagi, Toshiyuki; Neumark, Daniel M

2015-07-14

The dynamics of electron attachment to the DNA base thymine are investigated using femtosecond time-resolved photoelectron imaging of the gas phase iodide-thymine (I(-)T) complex. An ultraviolet pump pulse ejects an electron from the iodide and prepares an iodine-thymine temporary negative ion that is photodetached with a near-IR probe pulse. The resulting photoelectrons are analyzed with velocity-map imaging. At excitation energies ranging from -120 meV to +90 meV with respect to the vertical detachment energy (VDE) of 4.05 eV for I(-)T, both the dipole-bound and valence-bound negative ions of thymine are observed. A slightly longer rise time for the valence-bound state than the dipole-bound state suggests that some of the dipole-bound anions convert to valence-bound species. No evidence is seen for a dipole-bound anion of thymine at higher excitation energies, in the range of 0.6 eV above the I(-)T VDE, which suggests that if the dipole-bound anion acts as a "doorway" to the valence-bound anion, it only does so at excitation energies near the VDE of the complex.

Microhydration of cytosine and its radical anion: cytosine.(H2O)n (n=1-5).

PubMed

Kim, Sunghwan; Schaefer, Henry F

2007-02-14

Microhydration effects on cytosine and its radical anion have been investigated theoretically, by explicitly considering various structures of cytosine complexes with up to five water molecules. Each successive water molecule (through n=5) is bound by 7-10 kcal mol(-1) to the relevant cytosine complex. The hydration energies are uniformly higher for the analogous anion systems. While the predicted vertical detachment energy (VDE) of the isolated cytosine is only 0.48 eV, it is predicted to increase to 1.27 eV for the lowest-lying pentahydrate of cytosine. The adiabatic electron affinity (AEA) of cytosine was also found to increase from 0.03 to 0.61 eV for the pentahydrate, implying that the cytosine anion, while questionable in the gas phase, is bound in aqueous solution. Both the VDE and AEA values for cytosine are smaller than those of uracil and thymine for a given hydration number. These results are in qualitative agreement with available experimental results from photodetachment-photoelectron spectroscopy studies of Schiedt et al. [Chem. Phys. 239, 511 (1998)].

Microhydration of cytosine and its radical anion: Cytosine.(H2O)n (n=1-5)

NASA Astrophysics Data System (ADS)

Kim, Sunghwan; Schaefer, Henry F.

2007-02-01

Microhydration effects on cytosine and its radical anion have been investigated theoretically, by explicitly considering various structures of cytosine complexes with up to five water molecules. Each successive water molecule (through n =5) is bound by 7-10kcalmol-1 to the relevant cytosine complex. The hydration energies are uniformly higher for the analogous anion systems. While the predicted vertical detachment energy (VDE) of the isolated cytosine is only 0.48eV, it is predicted to increase to 1.27eV for the lowest-lying pentahydrate of cytosine. The adiabatic electron affinity (AEA) of cytosine was also found to increase from 0.03to0.61eV for the pentahydrate, implying that the cytosine anion, while questionable in the gas phase, is bound in aqueous solution. Both the VDE and AEA values for cytosine are smaller than those of uracil and thymine for a given hydration number. These results are in qualitative agreement with available experimental results from photodetachment-photoelectron spectroscopy studies of Schiedt et al. [Chem. Phys. 239, 511 (1998)].

Matrix influences on the determination of common ions by using ion chromatography part 1--determination of inorganic anions.

PubMed

Michalski, Rajmund; Lyko, Aleksandra; Kurzyca, Iwona

2012-07-01

Ion chromatography is the most popular instrumental analytical method used for the determination of anions and cations in water and wastewater. Isocratic ion chromatography with suppressed conductivity detection is frequently used in laboratories carrying out routine analyses of inorganic anions. The paper presents the results of the research into the influence of selected inorganic anions dominant in environmental samples (Cl(-), NO(3)(-), SO(4)(2-)) on the possibility of simultaneous determination of F(-), Cl(-), NO(2)(-), NO(3)(-), PO(4)(3-) and SO(4)(2-) with the application of this most popular ion chromatography type in standard separation conditions. Four Dionex and four Metrohm anion-exchange columns were tested in standard separation conditions recommended by their manufacturers with both standard solutions and environmental samples with complex matrix.

Synthesis and spectroscopic studies of binuclear metal complexes of a tetradentate N2O2 Schiff base ligand derived from 4,6-diacetylresorcinol and benzylamine.

PubMed

Shebl, Magdy

2008-09-01

A tetradentate N2O2 donor Schiff base ligand, H2L, was synthesized by the condensation of 4,6-diacetylresorcinol with benzylamine. The structure of the ligand was elucidated by elemental analyses, IR, 1H NMR, electronic and mass spectra. Reaction of the Schiff base ligand with nickel(II), cobalt(II), iron(III), cerium(III), vanadyl(IV) and uranyl(VI) ions in 1:2 molar ratio afforded binuclear metal complexes. Also, reaction of the ligand with several copper(II) salts, including Cl-, NO3-, AcO-, ClO4- and SO42- afforded different metal complexes that reflect the non-coordinating or weakly coordinating power of the ClO(4)(-) anion as compared to the strongly coordinating power of SO42- and Cl- anions. Characterization and structure elucidation of the prepared complexes were achieved by elemental and thermal analyses, IR, 1H NMR, electronic, mass and ESR spectra as well as magnetic susceptibility measurements. The metal complexes exhibited different geometrical arrangements such as square planar, octahedral, square pyramidal and pentagonal bipyramidal arrangements. The variety in the geometrical arrangements depends on the nature of both the anion and the metal ion.

Influence of bidentate ligand donor types on the formation and stability in 2 + 1 fac-[MI(CO)3]+ (M = Re, 99mTc) complexes.

PubMed

Hayes, Thomas R; Bottorff, Shalina C; Slocumb, Winston S; Barnes, Charles L; Clark, Aurora E; Benny, Paul D

2017-01-24

In the last two decades, a number of chelate strategies have been proposed for the fac-[M I (CO) 3 ] + (M = Re, 99m Tc) core in radiopharmaceutical applications. However, the development of new ligands/complexes with improved function and in vivo performance has been limited in recent years. Expanding on our previous studies using the 2 + 1 labeling strategy, a series of bidentate ligands (neutral vs. anionic) containing an aromatic amine in combination with monodentate pyridine analogs or imidazole were explored to determine the influence of the bidentate and monodentate ligands on the formation and stability of the respective complexes. The 2 + 1 complexes with Re and 99m Tc were synthesized in two steps and characterized by standard radio/chemical methods. X-ray characterization and density functional theory analysis of the Re 2 + 1 complexes with the complete bidentate series with 4-dimethylaminopyridine were conducted, indicating enhanced ligand binding energies of the neutral over anionic ligands. In the 99m Tc studies, anionic bidentate ligands had significantly higher formation yields of the 2 + 1 product, but neutral ligands appear to have increased stability in an amino acid challenge assay. Both bidentate series exhibited improved stability by increasing the basicity of the pyridine ligands.

Influence of Bidentate Ligand Donor Types on the Formation and Stability in 2+1 fac-[MI(CO)3]+ (M = Re, 99mTc) Complexes

PubMed Central

Hayes, Thomas R.; Bottorff, Shalina C.; Slocumb, Winston S.; Barnes, Charles L.; Clark, Aurora E.; Benny, Paul D.

2017-01-01

In the last two decades, a number of chelate strategies have been proposed for the fac-[MI(CO)3]+ (M = Re, 99mTc) core in radiopharmaceutical applications. However, the development of new ligands/complexes with improved function and in vivo performance has been limited in recent years. Expanding on our previous studies using the 2+1 labeling strategy, a series of bidentate ligands (neutral vs. anionic) containing an aromatic amine in combination with monodentate pyridine analogs or imidazole were explored to determine the influence of the bidentate and monodentate ligands on the formation and stability of the respective complexes. The 2+1 complexes with Re and 99mTc were synthesized in two steps and characterized by standard radio/chemical methods. X-ray characterization and density functional theory analysis of the Re 2+1 complexes with the complete bidentate series with 4-dimethylaminopyridine were conducted, indicating enhanced ligand binding energies of the neutral over anionic ligands. In the 99mTc studies, anionic bidentate ligands had significantly higher formation yields of the 2+1 product, but neutral ligands appear to have increased stability in an amino acid challenge assay. Both bidentate series exhibited improved stability by increasing the basicity of the pyridine ligands. PMID:28045466

The Use of Electrospray Mass Spectrometry to Determine Speciation in a Dynamic Combinatorial Library for Anion Recognition

PubMed Central

Phillips, Hazel I A; Chernikov, Aleksey V; Fletcher, Nicholas C; Ashcroft, Alison E; Ault, James R; Filby, Maria H; Wilson, Andrew J

2012-01-01

The composition of a dynamic mixture of similar 2,2′-bipyridine complexes of iron(II) bearing either an amide (5-benzylamido-2,2′-bipyridine and 5-(2-methoxyethane)amido-2,2′-bipyridine) or an ester (2,2′-bipyridine-5-carboxylic acid benzylester and 2,2′-bipyridine-5-carboxylic acid 2-methoxyethane ester) side chain have been evaluated by electrospray mass spectroscopy in acetonitrile. The time taken for the complexes to come to equilibrium appears to be dependent on the counteranion, with chloride causing a rapid redistribution of two preformed heteroleptic complexes (of the order of 1 hour), whereas the time it takes in the presence of tetrafluoroborate salts is in excess of 24 h. Similarly the final distribution of products is dependent on the anion present, with the presence of chloride, and to a lesser extent bromide, preferring three amide-functionalized ligands, and a slight preference for an appended benzyl over a methoxyethyl group. Furthermore, for the first time, this study shows that the distribution of a dynamic library of metal complexes monitored by ESI-MS can adapt following the introduction of a different anion, in this case tetrabutylammonium chloride to give the most favoured heteroleptic complex despite the increasing ionic strength of the solution. PMID:22996943

Interaction between water-soluble rhodium complex RhCl(CO)(TPPTS)₂ and surfactants probed by spectroscopic methods.

PubMed

Zhou, Li-Mei; Guo, Cai-Hong; Fu, Hai-Yan; Jiang, Xiao-Hui; Chen, Hua; Li, Rui-Xiang; Li, Xian-Jun

2012-07-01

The interactions of rhodium complex RhCl(CO)(TPPTS)(2) [TPPTS=P(m-C(6)H(4)SO(3)Na)(3)] with cationic, nonionic, and anionic surfactants have been investigated by UV-vis, fluorescence and (1)H NMR measurements. The presence of four different species of RhCl(CO)(TPPTS)(2) in cationic cetyltrimethylammonium (CTAB) solution has been demonstrated: free rhodium complex, rhodium complex bound to CTAB monomer, rhodium complex bound to CTAB premicelles, rhodium complex bound to CTAB micelles. The spectroscopy data show that RhCl(CO)(TPPTS)(2) can adsorb on the interface of cationic CTAB micelles by strong electrostatic attraction, weakly bind to the nonionic polyoxyethylene (20) sorbitan monolaurate (Tween 20) micelles by hydrophobic interaction, and does not interact with anion sodium dodecyl sulfate (SDS) micelles due to the strong electrostatic repulsion. Copyright © 2012 Elsevier B.V. All rights reserved.

Squarylium-based chromogenic anion sensors.

PubMed

Lee, Eun-Mi; Gwon, Seon-Yeong; Son, Young-A; Kim, Sung-Hoon

2012-09-01

A squarylium (SQ) dye was synthesized by the reaction between squaric acid and 2,3,3-trimethylindolenine and its anion sensing properties were investigated using absorption and emission spectroscopy. This chemosensor exhibited high selectivity for CN(-) as compared with F(-), CH(3)CO(2)(-), Br(-), H(2)PO(4)(-), Cl(-), and NO(3)(-) in acetonitrile, which was attributed to the formation of a 1:1 squarylium:CN(-) coordination complex, the formation of which was supported by the calculated geometry of the complex. Copyright © 2012 Elsevier B.V. All rights reserved.

An anionic rhodium eta4-quinonoid complex as a multifunctional catalyst for the arylation of aldehydes with arylboronic acids.

PubMed

Son, Seung Uk; Kim, Sang Bok; Reingold, Jeffrey A; Carpenter, Gene B; Sweigart, Dwight A

2005-09-07

The pi-bonded rhodium quinonoid complex, K+[(1,4-benzoquinone)Rh(COD)]-, functions as a good catalyst for the coupling of arylboronic acid and aldehydes to afford diaryl alcohols. The catalysis is heterobimetallic in that both the transition metal and concomitant alkali metal counterion play an integral part in the reaction. In addition, the anionic quinonoid catalyst itself plays a bifunctional role by acting as a ligand to the boronic acid and as a Lewis acid receptor site for the transferring aryl group.

Anion-π interactions in active centers of superoxide dismutases.

PubMed

Ribić, Vesna R; Stojanović, Srđan Đ; Zlatović, Mario V

2018-01-01

We investigated 1060 possible anion-π interactions in a data set of 41 superoxide dismutase active centers. Our observations indicate that majority of the aromatic residues are capable to form anion-π interactions, mainly by long-range contacts, and that there is preference of Trp over other aromatic residues in these interactions. Furthermore, 68% of total predicted interactions in the dataset are multiple anion-π interactions. Anion-π interactions are distance and orientation dependent. We analyzed the energy contribution resulting from anion-π interactions using ab initio calculations. The results showed that, while most of their interaction energies lay in the range from -0 to -4kcalmol -1 , those energies can be up to -9kcalmol -1 and about 34% of interactions were found to be repulsive. Majority of the suggested anion-π interacting residues in ternary complexes are metal-assisted. Stabilization centers for these proteins showed that all the six residues found in predicted anion-π interactions are important in locating one or more of such centers. The anion-π interacting residues in these proteins were found to be highly conserved. We hope that these studies might contribute useful information regarding structural stability and its interaction in future designs of novel metalloproteins. Copyright © 2017 Elsevier B.V. All rights reserved.

Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes.

PubMed

Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

2016-12-01

The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (U VI O 2 2+ ) coordinated by formate or acetate ligands. Anionic complexes containing U VI O 2 2+ and formate ligands fragment by decarboxylation and elimination of CH 2 =O, ultimately to produce an oxo-hydride species [U VI O 2 (O)(H)] - . Cationic species ultimately dissociate to make [U VI O 2 (OH)] + . Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH 3 CO 2 •, with associated reduction of uranyl to U V O 2 + . Subsequent CID steps cause elimination of CO 2 and CH 4 , ultimately to produce [U V O 2 (O)] - . Loss of CH 4 occurs by an intra-complex H + transfer process that leaves U V O 2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH 2 =C=O to leave [U V O 2 (O)] - . Elimination of CH 4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H 2 O. The reactions of other anionic species with gas-phase H 2 O create hydroxyl products, presumably through the elimination of H 2 . Graphical Abstract ᅟ.

Gas Phase Reactions of Ions Derived from Anionic Uranyl Formate and Uranyl Acetate Complexes

NASA Astrophysics Data System (ADS)

Perez, Evan; Hanley, Cassandra; Koehler, Stephen; Pestok, Jordan; Polonsky, Nevo; Van Stipdonk, Michael

2016-12-01

The speciation and reactivity of uranium are topics of sustained interest because of their importance to the development of nuclear fuel processing methods, and a more complete understanding of the factors that govern the mobility and fate of the element in the environment. Tandem mass spectrometry can be used to examine the intrinsic reactivity (i.e., free from influence of solvent and other condensed phase effects) of a wide range of metal ion complexes in a species-specific fashion. Here, electrospray ionization, collision-induced dissociation, and gas-phase ion-molecule reactions were used to create and characterize ions derived from precursors composed of uranyl cation (UVIO2 2+) coordinated by formate or acetate ligands. Anionic complexes containing UVIO2 2+ and formate ligands fragment by decarboxylation and elimination of CH2=O, ultimately to produce an oxo-hydride species [UVIO2(O)(H)]-. Cationic species ultimately dissociate to make [UVIO2(OH)]+. Anionic complexes containing acetate ligands exhibit an initial loss of acetyloxyl radical, CH3CO2•, with associated reduction of uranyl to UVO2 +. Subsequent CID steps cause elimination of CO2 and CH4, ultimately to produce [UVO2(O)]-. Loss of CH4 occurs by an intra-complex H+ transfer process that leaves UVO2 + coordinated by acetate and acetate enolate ligands. A subsequent dissociation step causes elimination of CH2=C=O to leave [UVO2(O)]-. Elimination of CH4 is also observed as a result of hydrolysis caused by ion-molecule reaction with H2O. The reactions of other anionic species with gas-phase H2O create hydroxyl products, presumably through the elimination of H2.

Impact of Carrier Fluid Composition on Recovery of Nanoparticles and Proteins in Flow Field Flow Fractionation

PubMed Central

Schachermeyer, Samantha; Ashby, Jonathan; Kwon, MinJung; Zhong, Wenwan

2012-01-01

Flow field flow fractionation (F4) is an invaluable separation tool for large analytes, including nanoparticles and biomolecule complexes. However, sample loss due to analyte-channel membrane interaction limits extensive usage of F4 at present, which could be strongly affected by the carrier fluid composition. This work studied the impacts of carrier fluid (CF) composition on nanoparticle (NP) recovery in F4, with focus on high ionic strength conditions. Successful analysis of NPs in a biomolecules-friendly environment could expand the applicability of F4 to the developing field of nanobiotechnology. Recovery of the unfunctionalized polystyrene NPs of 199-, 102-, and 45-nm in CFs with various pH (6.2, 7.4 and 8.2), increasing ionic strength (0–0.1 M), and different types of co- and counter-ions, were investigated. Additionally, elution of the 85-nm carboxylate NPs and two proteins, human serum albumin (HSA) and immunoglobulin (IgG), at high ionic strengths (0–0.15 M) was investigated. Our results suggested that; 1) Electrostatic repulsion between the negatively charged NPs and the regenerated cellulose membrane was the main force to avoid particle adsorption on the membrane; 2) Larger particles experienced higher attractive force and thus were influenced more by variation in CF composition; and 3) Buffers containing weak anions or NPs with weak anion as the surface functional groups provided higher tolerance to the increase in ionic strength, owing to more anions being trapped inside the NP porous structure. Protein adsorption onto the membrane was also briefly investigated in salted CFs, using human serum albumin and immunoglobulin. We believe our findings could help to identify the basic carrier fluid composition for higher sample recovery in F4 analysis of nanoparticles in a protein-friendly environment, which will be useful for applying F4 in bioassays and in nanotoxicology studies. PMID:23058938

Two-Step Adsorption of PtCl 6 2– Complexes at a Charged Langmuir Monolayer: Role of Hydration and Ion Correlations

DOE PAGES

Uysal, Ahmet; Rock, William; Qiao, Baofu; ...

2017-11-03

Anion exchange at positively charged interfaces plays an important role in a variety of physical and chemical processes. However, the molecular-scale details of these processes, especially with heavy and large anionic complexes, are not well-understood. Here, we studied the adsorption of PtCl 6 2– anionic complexes to floating DPTAP monolayers in the presence of excess Cl– as a function of the bulk chlorometalate concentration. This system aims to simulate the industrial conditions for heavy metal separations with solvent extraction. In situ X-ray scattering and fluorescence measurements, which are element and depth sensitive, show that the chlorometalate ions only adsorb inmore » the diffuse layer at lower concentrations, while they adsorb predominantly in the Stern layer at higher concentrations. The response of DPTAP molecules to the adsorbed ions is determined independently by grazing incidence X-ray diffraction and supports this picture. Molecular dynamics simulations further elucidate the nanoscale structure of the interfacial complexes. The results suggest that ion hydration and ion–ion correlations play a key role in the competitive adsorption process.« less

Isolation and Characterization of FORMATE/NI(CYCLAM)^{2+} Complexes with Cryogenic Ion Vibrational Predissociation

NASA Astrophysics Data System (ADS)

Wolk, Arron B.; Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Mark A.

2013-06-01

Transition metal-based organometallic catalysts are a promising means of converting CO_{2} to transportable fuels. Ni(cyclam)^{2+}(cyclam = 1,4,8,11-tetraazacyclotetradecane), a Ni^{II} complex ligated by four nitrogen centers, has shown promise as a catalyst selective for CO_{2} reduction in aqueous solutions. The cyclam ligand has four NH hydrogen bond donors that can adopt five conformations, each offering distinct binding motifs for coordination of CO_{2} close to the metal center. To probe the ligand conformation and the role of hydrogen bonding in adduct binding, we extract Ni(cyclam)^{2+} complexes with the formate anion and some of its analogs from solution using electrospray ionization, and characterize their structures using cryogenic ion vibrational predissociation spectroscopy. Using the signature vibrational features of the embedded carboxylate anion and the NH groups as reporters, we compare the binding motifs of oxalate, benzoate, and formate anions to the Ni(cyclam)^{2+} framework. Finally, we comment on possible routes to generate the singly charged Ni(cyclam)^{+} complex, a key intermediate that has been invoked in the catalytic CO_{2} reduction cycle, but has never been isolated through ion processing techniques.

Parturient hypocalcemia in jersey cows fed alfalfa haylage-based diets with different cation to anion ratios.

PubMed

Gaynor, P J; Mueller, F J; Miller, J K; Ramsey, N; Goff, J P; Horst, R L

1989-10-01

Jersey cows were fed three alfalfa haylage-based diets with different cation-anion balances beginning 6 wk preceding third or later calving and ending 24 to 36 h postpartum. Sodium and Cl as percentages of dietary DM were .08 and 1.66 in diet 1 (anionic, 5 cows), .44 and .91 in diet 2 (intermediate, 6 cows), and 1.60 and .34 in diet 3 (cationic, 6 cows). Cation-anion balances were 22, 60, and 126 meq/100 g DM; Ca:P ratios averaged 4:1. Cows fed diet 1 in comparison with cows fed diets 2 or 3 over 6 wk had similar concentrations of Ca, P, and Na but higher concentrations of Mg and K in plasma and higher urinary excretions of Ca and Mg. Concentrations of 1,25-dihydroxyvitamin D 3 d before parturition were higher in cows fed diet 1 than in cows fed diets 2 or 3. Within 36 h after calving, mean concentrations of Ca in plasma (mg/dl, range) of cows fed diets 1 to 3, respectively, were 7 (8.7 to 6.2), 6.5 (7.8 to 3.9), and 6.3 (7.8 to 3.8). Number of cases of clinical milk fever by diet were 0 of 5, 2 of 6, and 1 of 6 cows. Alteration of dietary cation-anion balance by addition of Cl may effectively reduce incidence and severity of parturient hypocalcemia.

Functionalized guanidinium chloride based colourimetric sensors for fluoride and acetate: single crystal X-ray structural evidence of -NH deprotonation and complexation.

PubMed

Bose, Purnandhu; Ahamed, B Nisar; Ghosh, Pradyut

2011-03-21

A series of new symmetrically functionalized guanidinium chlorides (S1-S10) are synthesized in good yields and their sensing ability toward anions is studied in MeCN-DMF (24 : 1) (v/v). The absorption bands of these molecules in the presence of anions are tuned by varying the functional groups attached to the guanidinium moiety (which resembles urea) with respect to (i) aromaticity (S1-S4), (ii) electron induction effect (S1, S5-S9), (iii) positional isomeric effect (S7-S9), (iv) indole functionality (S10) of the conjugated aryl units. Anions that are above Cl(-) in the Hofmeister series (F(-), AcO(-), H(2)PO(4)(-)) are eligible as an analyte in this series of molecules whereas less basic anions than Cl(-) do not cause any interference. Thus, this series of molecules are suitable for the detection of anions in the narrow window of the Hofmeister series. Out of all the anions, only fluoride causes vivid colour changes from yellow to red to reddish orange and finally to blue, irrespective of the increasing aromaticity, induction and positional isomeric effect of the substituent that is attached to the guanidinium moiety. Interestingly, S9 has shown the ability to sense distinctly both F(-) and AcO(-) colourimetrically. Further S10, a sensor attached with indole functionality shows selective sensing of F(-) colourimetrically with a NIR signature at ∼930 nm though both these outputs are very unstable in nature. Stability constants for complex formation of S1-S10 (except S5) with F(-), AcO(-) are calculated by UV-vis titration experiments. Finally single crystal X-ray structural studies on the species 1 formed upon treating S6 with sodium fluoride confirms -NH deprotonation, whereas the reaction of S6 and S2 with sodium benzoate shows 1:1 host:guest binding that results in complexes 2 and 3 respectively.

Crystal structure of trans-diammine(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4 N)chromium(III) tetra­chlorido­zincate chloride monohydrate from synchrotron data

PubMed Central

Moon, Dohyun; Choi, Jong-Ha

2016-01-01

The asymmetric unit of the title complex salt, [Cr(C10H24N4)(NH3)2][ZnCl4]Cl·H2O, is comprised of four halves of the CrIII complex cations (the counterparts being generated by application of inversion symmetry), two tetra­chlorido­zincate anions, two chloride anions and two water mol­ecules. Each CrIII ion is coordinated by the four N atoms of the cyclam (1,4,8,11-tetra­aza­cyclo­tetra­deca­ne) ligand in the equatorial plane and by two N atoms of ammine ligands in axial positions, displaying an overall distorted octa­hedral coordination environment. The Cr—N(cyclam) bond lengths range from 2.0501 (15) to 2.0615 (15) Å, while the Cr—(NH3) bond lengths range from 2.0976 (13) to 2.1062 (13) Å. The macrocyclic cyclam moieties adopt the trans-III conformation with six- and five-membered chelate rings in chair and gauche conformations. The [ZnCl4]2− anions have a slightly distorted tetra­hedral shape. In the crystal, the Cl− anions link the complex cations, as well as the solvent water mol­ecules, through N—H⋯Cl and O—H⋯Cl hydrogen-bonding inter­actions. The supra­molecular set-up also includes N—H⋯Cl, C—H⋯Cl, N—H⋯O and O—H⋯Cl hydrogen bonding between N—H or C—H groups of cyclam, ammine N—H and water O—H donor groups, and O atoms of the water mol­ecules, Cl− anions or Cl atoms of the [ZnCl4]2− anions as acceptors, leading to a three-dimensional network structure. PMID:27375863

Psychological status as a function of residual scarring and facial asymmetry after surgical repair of cleft lip and palate.

PubMed

Millar, Keith; Bell, Aileen; Bowman, Adrian; Brown, Denise; Lo, Tsz-Wai; Siebert, Paul; Simmons, David; Ayoub, Ashraf

2013-03-01

Objective : Objective measure of scarring and three-dimensional (3D) facial asymmetry after surgical correction of unilateral cleft lip (UCL) and unilateral cleft lip (UCLP). It was hypothesized that the degree of scarring or asymmetry would be correlated with poorer psychological function. Design : In a cross-sectional design, children underwent 3D imaging of the face and completed standardized assessments of self-esteem, depression, and state and trait anxiety. Parents rated children's adjustment with a standard scale. Setting : Glasgow Dental School, School of Medicine, College of Medical, Veterinary and Life Sciences. Patients : Fifty-one children aged 10 years with UCLP and 43 with UCL were recruited from the cohort treated with the surgical protocol of the CLEFTSIS managed clinical network in Scotland. Methods : Objective assessment to determine the luminance and redness of the scar and facial asymmetry. Depression, anxiety, and a self-esteem assessment battery were used for the psychological analysis. Results : Cleft cases showed superior psychological adjustment when compared with normative data. Prevalence of depression matched the population norm. The visibility of the scar (luminance ratio) was significantly correlated with lower self-esteem and higher trait anxiety in UCLP children (P  =  .004). Similar but nonsignificant trends were seen in the UCL group. Parental ratings of poorer adjustment also correlated with greater luminance of the scar. Conclusions : The objectively defined degree of postoperative cleft scarring was associated with subclinical symptoms of anxiety, depression, and low self-esteem.

Pattern-based detection of anion pollutants in water with DNA polyfluorophores† †Electronic supplementary information (ESI) available: Additional figures and tables and experimental details. See DOI: 10.1039/c4sc03992k Click here for additional data file.

PubMed Central

Kwon, Hyukin; Jiang, Wei

2015-01-01

Many existing irrigation, industrial and chemical storage sites are currently introducing hazardous anions into groundwater, making the monitoring of such sites a high priority. Detecting and quantifying anions in water samples typically requires complex instrumentation, adding cost and delaying analysis. Here we address these challenges by development of an optical molecular method to detect and discriminate a broad range of anionic contaminants with DNA-based fluorescent sensors. A library of 1296 tetrameric-length oligodeoxyfluorosides (ODFs) composed of metal ligand and fluorescence modulating monomers was constructed with a DNA synthesizer on PEG-polystyrene microbeads. These oligomers on beads were incubated with YIII or ZnII ions to provide affinity and responsiveness to anions. Seventeen anions were screened with the library under an epifluorescence microscope, ultimately yielding eight chemosensors that could discriminate 250 μM solutions of all 17 anions in buffered water using their patterns of response. This sensor set was able to identify two unknown anion samples from ten closely-responding anions and could also function quantitatively, determining unknown concentrations of anions such as cyanide (as low as 1 mM) and selenate (as low as 50 μM). Further studies with calibration curves established detection limits of selected anions including thiocyanate (detection limit ∼300 μM) and arsenate (∼800 μM). The results demonstrate DNA-like fluorescent chemosensors as versatile tools for optically analyzing environmentally hazardous anions in aqueous environments. PMID:26146537

RIPK3 regulates p62-LC3 complex formation via the caspase-8-dependent cleavage of p62.

PubMed

Matsuzawa, Yu; Oshima, Shigeru; Nibe, Yoichi; Kobayashi, Masanori; Maeyashiki, Chiaki; Nemoto, Yasuhiro; Nagaishi, Takashi; Okamoto, Ryuichi; Tsuchiya, Kiichiro; Nakamura, Tetsuya; Watanabe, Mamoru

2015-01-02

RIPK3 is a key molecule for necroptosis, initially characterized by necrotic cell death morphology and the activation of autophagy. Cell death and autophagic signaling are believed to tightly regulate each other. However, the associated recruitment of signaling proteins remains poorly understood. p62/sequestosome-1 is a selective autophagy substrate and a selective receptor for ubiquitinated proteins. In this study, we illustrated that both mouse and human RIPK3 mediate p62 cleavage and that RIPK3 interacts with p62, resulting in complex formation. In addition, RIPK3-dependent p62 cleavage is restricted by the inhibition of caspases, especially caspase-8. Moreover, overexpression of A20, a ubiquitin-editing enzyme and an inhibitor of caspase-8 activity, inhibits RIPK3-dependent p62 cleavage. To further investigate the potential role of RIPK3 in selective autophagy, we analyzed p62-LC3 complex formation, revealing that RIPK3 prevents the localization of LC3 and ubiquitinated proteins to the p62 complex. In addition, RIPK3-dependent p62-LC3 complex disruption is regulated by caspase inhibition. Taken together, these results demonstrated that RIPK3 interacts with p62 and regulates p62-LC3 complex formation. These findings suggested that RIPK3 serves as a negative regulator of selective autophagy and provides new insights into the mechanism by which RIPK3 regulates autophagic signaling. Copyright © 2014 Elsevier Inc. All rights reserved.

Tetrel bond of pseudohalide anions with XH3F (X = C, Si, Ge, and Sn) and its role in SN2 reaction.

PubMed

Liu, Mingxiu; Li, Qingzhong; Cheng, Jianbo; Li, Wenzuo; Li, Hai-Bei

2016-12-14

The complexes of XH 3 F⋯N 3 - /OCN - /SCN - (X = C, Si, Ge, and Sn) have been investigated at the MP2/aug-cc-pVTZ(PP) level. The σ-hole of X atom in XH 3 F acts as a Lewis acid forming a tetrel bond with pseudohalide anions. Interaction energies of these complexes vary from -8 to -50 kcal/mol, mainly depending on the nature of X and pseudohalide anions. Charge transfer from N/O/S lone pair to X-F and X-H σ * orbitals results in the stabilization of these complexes, and the former orbital interaction is responsible for the large elongation of X-F bond length and the remarkable red shift of its stretch vibration. The tetrel bond in the complexes of XH 3 F (X = Si, Ge, and Sn) exhibits a significant degree of covalency with XH 3 F distorted significantly in these complexes. A breakdown of the individual forces involved attributes the stability of the interaction to mainly electrostatic energy, with a relatively large contribution from polarization. The transition state structures that connect the two minima for CH 3 Br⋯N 3 - complex have been localized and characterized. The energetic, geometrical, and topological parameters of the complexes were analyzed in the different stages of the S N 2 reaction N 3 - + CH 3 Br → Br - + CH 3 N 3 .

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

Christopher M. Leavitt; Garold L. Gresham; Michael T. Benson

Diphenyldithiophosphinate (DTP) ligands modified with electron-withdrawing trifluoromethyl (TFM) substitutents are of high interest because they have demonstrated potential for exceptional separation of Am3+ from lanthanide3+ cations. Specifically, the bis(ortho-TFM) (L1-) and (ortho-TFM)(meta-TFM) (L2-) derivatives have shown excellent separation selectivity, while the bis(meta-TFM) (L3)- and unmodified DTP (Lu-) did not. Factors responsible for selective coordination have been investigated using density functional theory (DFT) calculations in concert with competitive dissociation reactions in the gas phase. To evaluate the role of (DTP+H) acidity, density functional calculations were used to predict pKa values, which followed the trend of L3 < L2 < L1 L1- > L2- > L3-.« less

Cocrystal solubility product analysis - Dual concentration-pH mass action model not dependent on explicit solubility equations.

PubMed

Avdeef, Alex

2017-12-15

A novel general computational approach is described to address many aspects of cocrystal (CC) solubility product (K sp ) determination of drug substances. The CC analysis program, pDISOL-X, was developed and validated with published model systems of various acid-base combinations of active pharmaceutical ingredients (APIs) and coformers: (i) carbamazepine cocrystal systems with 4-aminobenzoic acid, cinnamic acid, saccharin, and salicylic acid, (ii) for indomethacin with saccharin, (iii) for nevirapine with maleic acid, saccharin, and salicylic acid, and (iv) for gabapentin with 3-hydroxybenzoic acid. In all systems but gabapentin, the coformer is much more soluble than the API. The model systems selected are those with available published dual concentration-pH data, one set for the API and one set for the coformer, generally measured at eutectic points (thermodynamically-stable three phases: solution, cocrystal, and crystalline API or coformer). The carbamazepine-cinnamic acid CC showed a substantial elevation in the API equilibrium concentration above pH5, consistent with the formation of a complex between carbamazepine and cinnamate anion. The analysis of the gabapentin:3-hydroxybenzoic acid 1:1 CC system indicated four zones of solid suspensions: coformer (pH<3.25), coformer and cocrystal eutectic (pH3.25-4.44), cocrystal (pH4.44-5.62), and API (pH>5.62). The general approach allows for testing of many possible equilibrium models, including those comprising drug-coformer complexation. The program calculates the ionic strength at each pH. From this, the equilibrium constants are adjusted for activity effects, based on the Stokes-Robinson hydration theory. The complete speciation analysis of the CC systems may provide useful insights into pH-sensitive dissolution effects that could potentially influence bioavailability. Copyright © 2017 Elsevier B.V. All rights reserved.

Two three-dimensional coordination polymers of lead(II) with iminodiacetate and naphthalene-dicarboxylate anions: Synthesis, characterization and luminescence behavior

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

Hazari, Debdoot; Jana, Swapan Kumar; Fleck, Michel

2014-11-15

Two lead(II) compounds [Pb{sub 3}(idiac){sub 3}(phen){sub 2}(H{sub 2}O)]·2(H{sub 2}O) (1) and [Pb(ndc)]{sub n} (2), where H{sub 2}idiac=iminodiacetic acid, phen=1,10-phenanthroline and H{sub 2}ndc=naphthalene-2,6-dicarboxylic acid, have been synthesized and structurally characterized. Single crystal X-ray diffraction analysis showed that compound 1 is a discrete trinuclear complex (of two-fold symmetry) which evolves to a supramolecular 3D network via π–π interactions, while in compound 2 the naphthalene dicarboxylate anion act as a linker to form a three dimensional architecture, where the anion adopts a bis-(bidentate bridging) coordination mode connecting four Pb(II) centers. The photoluminescence property of the two complexes has been studied. - graphical abstract:more » Two new topologically different 1D coordination polymers formed by Pb{sub 4} clusters have been synthesized and characterized by x-ray analysis. The luminescence and thermal properties have been studied. - Highlights: • 1 is a trinuclear complex of Pb(II) growing to 3D network via weak interactions. • In 1, layers of (4,4) rhomboidal topology are identified. • In 2, the ndc anion adopts interesting bis-(bidentate bridging) coordination. • In 2, network is reinforced by C–H…π-ring interactions between the ndc rings.« less

Selective Anion Binding by a Cofacial Binuclear Zinc Complex of a Schiff-Base Pyrrole Macrocycle

PubMed Central

Devoille, Aline M. J.; Richardson, Patricia; Bill, Nathan; Sessler, Jonathan L.; Love, Jason B.

2011-01-01

The synthesis of the new cofacial binuclear zinc complex [Zn2(L)] of a Schiff-base pyrrole macrocycle is reported. It was discovered that the binuclear microenvironment between the two metals of [Zn2(L)] is suited for the encapsulation of anions, leading to the formation of [K(THF)6][Zn2(μ-Cl)(L)].2THF and [Bun4N][Zn2(μ-OH)(L)] which were characterized by X-ray crystallography. Unusually obtuse Zn-X-Zn angles (X=Cl: 150.54(9)° and OH: 157.4(3)°) illustrate the weak character of these interactions and the importance of the cleft pre-organization to stabilize the host. In the absence of added anion, aggregation of [Zn2(L)] was inferred and investigated by successive dilutions and by the addition of coordinating solvents to [Zn2(L)] solutions using NMR spectroscopy as well as isothermal microcalorimetry (ITC). On anion addition, evidence for de-aggregation of [Zn2(L)], combined with the formation of the 1:1 host-guest complex, was observed by NMR spectroscopy and ITC titrations. Furthermore, [Zn2(L)] binds to Cl− selectively in THF as deduced from the ITC analyses, while other halides induce only de-aggregation. These conclusions were reinforced by DFT calculations, which indicated that the binding energies of OH− and Cl− were significantly greater than for the other halides. PMID:21391550

A novel upconversion@polydopamine core@shell nanoparticle based aptameric biosensor for biosensing and imaging of cytochrome c inside living cells.

PubMed

Ma, Lina; Liu, Fuyao; Lei, Zhen; Wang, Zhenxin

2017-01-15

Herein, a novel upconversion@polydopamine core@shell nanoparticle (termed as UCNP@PDA NP) -based aptameric biosensor has been fabricated for the quantitative analysis of cytochrome c (Cyt c) inside living cells, which comprises an UCNP@PDA NP, acting as an internal reference and fluorescence quenching agent, and Cy3 modified aptamer enabling ratiometric quantitative Cyt c measurement. After the hybridization of Cy3 labeled aptamer with amino-terminated single DNA on the UCNP@PDA NP surface (termed as UCNP@PDA@AP), the fluorescence of Cy3 can be efficiently quenched by the PDA shell. With the spontaneous cellular uptake of UCNP@PDA@AP, the Cyt c aptamer dissociates from UCNP@PDA NP surface through formation of aptamer-Cyt c complex, resulting in concomitant activation of the Cy3 fluorescence. High amount of Cyt c leads to high fluorescence emission, enabling direct visualization/measurement of the Cyt c by fluorescence microscopy/spectroscopy. The steady upconversion luminescent (UCL) signals can be employed not only for intracellular imaging, but also as an internal reference for evaluating intracellular Cyt c amount using the ratio of fluorescence intensity of Cy3 with the UCL intensity of UCNP. The UCNP@PDA@AP shows a reasonable detection limit (20nM) and large dynamic range (50nM to 10μM, which covers the literature reported values (1-10μM) for cytosolic Cyt c in apoptotic cells) for detecting Cyt c in buffer with excellent selectivity. In addition, the UCNP@PDA@AP has been successfully used to monitor etoposide induced intracellular releasing of Cyt c, providing the possibility for cell-based screening of apoptosis-inducing drugs. Copyright © 2016 Elsevier B.V. All rights reserved.

Activator anion binding site in pyridoxal phosphorylase b: the binding of phosphite, phosphate, and fluorophosphate in the crystal.

PubMed Central

Oikonomakos, N. G.; Zographos, S. E.; Tsitsanou, K. E.; Johnson, L. N.; Acharya, K. R.

1996-01-01

It has been established that phosphate analogues can activate glycogen phosphorylase reconstituted with pyridoxal in place of the natural cofactor pyridoxal 5'-phosphate (Change YC. McCalmont T, Graves DJ. 1983. Biochemistry 22:4987-4993). Pyridoxal phosphorylase b has been studied by kinetic, ultracentrifugation, and X-ray crystallographic experiments. In solution, the catalytically active species of pyridoxal phosphorylase b adopts a conformation that is more R-state-like than that of native phosphorylase b, but an inactive dimeric species of the enzyme can be stabilized by activator phosphite in combination with the T-state inhibitor glucose. Co-crystals of pyridoxal phosphorylase b complexed with either phosphite, phosphate, or fluorophosphate, the inhibitor glucose, and the weak activator IMP were grown in space group P4(3)2(1)2, with native-like unit cell dimensions, and the structures of the complexes have been refined to give crystallographic R factors of 18.5-19.2%, for data between 8 and 2.4 A resolution. The anions bind tightly at the catalytic site in a similar but not identical position to that occupied by the cofactor 5'-phosphate group in the native enzyme (phosphorus to phosphorus atoms distance = 1.2 A). The structural results show that the structures of the pyridoxal phosphorylase b-anion-glucose-IMP complexes are overall similar to the glucose complex of native T-state phosphorylase b. Structural comparisons suggest that the bound anions, in the position observed in the crystal, might have a structural role for effective catalysis. PMID:8976550

trans-Bis[4-amino-3,5-bis­(2-pyrid­yl)-4H-1,2,4-triazole-κN 3]diaqua­cobalt(II) bis­(3-carb­oxy-5-nitro­benzoate)

PubMed Central

Wang, Xi; Shao, Chun-Fu; Li, Cheng-Peng

2011-01-01

The title complex, [Co(C12H10N6)2(H2O)2](C8H4NO6)2, is composed of a mononuclear cobalt(II) cation and two 3-carb­oxy-5-nitro­benzoate anions for charge balance. In the cation, the CoII atom is six-coordinated in a distorted octa­hedral geometry. It bonds to two O atoms of two water mol­ecules, and two pairs of N atoms from two 4-amino-3,5-bis­(2-pyrid­yl)-4H-1,2,4-triazole mol­ecules, which behave as bidentate chelating ligands. There are intra­molecular N—H⋯N hydrogen bonds in the cation. In the crystal, there are a number of inter­molecular N—H⋯O and O—H⋯O hydrogen bonds, as well as inter­molecular π–π stacking inter­actions [centroid–centroid distances = 3.657 (2) and 3.847 (2) Å], that link the mol­ecules into two-dimensional networks lying parallel to the ab plane. The presence of C—H⋯O inter­actions leads to the formation of a three-dimensional network. PMID:22058688

A highly selective and turn-on fluorescence sensor for detection of cyanide.

PubMed

Jhong, Yi; Hsieh, Wei Hsun; Chir, Jiun-Ly; Wu, An-Tai

2014-11-01

2-Hydroxy-1-naphthaldehyde (receptor 1) serves as a selective chemosensor for cyanide anion (CN(-)). In the presence of CN(-), an enhanced fluorescent intensity and red shift were observed. The observed complexation between receptor 1 and CN(-) may cause from a formation of phenoxide anion by nucleophilic addition of the CN(-) to carbonyl group.

Aza compounds as anion receptors

DOEpatents

Lee, H.S.; Yang, X.Q.; McBreen, J.

1998-01-06

A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li{sup +} ion in alkali metal batteries. 3 figs.

Aza compounds as anion receptors

DOEpatents

Lee, Hung Sui; Yang, Xiao-Qing; McBreen, James

1998-01-06

A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li.sup.+ ion in alkali metal batteries.

Crystal structure of (18-crown-6)potassium(I) [(1,2,3,4,5-η)-cyclo-hepta-dien-yl][(1,2,3-η)-cyclo-hepta-trien-yl]cobalt(I).

PubMed

Brennessel, William W; Ellis, John E

2015-03-01

The reaction of bis-(anthracene)cobaltate(-I) with excess cyclo-hepta-triene, C7H8, resulted in a new 18-electron cobaltate containing two different seven-membered ring ligands, based on single-crystal X-ray diffraction. The asymmetric unit of this structure contains two independent cation-anion pairs of the title complex, [K(18-crown-6)][Co(η(3)-C7H7)(η(5)-C7H9)], where 18-crown-6 stands for 1,4,7,10,13,16-hexa-oxa-cyclo-octa-decane (C12H24O6), in general positions and well separated. Each (18-crown-6)potassium cation is in contact with the η(3)-coordinating ligand of one cobaltate complex. Each η(3)-coordinating ligand behaves as an allylic anion whose exo-diene moiety is bent away from the allylic plane, and thus is not involved directly in the bonding. The metal-coordinating portions of the anionic η(5) ligands are planar and one of these ligands is modeled as disordered over two positions, with occupancy ratio 0.699 (5):0.301 (5), such that one orientation is rotated by one carbon atom with respect to the other. The diffraction intensities were integrated according to non-merohedral twin law [-1 0 0/0 -1 0/0.064 0 1], a 180° rotation about reciprocal lattice axis [001], and the masses of the twin domains refined to equal amounts. As both ligands are formally coordinated as anions, the cobalt atom is best considered to be Co(I). This compound is of inter-est as the first to possess cyclo-hepta-trienyl and cyclo-hepta-dienyl ligands in an anionic metal complex.

Detection of anions by normal Raman spectroscopy and surface-enhanced Raman spectroscopy of cationic-coated substrates.

PubMed

Mosier-Boss, P A; Lieberman, S H

2003-09-01

The use of normal Raman spectroscopy and surface-enhanced Raman spectroscopy (SERS) of cationic-coated silver and gold substrates to detect polyatomic anions in aqueous environments is examined. For normal Raman spectroscopy, using near-infrared excitation, linear concentration responses were observed. Detection limits varied from 84 ppm for perchlorate to 2600 ppm for phosphate. In general, detection limits in the ppb to ppm concentration range for the polyatomic anions were achieved using cationic-coated SERS substrates. Adsorption of the polyatomic anions on the cationic-coated SERS substrates was described by a Frumkin isotherm. The SERS technique could not be used to detect dichromate, as this anion reacted with the coatings to form thiol esters. A competitive complexation method was used to evaluate the interaction of chloride ion with the cationic coatings. Hydrogen bonding and pi-pi interactions play significant roles in the selectivity of the cationic coatings.

Gadolinium sulfate modified by formate to obtain optimized magneto-caloric effect.

PubMed

Xu, Long-Yang; Zhao, Jiong-Peng; Liu, Ting; Liu, Fu-Chen

2015-06-01

Three new Gd(III) based coordination polymers [Gd2(C2H6SO)(SO4)3(H2O)2]n (1), {[Gd4(HCOO)2(SO4)5(H2O)6]·H2O}n (2), and [Gd(HCOO)(SO4)(H2O)]n (3) were obtained by modifying gadolinium sulfate. With the gradual increase of the volume ratio of HCOOH and DMSO in synthesis, the formate anions begin to coordinate with metal centers; this results in the coordination numbers of sulfate anion increasing and the contents of water and DMSO molecules decreasing in target complexes. Accordingly, spin densities both per mass and per volume were enhanced step by step, which are beneficial for the magneto-caloric effect (MCE). Magnetic studies reveal that with the more formate anions present, the larger the negative value of magnetic entropy change (-ΔSm) is. Complex 3 exhibits the largest -ΔSm = 49.91 J kg(-1) K(-1) (189.51 mJ cm(-3) K(-1)) for T = 2 K and ΔH = 7 T among three new complexes.

Synthesis of Potential Prophylactic Agents Against Cyanide Intoxication

DTIC Science & Technology

1993-05-06

34/21) S 2,6-C 2 Ad 72 mp 139" CsH3C12NO 163 (lie mp 139.5-140.5") 6 4-OMe A 45 Mp 73-79e CH 7N0% (lit t mp 73-741) 7 2-OMe A 50 Mp 66" C*HNO 126 (litf...Form. Found cation. Compd. No. Reactants Yield, % Mp, *C (cation.anion) %C %H %N anion Part A. 1 -Alkoxypyridinium salts. 14 2,3-Mes, 87 120-122 CH ...111 + 4(C6H6CVs O, 28.62 3.22 4.40 ..... (MeO)2SO2 _OSO 2 CH s ) is 4-OMe,6 + 78 46-48 CSH 121NO 2 34.18 4.30 4.91 154, 126 Ed (CsH12NO2-) 34.02

H-Bonding Assisted Self-Assembly of Anionic and Neutral Ligand on Metal: A Comprehensive Strategy To Mimic Ditopic Ligands in Olefin Polymerization.

PubMed

Mote, Nilesh R; Patel, Ketan; Shinde, Dinesh R; Gaikwad, Shahaji R; Koshti, Vijay S; Gonnade, Rajesh G; Chikkali, Samir H

2017-10-16

Self-assembly of two neutral ligands on a metal to mimic bidentate ligand coordination has been frequently encountered in the recent past, but self-assembly of an anionic ligand on a metal template alongside a neutral ligand remains an elusive target. Such a self-assembly is hampered by additional complexity, wherein a highly negatively charged anion can form intermolecular hydrogen bonding with the supramolecular motif, leaving no scope for self-assembly with neutral ligand. Presented here is the self-association of anionic ligand 3-ureidobenzoic acid (2a) and neutral ligand 1-(3-(diphenylphosphanyl)phenyl)urea (1a) on a metal template to yield metal complex [{COOC 6 H 4 NH(CO)NH 2 }{Ph 2 PC 6 H 4 NH(CO)NH 2 }PdMeDMSO] (4a). The identity of 4a was established by NMR and mass spectroscopy. Along the same lines, 3-(3-phenylureido)benzoic acid (2b) and 1-(3-(diphenylphosphanyl)phenyl)-3-phenylurea (1b) self-assemble on a metal template to produce palladium complex [{COOC 6 H 4 NH(CO)NHPh}{Ph 2 PC 6 H 4 NH(CO)NHPh}PdMePy] (5c). The existence of 5c was confirmed by Job plot, 1-2D NMR spectroscopy, deuterium labeling, IR spectroscopy, UV-vis spectroscopy, model complex synthesis, and DFT calculations. These solution and gas phase investigations authenticated the presence of intramolecular hydrogen bonding between hydrogen's of 1b and carbonyl oxygen of 2b. The generality of the supramolecular approach has been validated by preparing six complexes from four monodentate ligands, and their synthetic utility was demonstrated in ethylene polymerization. Complex 4a was found to be the most active, leading to the production of highly branched polyethylene with a molecular weight of 55700 g/mol and melting temperature of 112 °C.

Syntheses of amide based anion receptors and investigation of their associations with anions and their molecular structures using proton NMR titration and DFT methods

NASA Astrophysics Data System (ADS)

Navakhun, Korakot; Sawangsri, Ranu; Ruangpornvisuti, Vithaya

2014-03-01

The synthesized disubstituted isophthalamide and pyridine-2,6dicarboxamide derivatives of nine compounds were prepared. Their association constants with tetrabutylammonium fluoride (TBA·F), tetrabutylammonium chloride (TBA·Cl), tetrabutylammonium bromide (TBA·Br), tetrabutylammonium dihydrogenphosphate (TBA·H2PO4), tetrabutylammonium hydrogensulphate (TBA·HSO4) and tetrabutylammonium nitrate (TBA·NO3) were obtained by 1H NMR titration technique. The optimized structures of compounds 1-9 and their association with F-, Cl-, Br-, HPO4-, HSO4- and NO3- were obtained using the B3LYP/6-31+G(d) method. The most favorable complex of compound 3 with Br- was found. The high association constants of complexes 1-6 with F- are expected. Associations of all receptors with anions are exothermic and spontaneous reactions. Thermodynamic properties of all associations obtained using B3LYP/6-31+G(d) method are reported.

Capped Mesoporous Silica Nanoparticles for the Selective and Sensitive Detection of Cyanide.

PubMed

Sayed, Sameh El; Licchelli, Maurizio; Martínez-Máñez, Ramón; Sancenón, Félix

2017-10-18

The development of easy and affordable methods for the detection of cyanide is of great significance due to the high toxicity of this anion and the potential risks associated with its pollution. Herein, optical detection of cyanide in water has been achieved by using a hybrid organic-inorganic nanomaterial. Mesoporous silica nanoparticles were loaded with [Ru(bipy) 3 ] 2+ , functionalized with macrocyclic nickel(II) complex subunits, and capped with a sterically hindering anion (hexametaphosphate). Cyanide selectively induces demetallation of nickel(II) complexes and the removal of capping anions from the silica surface, allowing the release of the dye and the consequent increase in fluorescence intensity. The response of the capped nanoparticles in aqueous solution is highly selective and sensitive towards cyanide with a limit of detection of 2 μm. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlling Second Coordination Sphere Effects in Luminescent Ruthenium Complexes by Means of External Pressure.

PubMed

Pannwitz, Andrea; Poirier, Stéphanie; Bélanger-Desmarais, Nicolas; Prescimone, Alessandro; Wenger, Oliver S; Reber, Christian

2018-06-04

Two luminescent heteroleptic Ru II complexes with a 2,2'-biimidazole (biimH 2 ) ligand form doubly hydrogen-bonded salt bridges to 4-sulfobenzoate anions in single crystals. The structure of one of these cation-anion adducts shows that the biimH 2 ligand is deprotonated. Its 3 MLCT luminescence band does not shift significantly under the influence of an external hydrostatic pressure, a behavior typical for these electronic transitions. In contrast, hydrostatic pressure on the other crystalline cation-anion adduct induces a shift of proton density from the peripheral N-H groups of biimH 2 towards benzoate, leading to a pronounced redshift of the 3 MLCT luminescence band. Such a significant and pressure-tunable influence from an interaction in the second coordination sphere is unprecedented in artificial small-molecule-based systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

3D Tomographic SAR Imaging in Densely Vegetated Mountainous Rural Areas in China and Sweden

NASA Astrophysics Data System (ADS)

Feng, L.; Muller, J. P., , Prof

2017-12-01

3D SAR Tomography (TomoSAR) and 4D SAR Differential Tomography (Diff-TomoSAR) exploit multi-baseline SAR data stacks to create an important new innovation of SAR Interferometry, to unscramble complex scenes with multiple scatterers mapped into the same SAR cell. In addition to this 3-D shape reconstruction and deformation solution in complex urban/infrastructure areas, and recent cryospheric ice investigations, emerging tomographic remote sensing applications include forest applications, e.g. tree height and biomass estimation, sub-canopy topographic mapping, and even search, rescue and surveillance. However, these scenes are characterized by temporal decorrelation of scatterers, orbital, tropospheric and ionospheric phase distortion and an open issue regarding possible height blurring and accuracy losses for TomoSAR applications particularly in densely vegetated mountainous rural areas. Thus, it is important to develop solutions for temporal decorrelation, orbital, tropospheric and ionospheric phase distortion.We report here on 3D imaging (especially in vertical layers) over densely vegetated mountainous rural areas using 3-D SAR imaging (SAR tomography) derived from data stacks of X-band COSMO-SkyMed Spotlight and L band ALOS-1 PALSAR data stacks over Dujiangyan Dam, Sichuan, China and L and P band airborne SAR data (BioSAR 2008 - ESA) in the Krycklan river catchment, Northern Sweden. The new TanDEM-X 12m DEM is used to assist co - registration of all the data stacks over China first. Then, atmospheric correction is being assessed using weather model data such as ERA-I, MERRA, MERRA-2, WRF; linear phase-topography correction and MODIS spectrometer correction will be compared and ionospheric correction methods are discussed to remove tropospheric and ionospheric delay. Then the new TomoSAR method with the TanDEM-X 12m DEM is described to obtain the number of scatterers inside each pixel, the scattering amplitude and phase of each scatterer and finally extract tomograms (imaging), their 3D positions and motion parameters (deformation). A progress report will be shown on these different aspects.This work is partially supported by the CSC and UCL MAPS Dean prize through a PhD studentship at UCL-MSSL.

Dissociation of Rac1(GDP)·RhoGDI Complexes by the Cooperative Action of Anionic Liposomes Containing Phosphatidylinositol 3,4,5-Trisphosphate, Rac Guanine Nucleotide Exchange Factor, and GTP*

PubMed Central

Ugolev, Yelena; Berdichevsky, Yevgeny; Weinbaum, Carolyn; Pick, Edgar

2008-01-01

Rac plays a pivotal role in the assembly of the superoxide-generating NADPH oxidase of phagocytes. In resting cells, Rac is found in the cytosol in complex with Rho GDP dissociation inhibitor (RhoGDI). NADPH oxidase assembly involves dissociation of the Rac·RhoGDI complex and translocation of Rac to the membrane. We reported that liposomes containing high concentrations of monovalent anionic phospholipids cause Rac·RhoGDI complex dissociation (Ugolev, Y., Molshanski-Mor, S., Weinbaum, C., and Pick, E. (2006) J. Biol. Chem.281 ,19204 -1921916702219). We now designed an in vitro model mimicking membrane phospholipid remodeling during phagocyte stimulation in vivo. We showed that liposomes of “resting cell membrane” composition (less than 20 mol % monovalent anionic phospholipids), supplemented with 1 mol % of polyvalent anionic phosphatidylinositol 3,4,5-trisphosphate (PtdIns(3,4,5)P3) in conjunction with constitutively active forms of the guanine nucleotide exchange factors (GEFs) for Rac, Trio, or Tiam1 and a non-hydrolyzable GTP analogue, cause dissociation of Rac1(GDP)·RhoGDI complexes, GDP to GTP exchange on Rac1, and binding of Rac1(GTP) to the liposomes. Complexes were not dissociated in the absence of GEF and GTP, and optimal dissociation required the presence of PtdIns(3,4,5)P3 in the liposomes. Dissociation of Rac1(GDP)·RhoGDI complexes was correlated with the affinity of particular GEF constructs, via the N-terminal pleckstrin homology domain, for PtdIns(3,4,5)P3 and involved GEF-mediated GDP to GTP exchange on Rac1. Phagocyte membranes enriched in PtdIns(3,4,5)P3 responded by NADPH oxidase activation upon exposure in vitro to Rac1(GDP)·RhoGDI complexes, p67phox, GTP, and Rac GEF constructs with affinity for PtdIns(3,4,5)P3 at a level superior to that of native membranes. PMID:18505730

Preparation and performance evaluation of novel alkaline stable anion exchange membranes

NASA Astrophysics Data System (ADS)

Irfan, Muhammad; Bakangura, Erigene; Afsar, Noor Ul; Hossain, Md. Masem; Ran, Jin; Xu, Tongwen

2017-07-01

Novel alkaline stable anion exchange membranes are prepared from various amounts of N-methyl dipicolylamine (MDPA) and brominated poly (2,6-dimethyl-1,4-phenylene oxide) (BPPO). The dipicolylamine and MDPA are synthesized through condensation reaction and confirmed by 1H NMR spectroscopy. The morphologies of prepared membranes are investigated by atomic force microscopy (AFM), fourier transform infrared spectroscopy (FTIR), 1H NMR spectroscopy and scanning electron microscopy (SEM). The electrochemical and physical properties of AEMs are tested comprising water uptake (WU), ion exchange capacity (IEC), alkaline stability, linear expansion ratio (LER), thermal stability and mechanical stability. The obtained hydroxide conductivity of MDPA-4 is 66.5 mS/cm at 80 °C. The MDPA-4 membrane shows good alkaline stability, high hydroxide conductivity, low methanol permeability (3.43 × 10-7 cm2/s), higher selectivity (8.26 × 107 mS s/cm3), less water uptake (41.1%) and lower linear expansion (11.1%) despite of high IEC value (1.62 mmol/g). The results prove that MDPA membranes have great potential application in anion exchange membrane fuel cell.

Influence of Polyoxometalate Protecting Ligands on Catalytic Aerobic Oxidation at the Surfaces of Gold Nanoparticles in Water.

PubMed

Zhang, Mingfu; Hao, Jingcheng; Neyman, Alevtina; Wang, Yifeng; Weinstock, Ira A

2017-03-06

Metal oxide cluster-anion (polyoxometalate, or POM) protecting ligands, [α-PW 11 O 39 ] 7- (1), modify the rates at which 14 nm gold nanoparticles (Au NPs) catalyze an important model reaction, the aerobic (O 2 ) oxidation of CO to CO 2 in water. At 20 °C and pH 6.2, the following stoichiometry was observed: CO + O 2 + H 2 O = CO 2 + H 2 O 2 . After control experiments verified that the H 2 O 2 product was sufficiently stable and did not react with 1 under turnover conditions, quantitative analysis of H 2 O 2 was used to monitor the rates of CO oxidation, which increased linearly with the percent coverage of the Au NPs by 1 (0-64% coverage, with the latter value corresponding to 211 ± 19 surface-bound molecules of 1). X-ray photoelectron spectroscopy of Au NPs protected by a series of POM ligands (K + salts): 1, the Wells-Dawson ion [α-P 2 W 18 O 62 ] 6- (2) and the monodefect Keggin anion [α-SiW 11 O 39 ] 8- (3) revealed that binding energies of electrons in the Au 4f 7/2 and 4f 5/2 atomic orbitals decreased as a linear function of the POM charge and percent coverage of Au NPs, providing a direct correlation between the electronic effects of the POMs bound to the surfaces of the Au NPs and the rates of CO oxidation by O 2 . Additional data show that this effect is not limited to POMs but occurs, albeit to a lesser extent, when common anions capable of binding to Au-NP surfaces, such as citrate or phosphate, are present.

Syntheses, crystallographic, mass-spectroscopic determination and antioxidant studies of Co(II), Ni(II) and Cu(II) complexes of a new imidazol based Schiff base.

PubMed

Demir, Serkan; Güder, Aytaç; Yazıcılar, Turan K; Çağlar, Sema; Büyükgüngör, Orhan

2015-01-01

A new imidazole-based Schiff base, 2-((1H-imidazol-4-yl)methyleneamino)benzylalcohol (HL) and corresponding analogous bis(2-((1H-imidazol-4-yl)methyleneimino)benzylalcohol)metal(II) perchlorates (M: Co(1), Ni(2), Cu(3)) have prepared and characterized by elemental analyses, ESI-MS, IR, UV-Vis spectroscopies and conductivity measurements. X-ray single crystal structures of 1 and 2 have been also determined. Elemental analyses, spectroscopic and conductance data of 3 demonstrated similar structural features with these of crystallographically characterized complexes and based upon this relevances, HL ligands are neutrally coordinated to metal(II) ions in tridentate mode and all complexes are isostructural, dicathionic, contain perchlorate anions as complementary ions and, are in octahedral geometry with the formulae of [M(HL)2](ClO4)2 (for 3) and [M(HL)2](ClO4)2·H2O (for 1 and 2). Radical scavenging activities of the complexes have been evaluated by using DPPH, DMPD(+), and ABTS(+) assays. SC50 values (μg/mL) of the complexes and standards on DPPH, DMPD(+), ABTS(+) follow the sequences, BHA (9.06±0.33)>CMPD3 (15.62±0.52)>CMPD2 (17.43±0.29)>Rutin (21.65±0.60)>CMPD1 (25.67±0.51)>Trolox (28.57±0.37), Rutin>BHA>CMPD3>CMPD2>Trolox>CMPD1, and Trolox>BHA>CMPD3>CMPD2>Rutin>CMPD1 respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Mechanism of action of anions on the electron transport chain in thylakoid membranes of higher plants.

PubMed

Singh-Rawal, Pooja; Zsiros, Ottó; Bharti, Sudhakar; Garab, Gyozo; Jajoo, Anjana

2011-04-01

With an aim to improve our understanding of the mechanisms behind specific anion effects in biological membranes, we have studied the effects of sodium salts of anions of varying valency in thylakoid membranes. Rates of electron transport of PS II and PS I, 77K fluorescence emission and excitation spectra, cyclic electron flow around PS I and circular dichroism (CD) spectra were measured in thylakoid membranes in order to elucidate a general mechanism of action of inorganic anions on photosynthetic electron transport chain. Re-distribution of absorbed excitation energy has been observed as a signature effect of inorganic anions. In the presence of anions, such as nitrite, sulphate and phosphate, distribution of absorbed excitation energy was found to be more in favor of Photosystem I (PS I). The amount of energy distributed towards PS I depended on the valency of the anion. In this paper, we propose for the first time that energy re-distribution and its valence dependence may not be the effect of anions per se. The entry of negative charge (anion) is accompanied by influx of positive charge (protons) to maintain a balance of charge across the thylakoid membranes. As reflected by the CD spectra, the observed energy re-distribution could be a result of structural rearrangements of the protein complexes of PS II caused by changes in the ionic environment of the thylakoid lumen.

Probing the formation mechanism and chemical states of carbon-supported Pt-Ru nanoparticles by in situ X-ray absorption spectroscopy.

PubMed

Hwang, Bing Joe; Chen, Ching-Hsiang; Sarma, Loka Subramanyam; Chen, Jiun-Ming; Wang, Guo-Rung; Tang, Mau-Tsu; Liu, Din-Goa; Lee, Jyh-Fu

2006-04-06

The understanding of the formation mechanism of nanoparticles is essential for the successful particle design and scaling-up process. This paper reports findings of an X-ray absorption spectroscopy (XAS) investigation, comprised of X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions, to understand the mechanism of the carbon-supported Pt-Ru nanoparticles (NPs) formation process. We have utilized Watanabe's colloidal reduction method to synthesize Pt-Ru/C NPs. We slightly modified the Watanabe method by introducing a mixing and heat treatment step of Pt and Ru oxidic species at 100 degrees C for 8 h with a view to enhance the mixing efficiency of the precursor species, thereby one can achieve improved homogeneity and atomic distribution in the resultant Pt-Ru/C NPs. During the reduction process, in situ XAS measurements allowed us to follow the evolution of Pt and Ru environments and their chemical states. The Pt LIII-edge XAS indicates that when H2PtCl6 is treated with NaHSO3, the platinum compound is found to be reduced to a Pt(II) form corresponding to the anionic complex [Pt(SO3)4]6-. Further oxidation of this anionic complex with hydrogen peroxide forms dispersed [Pt(OH)6]2- species. Analysis of Ru K-edge XAS results confirms the reduction of RuIIICl3 to [RuII(OH)4]2- species upon addition of NaHSO3. Addition of hydrogen peroxide to [RuII(OH)4]2- causes dehydrogenation and forms RuOx species. Mixing of [Pt(OH)6]2- and RuOx species and heat treatment at 100 degrees C for 8 h produced a colloidal sol containing both Pt and Ru metallic as well as ionic contributions. The reduction of this colloidal mixture at 300 degrees C in hydrogen atmosphere for 2 h forms Pt-Ru nanoparticles as indicated by the presence of Pt and Ru atoms in the first coordination shell. Determination of the alloying extent or atomic distribution of Pt and Ru atoms in the resulting Pt-Ru/C NPs reveals that the alloying extent of Ru (JRu) is greater than that of the alloying extent of Pt (JPt). The XAS results support the Pt-rich core and Ru-rich shell structure with a considerable amount of segregation in the Pt region and with less segregation in the Ru region for the obtained Pt-Ru/C NPs.

Synthesis of 1,8-naphthyridines and their application in the development of anionic fluorogenic chemosensors.

PubMed

Nicoleti, Celso R; Garcia, Diogo N; da Silva, Luiz E; Begnini, Iêda M; Rebelo, Ricardo A; Joussef, Antonio C; Machado, Vanderlei G

2012-07-01

Two 1,8-naphthyridines were synthesized and found to be fluorescent in solution. These compounds were studied in the presence of Cu(+) and Cu(2+) ions and it was verified that the metal causes the quenching of their fluorescence emission, due to the formation of complexes between the naphthyridine and the metal. A displacement assay was carried out in a DMSO-water mixture with the addition of various anions to the solutions of the complexes, and it was observed that these systems have a high capacity to selectively detect cyanide.

Synthesis, characterization, biological evaluation and docking studies of macrocyclic binuclear manganese(II) complexes containing 3,5-dinitrobenzoyl pendant arms

NASA Astrophysics Data System (ADS)

Arthi, P.; Shobana, S.; Srinivasan, P.; Mitu, L.; Kalilur Rahiman, A.

2015-05-01

A series of bis(phenoxo) bridged binuclear manganese(II) complexes of the type [Mn2L1-3](ClO4)2 (1-3) containing 3,5-dinitrobenzoyl pendant-arms have been synthesized by cyclocondensation of 2,6-diformyl-4-R-phenols (where R = sbnd CH3, sbnd C(CH3)3 or sbnd Br) with 2,2‧-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride in the presence of manganese(II) perchlorate. The IR spectra of complexes indicate the presence of uncoordinated perchlorate anions. The UV-Vis spectra of complexes suggest the distorted octahedral geometry around manganese(II) nuclei. The EPR spectra of Mn(II) complexes show a broad signal with g value 2.03-2.04, which is characteristic for octahedral high spin Mn2+ complex. The observed room temperature magnetic moment values of the Mn(II) complexes (5.60-5.62 B.M.) are less than the normal value (5.92 B.M.), indicating weak antiferromagnetic coupling interaction between the two metal ions. Electrochemical studies of the complexes show two distinct quasi-reversible one electron transfer processes in the cathodic (E1pc = -0.73 to -0.76 V, E2pc = -1.30 to -1.36 V), and anodic (E1pa = 1.02-1.11 V, E2pa = 1.32-1.79 V) potential regions. Antibacterial efficacy of complexes have been screened against four Gram (-ve) and two Gram (+ve) bacterial strains. The DNA interaction studies suggest that these complexes bind with CT-DNA by intercalation, giving the binding affinity in the order 1 > 2 > 3. All the complexes display significant cleavage activity against circular plasmid pBR322 DNA. Docking simulation was performed to insert complexes into the crystal structure of EGFR tyrosine kinase and B-DNA at active site to determine the probable binding mode.

Study of the structural organization of cyclodextrin-DNA complex loaded anionic and pH-sensitive liposomes

NASA Astrophysics Data System (ADS)

Silva, Sônia M. L.; Coelho, Letícia N.; Malachias, Ângelo; Perez, Carlos A.; Pesquero, Jorge L.; Magalhães-Paniago, Rogério; de Oliveira, Mônica C.

2011-04-01

The present study investigated the effect of the 6-monodeoxy-6-monoamine-β-cyclodextrin(Am-β-CD)/DNA (Am-β-CD/DNA) complex, as well as of culture medium components and proteins, at pH 7.4 and 5.0, on membranes of anionic and pH-sensitive liposomes comprised of DOPE-CHEMS, using energy dispersive X-ray diffraction (EDXD). At pH 7.4, the Am-β-CD/DNA complex induced the appearance of lamellar and hexagonal phases of DOPE. However, at pH 5.0, only non-lamellar phases could be observed. The presence of biological components led to a disruption of lipid order, but the pH-sensitivity of liposomes was maintained.

Tetrel bond of pseudohalide anions with XH3F (X = C, Si, Ge, and Sn) and its role in SN2 reaction

NASA Astrophysics Data System (ADS)

Liu, Mingxiu; Li, Qingzhong; Cheng, Jianbo; Li, Wenzuo; Li, Hai-Bei

2016-12-01

The complexes of XH3F⋯ N3-/OCN-/SCN- (X = C, Si, Ge, and Sn) have been investigated at the MP2/aug-cc-pVTZ(PP) level. The σ-hole of X atom in XH3F acts as a Lewis acid forming a tetrel bond with pseudohalide anions. Interaction energies of these complexes vary from -8 to -50 kcal/mol, mainly depending on the nature of X and pseudohalide anions. Charge transfer from N/O/S lone pair to X-F and X-H σ* orbitals results in the stabilization of these complexes, and the former orbital interaction is responsible for the large elongation of X-F bond length and the remarkable red shift of its stretch vibration. The tetrel bond in the complexes of XH3F (X = Si, Ge, and Sn) exhibits a significant degree of covalency with XH3F distorted significantly in these complexes. A breakdown of the individual forces involved attributes the stability of the interaction to mainly electrostatic energy, with a relatively large contribution from polarization. The transition state structures that connect the two minima for CH3Br⋯ N3-complexhave been localized and characterized. The energetic, geometrical, and topological parameters of the complexes were analyzed in the different stages of the SN2 reaction N3- + CH3Br → Br- + CH3N3.

Temperature-dependent IR spectroscopic and structural study of 18-crown-6 chelating ligand in the complexation with sodium surfactant salts and potassium picrate.

PubMed

Mihelj, Tea; Tomašić, Vlasta; Biliškov, Nikola; Liu, Feng

2014-04-24

18-crown-6 ether (18C6) complexes with the following anionic surfactants: sodium n-dodecylsulfate (18C6-NaDS), sodium 4-(1-pentylheptyl)benzenesulfonate (18C6-NaDBS); and potassium picrate (18C6-KP) were synthesized and studied in terms of their thermal and structural properties. Physico-chemical properties of new solid 1:1 coordination complexes were characterized by infrared (IR) spectroscopy, thermogravimetry and differential thermal analysis, differential scanning calorimetry, X-ray diffraction and microscopic observations. The strength of coordination between Na(+) and oxygen atoms of 18C6 ligand does not depend on anionic part of the surfactant, as established by thermodynamical parameters obtained by temperature-dependent IR spectroscopy. Each of these complexes exhibit different kinds of endothermic transitions in heating scan. Diffraction maxima obtained by SAXS and WAXS, refer the behavior of the compounds 18C6-NaDS and 18C6-NaDBS as smectic liquid crystalline. Distortion of 18C6-NaDS and 18C6-KP complexes occurs in two steps. Temperature of the decomplexation of solid crystal complex 18C6-KP is considerably higher than of mesophase complexes, 18C6-NaDS, and 18C6-NaDBS. The structural and liquid crystalline properties of novel 18-crown-ether complexes are function of anionic molecule geometry, type of chosen cation (Na(+), K(+)), as well as architecture of self-organized aggregates. A good combination of crown ether unit and amphiphile may provide a possibility for preparing new functionalized materials, opening the research field of ion complexation and of host-guest type behavior. Copyright © 2013 Elsevier B.V. All rights reserved.

ProUCL Version 4.0 Technical Guide

EPA Science Inventory

Statistical inference, including both estimation and hypotheses testing approaches, is routinely used to: estimate environmental parameters of interest, such as exposure point concentration (EPC) terms, not-to-exceed values, and background level threshold values (BTVs) for contam...

Total Synthesis of the Marine Phosphomacrolide, (-)-Enigmazole A, Exploiting Multicomponent Type I Anion Relay Chemistry (ARC) in Conjunction with a Late-Stage Petasis-Ferrier Union/Rearrangement.

PubMed

Ai, Yanran; Kozytska, Mariya V; Zou, Yike; Khartulyari, Anton S; Maio, William A; Smith, Amos B

2018-06-01

An effective late-stage large-fragment union/rearrangement exploiting the Petasis-Ferrier protocol, in conjunction with multicomponent Type I Anion Relay Chemistry (ARC) to access advanced intermediates, permits completion of a convergent, stereocontrolled total synthesis of the architecturally complex phosphomacrolide (-)-enigmazole A (1).

Anion receptor compounds for non-aqueous electrolytes

DOEpatents

Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

2000-09-19

A new family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

Aza crown ether compounds as anion receptors

DOEpatents

Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

1998-08-04

A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

Aza crown ether compounds as anion receptors

DOEpatents

Lee, H.S.; Yang, X.O.; McBreen, J.

1998-08-04

A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI{sup +} ion in alkali metal batteries. 3 figs.

Infrared spectra of the CO2- and C2O4- anions isolated in solid argon

NASA Astrophysics Data System (ADS)

Zhou, Mingfei; Andrews, Lester

1999-02-01

Laser ablation of transition metal targets with concurrent 11 to 12 K condensation of CO2-Ar mixtures produces a sharp metal independent infrared absorption at 1657.0 cm-1 due to CO2-, which is formed from the capture of ablated electrons by CO2 molecules during the condensation process. Two additional metal independent absorptions are produced at 1856.7 and 1184.7 cm-1 on matrix annealing to 25 K to allow diffusion and reaction of CO2 and CO2-. Isotopic substitution (13CO2, C18O2, C16,18O2, and mixtures) shows that these two vibrations involve two equivalent CO2 subunits. The excellent agreement with frequencies, intensities, and isotopic frequency ratios from density-functional calculations supports assignment to the symmetrical C2O4- anion with D2d symmetry. Photodissociation (470-580 nm) and failure to observe these absorptions in identical experiments doped with the electron trapping molecule CCl4 further support the molecular anion assignments. Although absorptions were observed for weak (CO2)(CO2-) complexes, no evidence was found for the asymmetric O2CṡOCO- molecule-anion complex characterized by calculations.

A novel dichromate-sensitive fluorescent nano-chemosensor using new functionalized SBA-15.

PubMed

Hosseini, Morteza; Gupta, Vinod Kumar; Ganjali, Mohammad Reza; Rafiei-Sarmazdeh, Zahra; Faridbod, Farnoush; Goldooz, Hassan; Badiei, Ali Reza; Norouzi, Parviz

2012-02-17

A novel fluorescence nano-chemosensor for Cr(2)O(7)(2-) anion has been developed by assembly of fluorescent aluminum complex of 8-hydroxyquinoline (AlQ(x)) within the channels of modified SBA-15. SBA-SPS-AlQ(x) shows a fluorescence emission at 486 nm. The observed remarkable fluorescence of SBA-SPS-AlQ(x) quenches in presence of Cr(2)O(7)(2-) anion. The results showed that this fluorescent nano-material can be a useful chemo-sensor for determination of dichromate anions in aqueous solutions. The linear detecting range of fluorescent nano-chemosensor for Cr(2)O(7)(2-) anion was 0.16-2.9 μmol L(-1). The lowest limit of detection (LDL) was also found to be 0.2 ng mL(-1) in aqueous solutions. SBA-SPS-AlQ(x) showed selectively and sensitively fluorescent quenching response toward Cr(2)O(7)(2-) ion in comparison with I(3)(-), NO(3)(-), CN(-), CO(3)(2-), Br(-), Cl(-), F(-), H(2)PO(4)(-) and SO(4)(2-) ions, which was because of the higher stability of its inorganic complex with dichromate ion. Copyright © 2011 Elsevier B.V. All rights reserved.

Crystal structure of bis­{μ2-2,2′-[(4,10-dimethyl-1,4,7,10-tetra­aza­cyclo­dodecane-1,7-di­yl)bis(meth­yl­ene)]bis­(4-oxo-4H-pyran-3-olato)}dicobalt­calcium bis­(perchlorate) 1.36-hydrate

PubMed Central

Rossi, Patrizia; Paoli, Paola; Giorgi, Luca; Formica, Mauro; Fusi, Vieri

2017-01-01

The title compound, [CaCo2(C22H30N4O6)2](ClO4)2·1.36H2O or {Ca[Co(H–2 L1)]2}·2ClO4·1.36H2O {where L1 is 4,10-bis­[(3-hy­droxy-4-pyron-2-yl)meth­yl]-1,7-dimethyl-1,4,7,10-tetra­aza­cyclo­dodecane}, is a trinuclear complex whose asymmetric unit comprises a quarter of the {Ca[Co(H–2 L1)]2}2+ trinuclear complex, half of a perchlorate ion and 0.34-water mol­ecules. In the neutral [Co(H–2 L1)] moiety, the cobalt ion is hexa­coordinated in a trigonal–prismatic fashion by the surrounding N4O2 donor set. A Ca2+ cation holds together two neutral [Co(H–2 L1)] moieties and is octa­coordinated in a distorted trigonal–dodeca­hedral fashion by the surrounding O atoms belonging to the deprotonated oxide and carbonyl groups of two [Co(H–2 L1)] units. The coordination of the CoII cation preorganizes L1 and an electron-rich area forms, which is able to host hard metal ions. The comparison between the present structure and the previously published ones suggests a high versatility of this ligand; indeed, hard metal ions with different nature and dimensions lead to complexes having different stoichiometry (mono- and dinuclear monomers and trinuclear dimers) or even a polymeric structure. The heterotrinuclear CoII–CaII–CoII complexes are connected in three dimensions via weak C—H⋯O hydrogen bonds, which are also responsible for the inter­actions with the perchlorate anions and the lattice water mol­ecules. The perchlorate anion is disordered about a twofold rotation axis and was refined giving the two positions a fixed occupancy factor of 0.5. The crystal studied was refined as a two-component inversion twin [BASF parameter = 0.14 (4)]. PMID:29250424

Production of high specific activity silicon-32

DOEpatents

Phillips, Dennis R.; Brzezinski, Mark A.

1994-01-01

A process for preparation of silicon-32 is provide and includes contacting an irradiated potassium chloride target, including spallation products from a prior irradiation, with sufficient water, hydrochloric acid or potassium hydroxide to form a solution, filtering the solution, adjusting pH of the solution to from about 5.5 to about 7.5, admixing sufficient molybdate-reagent to the solution to adjust the pH of the solution to about 1.5 and to form a silicon-molybdate complex, contacting the solution including the silicon-molybdate complex with a dextran-based material, washing the dextran-based material to remove residual contaminants such as sodium-22, separating the silicon-molybdate complex from the dextran-based material as another solution, adding sufficient hydrochloric acid and hydrogen peroxide to the solution to prevent reformation of the silicon-molybdate complex and to yield an oxidization state of the molybdate adapted for subsequent separation by an anion exchange material, contacting the solution with an anion exchange material whereby the molybdate is retained by the anion exchange material and the silicon remains in solution, and optionally adding sufficient alkali metal hydroxide to adjust the pH of the solution to about 12 to 13. Additionally, a high specific activity silicon-32 product having a high purity is provided.

High specific activity silicon-32

DOEpatents

Phillips, Dennis R.; Brzezinski, Mark A.

1996-01-01

A process for preparation of silicon-32 is provided and includes contacting an irradiated potassium chloride target, including spallation products from a prior irradiation, with sufficient water, hydrochloric acid or potassium hydroxide to form a solution, filtering the solution, adjusting pH of the solution to from about 5.5 to about 7.5, admixing sufficient molybdate-reagent to the solution to adjust the pH of the solution to about 1.5 and to form a silicon-molybdate complex, contacting the solution including the silicon-molybdate complex with a dextran-based material, washing the dextran-based material to remove residual contaminants such as sodium-22, separating the silicon-molybdate complex from the dextran-based material as another solution, adding sufficient hydrochloric acid and hydrogen peroxide to the solution to prevent reformation of the silicon-molybdate complex and to yield an oxidization state of the molybdate adapted for subsequent separation by an anion exchange material, contacting the solution with an anion exchange material whereby the molybdate is retained by the anion exchange material and the silicon remains in solution, and optionally adding sufficient alkali metal hydroxide to adjust the pH of the solution to about 12 to 13. Additionally, a high specific activity silicon-32 product having a high purity is provided.

High specific activity silicon-32

DOEpatents

Phillips, D.R.; Brzezinski, M.A.

1996-06-11

A process for preparation of silicon-32 is provided and includes contacting an irradiated potassium chloride target, including spallation products from a prior irradiation, with sufficient water, hydrochloric acid or potassium hydroxide to form a solution, filtering the solution, adjusting pH of the solution from about 5.5 to about 7.5, admixing sufficient molybdate-reagent to the solution to adjust the pH of the solution to about 1.5 and to form a silicon-molybdate complex, contacting the solution including the silicon-molybdate complex with a dextran-based material, washing the dextran-based material to remove residual contaminants such as sodium-22, separating the silicon-molybdate complex from the dextran-based material as another solution, adding sufficient hydrochloric acid and hydrogen peroxide to the solution to prevent reformation of the silicon-molybdate complex and to yield an oxidation state of the molybdate adapted for subsequent separation by an anion exchange material, contacting the solution with an anion exchange material whereby the molybdate is retained by the anion exchange material and the silicon remains in solution, and optionally adding sufficient alkali metal hydroxide to adjust the pH of the solution to about 12 to 13. Additionally, a high specific activity silicon-32 product having a high purity is provided.

Cooperativity and complexity in the binding of anions and cations to a tetratopic ion-pair host.

PubMed

Howe, Ethan N W; Bhadbhade, Mohan; Thordarson, Pall

2014-05-21

Cooperative interactions play a very important role in both natural and synthetic supramolecular systems. We report here on the cooperative binding properties of a tetratopic ion-pair host 1. This host combines two isophthalamide anion recognition sites with two unusual "half-crown/two carbonyl" cation recognition sites as revealed by the combination of single-crystal X-ray analysis of the free host and the 1:2 host:calcium cation complex, together with two-dimensional NMR and computational studies. By systematically comparing all of the binding data to several possible binding models and focusing on four different variants of the 1:2 binding model, it was in most cases possible to quantify these complex cooperative interactions. The data showed strong negative cooperativity (α = 0.01-0.05) of 1 toward chloride and acetate anions, while for cations the results were more variable. Interestingly, in the competitive (CDCl3/CD3OD (9:1, v/v)) solvent, the addition of calcium cations to the tetratopic ion-pair host 1 allosterically switched "on" chloride binding that is otherwise not present in this solvent system. The insight into the complexity of cooperative interactions revealed in this study of the tetratopic ion-pair host 1 can be used to design better cooperative supramolecular systems for information transfer and catalysis.

Towards high conductivity in anion-exchange membranes for alkaline fuel cells.

PubMed

Li, Nanwen; Guiver, Michael D; Binder, Wolfgang H

2013-08-01

Quaternized poly(2,6-dimethylphenylene oxide) materials (PPOs) containing clicked 1,2,3-triazoles were first prepared through Cu(I) -catalyzed "click chemistry" to improve the anion transport in anion-exchange membranes (AEMs). Clicked 1,2,3-triazoles incorporated into AEMs provided more sites to form efficient and continuous hydrogen-bond networks between the water/hydroxide and the triazole for anion transport. Higher water uptake was observed for these triazole membranes. Thus, the membranes showed an impressive enhancement of the hydroxide diffusion coefficient and, therefore, the anion conductivities. The recorded hydroxide conductivity was 27.8-62 mS cm(-1) at 20 °C in water, which was several times higher than that of a typical PPO-based AEM (TMA-20) derived from trimethylamine (5 mS cm(-1) ). Even at reduced relative humidity, the clicked membrane showed superior conductivity to a trimethylamine-based membrane. Moreover, similar alkaline stabilities at 80 °C in 1 M NaOH were observed for the clicked and non-clicked membranes. The performance of a H2 /O2 single cell assembled with a clicked AEM was much improved compared to that of a non-clicked TMA-20 membrane. The peak power density achieved for an alkaline fuel cell with the synthesized membrane 1a(20) was 188.7 mW cm(-2) at 50 °C. These results indicated that clicked AEM could be a viable strategy for improving the performance of alkaline fuel cells. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unexpected Reactivity of [(η(5) -1,2,4-tBu3 C5 H2 )Ni(η(3) -P3 )] towards Main Group Nucleophiles and by Reduction.

PubMed

Mädl, Eric; Balázs, Gábor; Peresypkina, Eugenia V; Scheer, Manfred

2016-06-27

The reduction of [Cp'''Ni(η(3) -P3 )] (1; Cp'''=η(5) -1,2,4-tBu3 C5 H2 ) with potassium produces the complex anion [(Cp'''Ni)2 (μ,η(2:2) -P8 )](2-) (2), which contains a realgar-like P8 unit. The anionic triple-decker sandwich complex [(Cp'''Ni)2 (μ,η(3:3) -P3 )](-) (3) with a cyclo-P3 middle deck is obtained when 1 is treated with NaNH2 as a nucleophile. Na[3] can subsequently be oxidized with AgOTf to the neutral triple-decker complex [(Cp'''Ni)2 (μ,η(3:3) -P3 )] (4). In contrast, 1 reacts with LiPPh2 to give the anionic compound [(Cp'''Ni)2 (μ,η(2:2) -P6 PPh2 )](-) (5), a complex containing a bicyclic P7 fragment capped by two Cp'''Ni units. Protonation of Li[5] with HBF4 leads to the neutral complex [(Cp'''Ni)2 (μ,η(2:2) -(HP6 PPh2 )] (6). Adding LiNMe2 to 1 results in [Cp'''Ni(η(2) -P3 NMe2 )](-) (7) becoming accessible, a complex which forms as a result of nucleophilic attack at the cyclo-P3 ring of 1. The complexes K2 [2], Na[3], 4, 6, and Li[7] were fully characterized and their structures determined by single-crystal X-ray diffraction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biodegradation potential of cyano-based ionic liquid anions in a culture of Cupriavidus spp. and their in vitro enzymatic hydrolysis by nitrile hydratase.

PubMed

Neumann, Jennifer; Pawlik, Magdalena; Bryniok, Dieter; Thöming, Jorg; Stolte, Stefan

2014-01-01

Biodegradation tests with bacteria from activated sludge revealed the probable persistence of cyano-based ionic liquid anions when these leave waste water treatment plants. A possible biological treatment using bacteria capable of biodegrading similar compounds, namely cyanide and cyano-complexes, was therefore examined. With these bacteria from the genera Cupriavidus, the ionic liquid anions B(CN)₄(-), C(CN)₃(-), N(CN)₂(-) combined with alkaline cations were tested in different growth media using ion chromatography for the examination of their primary biodegradability. However, no enhanced biodegradability of the tested cyano-based ionic liquids was observed. Therefore, an in vitro enzymatic hydrolysis test was additionally run showing that all tested ionic liquid (IL) anions can be hydrolysed to their corresponding amides by nitrile hydratase, but not by nitrilase under the experimental conditions. The biological stability of the cyano-based anions is an advantage in technological application, but the occurrence of enzymes that are able to hydrolyse the parent compound gives a new perspective on future cyano-based IL anion treatment.

Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids

DOE PAGES

Wu, Boning; Liang, Min; Maroncelli, Mark; ...

2015-10-26

Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyano-borate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients andmore » time-integrated spectra. Finally, application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V 0, where D is the relative diffusion coefficient between donor and acceptor and V 0 is the value of the electronic coupling at donor-acceptor contact.« less

Silica nanoparticles with a substrate switchable luminescence

NASA Astrophysics Data System (ADS)

Bochkova, O. D.; Mustafina, A. R.; Fedorenko, S. V.; Konovalov, A. I.

2011-04-01

Silica nanoparticles with visible (Tb and Ru doped), near IR (Yb doped) and dual visible-near IR luminescence (Ru-Yb doped) were obtained by reverse w/o microemulsion procedure. Plenty of luminescent complexes (from 4900 to 10000) encapsulated into each nanoparticle ensures the intensive luminescence of nanoparticles and their applicability as biomarkers. The silica surface decoration by definite anchor groups is the required step for the gaining to these nanoparticles marking and sensing functions. Thus covalent and non-covalent surface modification of these nanoparticles was developed to provide the binding with biotargets and sensing of anions. The dicationic surfactant coating of negatively charged Tb(III)-TCAS doped silica nanoparticles was chosen as the basis for the anion responsible system. The reversible insertion of the quenching anions (namely phenol red) into the surfactant based layer at the surface of luminescent nanoparticles switches off the Tb-centered luminescence. In turn the reversible reestablishment of the luminescence results from the competitive insertion of the non-quenching anions into the surfactant layer at the silica/water interface. The hydrophobic anions exemplified by dodecylsulfates versus hydrophilic ones (hydrophosphates) are preferable in the competition with phenol red anions.

Anion-cation charge-transfer properties and spectral studies of [M(phen)3][Cd4(SPh)10] (M = Ru, Fe, and Ni).

PubMed

Jiang, Jian-Bing; Bian, Guo-Qing; Zhang, Ya-Ping; Luo, Wen; Zhu, Qin-Yu; Dai, Jie

2011-10-07

Three anion-cation compounds 1-3 with formula [M(phen)(3)][Cd(4)(SPh)(10)]·Sol (M = Ru(2+), Fe(2+), and Ni(2+), Sol = MeCN and H(2)O) have been synthesized and characterized by single-crystal analysis. Both the cations and anion are well-known ions, but the properties of the co-assembled compounds are interesting. Molecular structures and charge-transfer between the cations and anions in crystal and even in solution are discussed. These compounds are isomorphous and short inter-ion interactions are found in these crystals, such as π···π stacking and C-H···π contacts. Both spectroscopic and theoretical calculated results indicate that there is anion-cation charge-transfer (ACCT) between the Ru-phen complex dye and the Cd-SPh cluster, which plays an important role in their photophysical properties. The intensity of the fluorescent emission of the [Ru(phen)(3)](2+) is enhanced when the cation interacts with the [Cd(4)(SPh)(10)](2-) anion. The mechanism for the enhancement of photoluminescence has been proposed.

Thermodynamic study of dihydrogen phosphate dimerisation and complexation with novel urea- and thiourea-based receptors.

PubMed

Bregović, Nikola; Cindro, Nikola; Frkanec, Leo; Užarević, Krunoslav; Tomišić, Vladislav

2014-11-24

Complexation of dihydrogen phosphate by novel thiourea and urea receptors in acetonitrile and dimethyl sulfoxide was studied in detail by an integrated approach by using several methods (isothermal titration calorimetry, ESI-MS, and (1)H NMR and UV spectroscopy). Thermodynamic investigations into H2PO4(-) dimerisation, which is a process that has been frequently recognised, but rarely quantitatively described, were carried out as well. The corresponding equilibrium was taken into account in the anion-binding studies, which enabled reliable determination of the complexation thermodynamic quantities. In both solvents the thiourea derivatives exhibited considerably higher binding affinities with respect to those containing the urea moiety. In acetonitrile, 1:1 and 2:1 (anion/receptor) complexes formed, whereas in dimethyl sulfoxide only the significantly less stable complexes of 1:1 stoichiometry were detected. The solvent effects on the thermodynamic parameters of dihydrogen phosphate dimerisation and complexation reactions are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sleep fragmentation: comparison of two definitions of short arousals during sleep in OSAS patients.

PubMed

Smurra, M V; Dury, M; Aubert, G; Rodenstein, D O; Liistro, G

2001-04-01

The measurement of arousals during sleep is useful to quantify sleep fragmentation. The criteria for electroencephalography (EEG) arousals defined by the American Sleep Disorders Association (ASDA) have recently been criticized because of lack of interobserver agreement. The authors have adopted a scoring method that associates the increase in chin electromyography (EMG) with the occurrence of an alpha-rhythm in all sleep stages (Université Catholique de Louvain (UCL) definition of arousals). The aim of the present study was to compare the two scoring definitions in terms of agreement and repeatability and the time taken for scoring in patients with obstructive sleep apnoea syndrome (OSAS) of varying severity. Two readers using both ASDA and UCL definitions scored twenty polysomnographies (PSGs) each on two occasions. The PSGs were chosen retrospectively to represent a wide range of arousal index (from 6-82) in OSAS patients. There was no difference in the arousal indices between readers and between scoring methods. The mean+/-SD difference between the two definitions (the bias) was 1.1+/-3.76 (95% confidence interval: -0.66-2.86). There was a strong linear relationship between the arousal index scored with the two definitions (r=0.981, p<0.001). Mean+/-SD scoring duration was significantly shorter for UCL than for ASDA definitions (18.5+/-5.4 versus 25.3+/-6.6 min, p<0.001). In conclusion, it has been found that in obstructive sleep apnoea syndrome patients, the American Sleep Disorders Association and Université Catholique de Louvain definitions were comparable in terms of agreement and repeatability.

Manufacture of small calibre quadruple lamina vascular bypass grafts using a novel automated extrusion-phase-inversion method and nanocomposite polymer.

PubMed

Sarkar, Sandip; Burriesci, Gaetano; Wojcik, Adam; Aresti, Nicholas; Hamilton, George; Seifalian, Alexander M

2009-04-16

Long-term patency of expanded polytetrafluoroethylene (ePTFE) small calibre cardiovascular bypass prostheses (<6mm) is poor because of thrombosis and intimal hyperplasia due to low compliance, stimulating the search for elastic alternatives. Wall porosity allows effective post-implantation graft healing, encouraging endothelialisation and a measured fibrovascular response. We have developed a novel poly (carbonate) urethane-based nanocomposite polymer incorporating polyhedral oligomeric silsesquioxane (POSS) nanocages (UCL-NANO) which shows anti-thrombogenicity and biostability. We report an extrusion-phase-inversion technique for manufacturing uniform-walled porous conduits using UCL-NANO. Image analysis-aided wall measurement showed that two uniform wall-thicknesses could be specified. Different coagulant conditions revealed the importance of low-temperature phase-inversion for graft integrity. Although minor reduction of pore-size variation resulted from the addition of ethanol or N,N-dimethylacetamide, high concentrations of ethanol as coagulant did not provide uniform porosity throughout the wall. Tensile testing showed the grafts to be elastic with strength being directly proportional to weight. The ultimate strengths achieved were above those expected from haemodynamic conditions, with anisotropy due to the manufacturing process. Elemental analysis by energy-dispersive X-ray analysis did not show a regional variation of POSS on the lumen or outer surface. In conclusion, the automated vertical extrusion-phase-inversion device can reproducibly fabricate uniform-walled small calibre conduits from UCL-NANO. These elastic microporous grafts demonstrate favourable mechanical integrity for haemodynamic exposure and are currently undergoing in-vivo evaluation of durability and healing properties.

A halogenophilic pathway in the reactions of transition metal carbonyl anions with [(η⁶-iodobenzene)Cr(CO)₃].

PubMed

Sazonov, Petr K; Ivushkin, Vasiliy A; Khrustalev, Victor N; Kolotyrkina, Natal'ya G; Beletskaya, Irina P

2014-09-21

The paper provides the first example of formal nucleophilic substitution by the halogenophilic pathway in Cr(CO)3 complexes of haloarenes with metal carbonyl anions. All metal carbonyl anions examined attack [(η(6)-iodobenzene)Cr(CO)3] at halogen, which is shown by aryl carbanion scavenging with t-BuOH. The reaction with K[CpFe(CO)2] gives only the dehalogenated arene, but the reaction with K[Cp*Fe(CO)2] (Cp* = η(5)-C5Me5) results in nucleophilic substitution to give [(η(6)-C6H5FeCp*(CO)2)Cr(CO)3]. Reaction with Na[Re(CO)5] quantitatively gives the iodo(acyl)rhenate anion Na[(η(6)-C6H5C(O)ReI(CO)4)Cr(CO)3] and in the case of K[Mn(CO)5] a mixture of σ-aryl complexes [(η(6)-C6H5Mn(CO)5)Cr(CO)3] and K[(η(6)-C6H5Mn(CO)4I)Cr(CO)3]. An analogous rhenium complex Na[(η(6)-C6H5Re(CO)4I)Cr(CO)3] is formed from the initial iodo(acyl)rhenate upon prolonged standing at 20 °C, and its structure (in the form of [NEt4](+) salt) is established by X-ray diffraction analysis. The reaction of [(η(6)-chlorobenzene)Cr(CO)3] with K[CpFe(CO)2], in contrast, proceeds by the common S(N)2Ar mechanism.

Photochemical oxidation of water and reduction of polyoxometalate anions at interfaces of water with ionic liquids or diethylether

PubMed Central

Bernardini, Gianluca; Wedd, Anthony G.; Zhao, Chuan; Bond, Alan M.

2012-01-01

Photoreduction of [P2W18O62]6-, [S2Mo18O62]4-, and [S2W18O62]4- polyoxometalate anions (POMs) and oxidation of water occurs when water–ionic liquid and water–diethylether interfaces are irradiated with white light (275–750 nm) or sunlight. The ionic liquids (ILs) employed were aprotic ([Bmim]X; Bmim = (1-butyl-3-methylimidazolium,X = BF4,PF6) and protic (DEAS = diethanolamine hydrogen sulphate; DEAP = diethanolamine hydrogen phosphate). Photochemical formation of reduced POMs at both thermodynamically stable and unstable water–IL interfaces led to their initial diffusion into the aqueous phase and subsequent extraction into the IL phase. The mass transport was monitored visually by color change and by steady-state voltammetry at microelectrodes placed near the interface and in the bulk solution phases. However, no diffusion into the organic phase was observed when [P2W18O62]6- was photo-reduced at the water–diethylether interface. In all cases, water acted as the electron donor to give the overall process: 4POM + 2H2O + hν → 4POM- + 4H+ + O2. However, more highly reduced POM species are likely to be generated as intermediates. The rate of diffusion of photo-generated POM- was dependent on the initial concentration of oxidized POM and the viscosity of the IL (or mixed phase system produced in cases in which the interface is thermodynamically unstable). In the water-DEAS system, the evolution of dioxygen was monitored in situ in the aqueous phase by using a Clark-type oxygen sensor. Differences in the structures of bulk and interfacial water are implicated in the activation of water. An analogous series of reactions occurred upon irradiation of solid POM salts in the presence of water vapor. PMID:22753501

Growth, strain relaxation properties and high-κ dielectric integration of mixed-anion GaAs{sub 1-y}Sb{sub y} metamorphic materials

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

Zhu, Y.; Clavel, M.; Goley, P.

Mixed-anion, GaAs{sub 1-y}Sb{sub y} metamorphic materials with a wide range of antimony (Sb) compositions extending from 15% to 62%, were grown by solid source molecular beam epitaxy (MBE) on GaAs substrates. The impact of different growth parameters on the Sb composition in GaAs{sub 1-y}Sb{sub y} materials was systemically investigated. The Sb composition was well-controlled by carefully optimizing the As/Ga ratio, the Sb/Ga ratio, and the substrate temperature during the MBE growth process. High-resolution x-ray diffraction demonstrated a quasi-complete strain relaxation within each composition of GaAs{sub 1-y}Sb{sub y}. Atomic force microscopy exhibited smooth surface morphologies across the wide range of Sbmore » compositions in the GaAs{sub 1-y}Sb{sub y} structures. Selected high-κ dielectric materials, Al{sub 2}O{sub 3}, HfO{sub 2}, and Ta{sub 2}O{sub 5} were deposited using atomic layer deposition on the GaAs{sub 0.38}Sb{sub 0.62} material, and their respective band alignment properties were investigated by x-ray photoelectron spectroscopy (XPS). Detailed XPS analysis revealed a valence band offset of >2 eV for all three dielectric materials on GaAs{sub 0.38}Sb{sub 0.62}, indicating the potential of utilizing these dielectrics on GaAs{sub 0.38}Sb{sub 0.62} for p-type metal-oxide-semiconductor (MOS) applications. Moreover, both Al{sub 2}O{sub 3} and HfO{sub 2} showed a conduction band offset of >2 eV on GaAs{sub 0.38}Sb{sub 0.62}, suggesting these two dielectrics can also be used for n-type MOS applications. The well-controlled Sb composition in several GaAs{sub 1-y}Sb{sub y} material systems and the detailed band alignment analysis of multiple high-κ dielectric materials on a fixed Sb composition, GaAs{sub 0.38}Sb{sub 0.62}, provides a pathway to utilize GaAs{sub 1-y}Sb{sub y} materials in future microelectronic and optoelectronic applications.« less

A new anion-deficient fluorite-related superstructure of Bi{sub 28}V{sub 8}O{sub 62}

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

Đorđević, T., E-mail: tamara.djordjevic@univie.ac.at; Karanović, Lj., E-mail: ljika2002@yahoo.com

2014-12-15

New hydrothermally synthesized Bi{sub 28}V{sub 8}O{sub 62} was structurally characterized using single-crystal X-ray diffraction data. Bi{sub 28}V{sub 8}O{sub 62} crystallizes in the novel type of defect fluorite structure related to the face-centered cubic δ-Bi{sub 2}O{sub 3}. It is monoclinic, s. g. P2{sub 1}/c, and the relation to the fluorite subcell is given as a∼(3/2)a{sub F}+(3/2)c{sub F}; b∼ −b{sub F}; c∼2a{sub F} −4c{sub F} (F in subscript indicate the unit cell parameter of fluorite). Its structure is characterized by slabs of edge sharing OBi{sub 4} tetrahedra surrounded by the OBi{sub 3} triangles. As a part of these OBi{sub 3} triangles, twomore » positionally disordered Bi{sup 3+} cations were observed in the marginal part of the slabs. The slabs are extending along b axis and are linked by inter-slab portion of the structure composed of VO{sub 4} tetrahedra and BiO{sub 6−x} coordination polyhedra, where x is a number of vacant oxygen sites. Raman spectra verified the coordination environment of vanadium atoms in the structure. - Graphical abstract: The [4{sup ¯}01] projection of two slabs and inter-slab part of the structure in one layer parallel to the (3{sup ¯}08)=(002{sup ¯}){sub F} plane (F in subscript indicate a fluorite type structure). The large green circles are Bi atoms. Small blue circles represent partly and fully occupied O sites, respectively. Pink (hatched black) are V1O{sub 4} and blue (hatched white) are V2O{sub 4} coordination tetrahedra. - Highlights: • Single crystals of Bi{sub 28}V{sub 8}O{sub 62} were grown using hydrothermal technique. • The crystal structure of Bi{sub 28}V{sub 8}O{sub 62} was solved using single-crystal XRD method. • Bi{sub 28}V{sub 8}O{sub 62} has an anion-deficient fluorite-related superstructure. • Raman spectrum confirmed the coordination environment of vanadium atoms. • Relation to the structurally related compound was discussed.« less

PROUCL VERSION 3.0

EPA Science Inventory

The computation ofa (l-a) 100% upper confidence limit (UCL) of the population mean depends upon the data distribution. Typically, environmental data are positively skewed, and a default lognormal distribution (EPA, 1992) is often used to model such data distributions. The H-stati...

Outcomes and Return to Sport After Ulnar Collateral Ligament Reconstruction in Adolescent Baseball Players.

PubMed

Saper, Michael; Shung, Joseph; Pearce, Stephanie; Bompadre, Viviana; Andrews, James R

2018-04-01

The number of ulnar collateral ligament (UCL) reconstructions in adolescent athletes has increased over the past 2 decades. Clinical results in this population have not been well studied. The purpose of this study was to evaluate the outcomes and return to sport after UCL reconstruction in a large group of adolescent baseball players. We hypothesized that excellent clinical outcomes and high rates of return to sport would be observed in this population at a minimum 2-year follow-up. Case series; Level of evidence, 4. We reviewed 140 adolescent (aged ≤19 years) baseball players who underwent UCL reconstruction with the American Sports Medicine Institute (ASMI) technique by a single surgeon. Medical records were reviewed for patient demographics, injury characteristics, operative details, and surgical complications. Patient-reported outcomes were assessed using the Conway scale, the Andrews-Timmerman (A-T) score, the Kerlan-Jobe Orthopaedic Clinic (KJOC) score, and a 0- to 100-point subjective scale for elbow function and satisfaction. Return to sporting activity was assessed using a custom-designed questionnaire. The mean age at the time of surgery was 18.0 years (range, 13-19 years), and the mean follow-up was 57.9 months (range, 32.4-115.4 months). Over half (60%) of patients were high school athletes. The mean duration of symptoms before surgery was 6.9 months (range, 0.5-60.0 months). Partial tears were identified in 57.9% of patients, and 41.3% of patients had preoperative ulnar nerve symptoms. Graft type included the ipsilateral palmaris in 77.1% of patients. Concomitant procedures were performed in 25% of patients. Outcomes on the Conway scale were "excellent" in 86.4% of patients. The mean A-T and KJOC scores were 97.3 ± 6.1 and 85.2 ± 14.6, respectively. Mean patient satisfaction was 94.4. Overall, 97.8% of patients reported returning to sport at a mean of 11.6 months (range, 5-24 months), and 89.9% of patients returned to sport at the same level of competition or higher. A total of 11.6% of patients went on to play professional baseball. UCL reconstruction with the ASMI technique is an effective surgical option in adolescents, with excellent outcome scores. At a minimum of 2-year follow-up, nearly 90% of patients returned to their preinjury level of sport.

Cyclometalated Iminophosphorane Gold(III) and Platinum(II) Complexes. A Highly Permeable Cationic Platinum(II) Compound with Promising Anticancer Properties

PubMed Central

2015-01-01

New organometallic gold(III) and platinum(II) complexes containing iminophosphorane ligands are described. Most of them are more cytotoxic to a number of human cancer cell lines than cisplatin. Cationic Pt(II) derivatives 4 and 5, which differ only in the anion, Hg2Cl62– or PF6– respectively, display almost identical IC50 values in the sub-micromolar range (25–335-fold more active than cisplatin on these cell lines). The gold compounds induced mainly caspase-independent cell death, as previously reported for related cycloaurated compounds containing IM ligands. Cycloplatinated compounds 3, 4, and 5 can also activate alternative caspase-independent mechanisms of death. However, at short incubation times cell death seems to be mainly caspase dependent, suggesting that the main mechanism of cell death for these compounds is apoptosis. Mercury-free compound 5 does not interact with plasmid (pBR322) DNA or with calf thymus DNA. Permeability studies of 5 by two different assays, in vitro Caco-2 monolayers and a rat perfusion model, have revealed a high permeability profile for this compound (comparable to that of metoprolol or caffeine) and an estimated oral fraction absorbed of 100%, which potentially makes it a good candidate for oral administration. PMID:26147404

Selective inclusion of PO4(3-) within persistent dimeric capsules of a tris(thiourea) receptor and evidence of cation/solvent sealed unimolecular capsules.

PubMed

Dey, Sandeep Kumar; Das, Gopal

2012-08-07

A tren-based tris(thiourea) receptor, L with electron-withdrawing p-nitrophenyl terminals has been established as a competent hydrogen-bonding scaffold that can selectively encapsulate PO(4)(3-) within persistent and rigid dimeric capsules, assembled by aromatic π-stacking interactions between the receptor side-arms. A quaternary ammonium salt of PO(4)(3-) capsules (complexes 1 and 1b, 2:1 host-guest) can reproducibly be obtained in quantitative yields by a solution-state deprotonation of [HL](+) moieties and a bound HPO(4)(2-) anion of complex 1a (HPO(4)(2-) complex of protonated L, 2:1 host-guest), induced by the presence of a large excess of anions such as HCO(3)(-), CH(3)CO(2)(-), and F(-). Qualitative as well as quantitative (1)H and (31)P NMR experiments (DMSO-d(6)) have been carried out in detail to demonstrate the selective and preferential inclusion of PO(4)(3-) by L in solution-states. Competitive crystallization experiments performed in the presence of an excess of anions such as HCO(3)(-), HSO(4)(-), CH(3)CO(2)(-), NO(3)(-) and halides (F(-) and Cl(-)) further establish the phenomenon of selective PO(4)(3-) encapsulation as confirmed by (1)H NMR, (31)P NMR, FT-IR and powder X-ray diffraction patterns of the isolated crystals. X-ray structural analyses and (31)P NMR studies of the isolated crystals of phosphate complexes (1, 1a and 1b) provide evidence of the binding discrepancy of inorganic phosphates with protonated and neutral form of L. Furthermore, extensive studies have been carried out with other anions of different sizes and dimensions in solid- and solution-states (complexes 2a, 3, 4 and 5). Crystal structure elucidation revealed the formation of a solvent (DMSO) sealed unimolecular capsule in the F(-) encapsulated complex, 2a (1:1 host-guest), a CO(3)(2-) encapsulated centrosymmetric molecular capsule in 3 (2:1 host-guest) and a cation (tetrabutylammonium) sealed SO(4)(2-) encapsulated unimolecular capsule in 4 (1:1 host-guest). 2D-NOESY NMR experiments carried out on these capsule complexes further confirm the relevant binding stoichiometry of complexes (2a-4) except for the PO(4)(3-)-encapsulated complex (1b) which showed a 1:1 host-guest stoichiometry in solution.

Carbonate formation within a nickel dimer: synthesis of a coordinatively unsaturated bis(mu-hydroxo) dinickel complex and its reactivity toward carbon dioxide.

PubMed

Wikstrom, Jeffrey P; Filatov, Alexander S; Mikhalyova, Elena A; Shatruk, Michael; Foxman, Bruce M; Rybak-Akimova, Elena V

2010-03-14

The tridentate aminopyridine ligand bearing a bulky tert-butyl substituent at the amine nitrogen, tert-butyl-dipicolylamine (tBuDPA), occupies three coordination sites in six-coordinate complexes of nickel(ii), leaving the remaining three sites available for additional ligand binding and activation. New crystallographically characterized complexes include two mononuclear species with 1:1 metal:ligand complexation: a trihydrate solvate (1.3H(2)O) and a monohydrate biacetonitrile solvate (1.H(2)O.2CH(3)CN). Complexation in the presence of sodium hydroxide results in a bis(mu-hydroxo) complex (2), the bridging hydroxide anions of which are labile and become displaced by methoxide anions in methanol solvent, affording bis-methoxo-bridged (4). Nickel(II) centers in 2 are five-coordinate and antiferromagnetically coupled (with J = -31.4(5) cm(-1), H = -2JS(1)S(2), in agreement with Ni-O-Ni angle of 103.7 degrees). Bridging hydroxide or alkoxide anions in coordinatively unsaturated dinuclear nickel(II) complexes with tBuDPA react as active nucleophiles. 2 readily performs carbon dioxide fixation, resulting in the formation of a bis(mu-carbonato) tetrameric complex (3), which features a novel binding geometry in the form of an inverted butterfly-type nickel-carbonate core. Temperature-dependent magnetic measurements of tetranuclear carbonato-bridged revealed relatively weak antiferromagnetic coupling (J(1) = -3.1(2) cm(-1)) between the two nickel centers in the core of the cluster, as well as weak antiferromagnetic pairwise interactions (J(2) = J(3) = -4.54(5) cm(-1)) between central and terminal nickel ions.

Smart responsive phosphorescent materials for data recording and security protection.

PubMed

Sun, Huibin; Liu, Shujuan; Lin, Wenpeng; Zhang, Kenneth Yin; Lv, Wen; Huang, Xiao; Huo, Fengwei; Yang, Huiran; Jenkins, Gareth; Zhao, Qiang; Huang, Wei

2014-04-07

Smart luminescent materials that are responsive to external stimuli have received considerable interest. Here we report ionic iridium (III) complexes simultaneously exhibiting mechanochromic, vapochromic and electrochromic phosphorescence. These complexes share the same phosphorescent iridium (III) cation with a N-H moiety in the N^N ligand and contain different anions, including hexafluorophosphate, tetrafluoroborate, iodide, bromide and chloride. The anionic counterions cause a variation in the emission colours of the complexes from yellow to green by forming hydrogen bonds with the N-H proton. The electronic effect of the N-H moiety is sensitive towards mechanical grinding, solvent vapour and electric field, resulting in mechanochromic, vapochromic and electrochromic phosphorescence. On the basis of these findings, we construct a data-recording device and demonstrate data encryption and decryption via fluorescence lifetime imaging and time-gated luminescence imaging techniques. Our results suggest that rationally designed phosphorescent complexes may be promising candidates for advanced data recording and security protection.

Anion Binding and Transport by Prodigiosin and Its Analogs

NASA Astrophysics Data System (ADS)

Davis, Jeffery T.

The red-colored prodiginines, exemplified by prodigiosin 1, are secondary metabolites produced by a number of microorganisms, including the bacterium Serratia marcescens. These tripyrrole natural products and their synthetic analogs have received renewed attention over the past deacade, primarily because of their promising immunosuppressive and anticancer activities. One of the hallmarks of prodiginin chemistry is the ability of the monoprotonated ligand to bind anions, including the essential chloride and bicarbonate ions. The resulting lipophilic ion pair is then able to diffuse across the hydrophobic barrier presented by phospholipid bilayers. Thus, prodiginines have been found to be potent transmembrane anion transporters and HCl cotransporters. In this chapter, the author reviews what is known about the solid-state structure of prodiginins and their anion complexes, the solution conformation of prodiginines, and the biochemcal evidence for the ability to bind anions and to transport HCl across cell membranes. Recent progress in making synthetic models of prodiginines and recent results on the ability of prodigiosin to transport HCO 3 - across lipid membranes are discussed.

The anionic (9-methyladenine)-(1-methylthymine) base pair solvated by formic acid. A computational and photoelectron spectroscopy study.

PubMed

Storoniak, Piotr; Mazurkiewicz, Kamil; Haranczyk, Maciej; Gutowski, Maciej; Rak, Janusz; Eustis, Soren N; Ko, Yeon Jae; Wang, Haopeng; Bowen, Kit H

2010-09-02

The photoelectron spectrum for (1-methylthymine)-(9-methyladenine)...(formic acid) (1MT-9MA...FA) anions with the maximum at ca. 1.87 eV was recorded with 2.54 eV photons and interpreted through the quantum-chemical modeling carried out at the B3LYP/6-31+G(d,p) level. The relative free energies of the anions and their calculated vertical detachment energies suggest that only seven anionic structures contribute to the observed PES signal. We demonstrate that electron binding to the (1MT-9MA...FA) complex can trigger intermolecular proton transfer from formic acid, leading to the strong stabilization of the resulting radical anion. The SOMO distribution indicates that an excess electron may localize not only on the pyrimidine but also on the purine moiety. The biological context of DNA-environment interactions concerning the formation of single-strand breaks induced by excess electrons has been briefly discussed.

Method of separating short half-life radionuclides from a mixture of radionuclides

DOEpatents

Bray, Lane A.; Ryan, Jack L.

1999-01-01

The present invention is a method of removing an impurity of plutonium, lead or a combination thereof from a mixture of radionuclides that contains the impurity and at least one parent radionuclide. The method has the steps of (a) insuring that the mixture is a hydrochloric acid mixture; (b) oxidizing the acidic mixture and specifically oxidizing the impurity to its highest oxidation state; and (c) passing the oxidized mixture through a chloride form anion exchange column whereupon the oxidized impurity absorbs to the chloride form anion exchange column and the 22.sup.9 Th or 2.sup.27 Ac "cow" radionuclide passes through the chloride form anion exchange column. The plutonium is removed for the purpose of obtaining other alpha emitting radionuclides in a highly purified form suitable for medical therapy. In addition to plutonium; lead, iron, cobalt, copper, uranium, and other metallic cations that form chloride anionic complexes that may be present in the mixture; are removed from the mixture on the chloride form anion exchange column.

Method of separating short half-life radionuclides from a mixture of radionuclides

DOEpatents

Bray, L.A.; Ryan, J.L.

1999-03-23

The present invention is a method of removing an impurity of plutonium, lead or a combination thereof from a mixture of radionuclides that contains the impurity and at least one parent radionuclide. The method has the steps of (a) insuring that the mixture is a hydrochloric acid mixture; (b) oxidizing the acidic mixture and specifically oxidizing the impurity to its highest oxidation state; and (c) passing the oxidized mixture through a chloride form anion exchange column whereupon the oxidized impurity absorbs to the chloride form anion exchange column and the {sup 229}Th or {sup 227}Ac ``cow`` radionuclide passes through the chloride form anion exchange column. The plutonium is removed for the purpose of obtaining other alpha emitting radionuclides in a highly purified form suitable for medical therapy. In addition to plutonium, lead, iron, cobalt, copper, uranium, and other metallic cations that form chloride anionic complexes that may be present in the mixture are removed from the mixture on the chloride form anion exchange column. 8 figs.

Investigation of atmospheric oxidation of propyl gallate in an anionic surfactant system in the absence and presence of ascorbic acid.

PubMed

Szymula, M

2004-01-01

The antioxidant efficiency of two hydrophilic species, ascorbic acid (AA) and propyl gallate (PG), in an anionic surfactant system are studied. Ascorbic acid and propyl gallate are dissolved/solubilized in a microemulsion formed by water, pentanol, and sodium dodecyl sulfate. The determination of propyl gallate decomposition/oxidation kinetics shows enhanced oxidation of PG with increasing pentanol concentration in the system. When ascorbic acid and propyl gallate are both present in water, in surfactant aqueous solution, and in the studied microemulsion systems, the molecular complex AAPG is formed. After some time the complex decomposes.

Spectrophotometric Study of the Complex Formation of Anionic Chelates of Cobalt(II) with Monotetrazolium Cations

NASA Astrophysics Data System (ADS)

Divarova, V. V.; Stojnova, K. T.; Racheva, P. V.; Lekova, V. D.

2017-05-01

The complex formation and extraction of anionic chelates of Co(II)-4-(2-thiazolylazo)resorcinol (TAR) with cations of monotetrazolium salts (TS) — (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) and 3-(2-naphthyl)-2,5-diphenyl-2H-tetrazolium chloride (TV) — in the liquid-liquid extraction system Co(II)-TAR-TS-H2O-CHCl3 were studied by spectrophotometric methods. The optimum conditions for the extraction of Co(II) were found. The molar ratio of the components and the form of the anionic chelates of Co(II) in the extracted compounds were determined by independent methods. The association process in the aqueous phase and the extraction process were investigated and quantitatively characterized. The following key constants were calculated: association constant, distribution constant, extraction constant, and recovery factor. The validity of the Beer's law was checked, and some analytical characteristics were calculated. Based on the obtained results and the lower price of the monotetrazolium salt MTT compared with that of TV, the ion-associated complex of Co(II)-TAR-MTT can be implemented for determination of cobalt(II) traces in alloys and biological, medical, and pharmaceutical samples.

Spectral and Fluorescent Studies of the Interaction of an Anionic Oxacarbocyanine Dye with Bovine Serum Albumin

NASA Astrophysics Data System (ADS)

Pronkin, P. G.; Tatikolov, A. S.

2017-01-01

The influence of the formation of noncovalent intermolecular complexes with bovine serum albumin (BSA) on the spectral and fluorescent properties of the anionic oxacarbocyanine dye 3,3'-di-(γ-sulfopropyl)-5,5'-diphenyl-9-ethyloxacarbocyanine betaine (OCC) was studied. Binding of OCC to BSA increased significantly the dye fluorescence. Changes in the absorption and fluorescence spectra of OCC upon interaction with BSA argued in favor of a shift of the dye cis-trans equilibrium in the complex. The effects of adding albumin-denaturing compounds (urea, sodium dodecyl sulfate) on the spectral and fluorescent properties of the dye in the OCC-BSA complex were studied. It was concluded that OCC can act as a probe for albumins and can be used to study protein denaturing.

Electron detachment of the hydrogen-bonded amino acid side-chain guanine complexes

NASA Astrophysics Data System (ADS)

Wang, Jing; Gu, Jiande; Leszczynski, Jerzy

2007-07-01

The photoelectron spectra of the hydrogen-bonded amino acid side-chain-guanine complexes has been studied at the partial third order (P3) self-energy approximation of the electron propagator theory. The correlation between the vertical electron detachment energy and the charge distributions on the guanine moiety reveals that the vertical electron detachment energy (VDE) increases as the positive charge distribution on the guanine increases. The low VDE values determined for the negatively charged complexes of the guanine-side-chain-group of Asp/Glu suggest that the influence of the H-bonded anionic groups on the VDE of guanine could be more important than that of the anionic backbone structure. The even lower vertical electron detachment energy for guanine is thus can be expected in the H-bonded protein-DNA systems.

Surface coating of siRNA-peptidomimetic nano-self-assemblies with anionic lipid bilayers: enhanced gene silencing and reduced adverse effects in vitro

NASA Astrophysics Data System (ADS)

Zeng, Xianghui; de Groot, Anne Marit; Sijts, Alice J. A. M.; Broere, Femke; Oude Blenke, Erik; Colombo, Stefano; van Eden, Willem; Franzyk, Henrik; Nielsen, Hanne Mørck; Foged, Camilla

2015-11-01

Cationic vectors have demonstrated the potential to facilitate intracellular delivery of therapeutic oligonucleotides. However, enhanced transfection efficiency is usually associated with adverse effects, which also proves to be a challenge for vectors based on cationic peptides. In this study a series of proteolytically stable palmitoylated α-peptide/β-peptoid peptidomimetics with a systematically varied number of repeating lysine and homoarginine residues was shown to self-assemble with small interfering RNA (siRNA). The resulting well-defined nanocomplexes were coated with anionic lipids giving rise to net anionic liposomes. These complexes and the corresponding liposomes were optimized towards efficient gene silencing and low adverse effects. The optimal anionic liposomes mediated a high silencing effect, which was comparable to that of the control (cationic Lipofectamine 2000), and did not display any noticeable cytotoxicity and immunogenicity in vitro. In contrast, the corresponding nanocomplexes mediated a reduced silencing effect with a more narrow safety window. The surface coating with anionic lipid bilayers led to partial decomplexation of the siRNA-peptidomimetic nanocomplex core of the liposomes, which facilitated siRNA release. Additionally, the optimal anionic liposomes showed efficient intracellular uptake and endosomal escape. Therefore, these findings suggest that a more efficacious and safe formulation can be achieved by surface coating of the siRNA-peptidomimetic nano-self-assemblies with anionic lipid bilayers.Cationic vectors have demonstrated the potential to facilitate intracellular delivery of therapeutic oligonucleotides. However, enhanced transfection efficiency is usually associated with adverse effects, which also proves to be a challenge for vectors based on cationic peptides. In this study a series of proteolytically stable palmitoylated α-peptide/β-peptoid peptidomimetics with a systematically varied number of repeating lysine and homoarginine residues was shown to self-assemble with small interfering RNA (siRNA). The resulting well-defined nanocomplexes were coated with anionic lipids giving rise to net anionic liposomes. These complexes and the corresponding liposomes were optimized towards efficient gene silencing and low adverse effects. The optimal anionic liposomes mediated a high silencing effect, which was comparable to that of the control (cationic Lipofectamine 2000), and did not display any noticeable cytotoxicity and immunogenicity in vitro. In contrast, the corresponding nanocomplexes mediated a reduced silencing effect with a more narrow safety window. The surface coating with anionic lipid bilayers led to partial decomplexation of the siRNA-peptidomimetic nanocomplex core of the liposomes, which facilitated siRNA release. Additionally, the optimal anionic liposomes showed efficient intracellular uptake and endosomal escape. Therefore, these findings suggest that a more efficacious and safe formulation can be achieved by surface coating of the siRNA-peptidomimetic nano-self-assemblies with anionic lipid bilayers. Electronic supplementary information (ESI) available: Non-fusogenic liposomes; cytotoxicity of naked siRNA and the empty vector; immunogenicity; low-magnification images; DOPE/DPPC liposomes. See DOI: 10.1039/c5nr04807a

Comparative density functional study of the complexes [UO2(CO3)3]4- and [(UO2)3(CO3)6]6- in aqueous solution.

PubMed

Schlosser, Florian; Moskaleva, Lyudmila V; Kremleva, Alena; Krüger, Sven; Rösch, Notker

2010-06-28

With a relativistic all-electron density functional method, we studied two anionic uranium(VI) carbonate complexes that are important for uranium speciation and transport in aqueous medium, the mononuclear tris(carbonato) complex [UO(2)(CO(3))(3)](4-) and the trinuclear hexa(carbonato) complex [(UO(2))(3)(CO(3))(6)](6-). Focusing on the structures in solution, we applied for the first time a full solvation treatment to these complexes. We approximated short-range effects by explicit aqua ligands and described long-range electrostatic interactions via a polarizable continuum model. Structures and vibrational frequencies of "gas-phase" models with explicit aqua ligands agree best with experiment. This is accidental because the continuum model of the solvent to some extent overestimates the electrostatic interactions of these highly anionic systems with the bulk solvent. The calculated free energy change when three mono-nuclear complexes associate to the trinuclear complex, agrees well with experiment and supports the formation of the latter species upon acidification of a uranyl carbonate solution.

Pentacoordinate silicon(IV): cationic, anionic and neutral complexes derived from the reaction of NHC→SiCl4 with highly Lewis acidic (C2F5)2SiH2.

PubMed

Böttcher, T; Steinhauer, S; Neumann, B; Stammler, H-G; Röschenthaler, G-V; Hoge, B

2014-06-14

Addition of NHC→SiCl4 to the highly Lewis acidic bis(pentafluoroethyl)silane ((C2F5)2SiH2) afforded the salt [(NHC)2SiCl2H][(C2F5)2SiCl3] with pentacoordinate silicon in the cation and the anion. The anion represents the first example of a chlorosilicate structurally characterized in the solid state. In this reaction, the long sought pentacoordinate NHC-adduct of silicochloroform was identified as an intermediate and its crystal structure is presented.

Theoretical study on the anion photoelectron spectra of Ln(COT)2- including the spin-orbit effects

NASA Astrophysics Data System (ADS)

Nakajo, Erika; Yabushita, Satoshi

2017-06-01

The multiplet level splittings for both anion and neutral sandwich complexes Ln(COT)2 (Ln = Ce-Yb, COT = 1,3,5,7-cyclooctatetraene) were calculated with spin-orbit interactions to analyze their anion photoelectron spectra. The theoretically simulated spectra obtained with these energies and the pole strengths are generally consistent with the experimental spectra for the X peak. The magnitudes of the energy splittings, relative peak intensities, and their Ln dependence are reproduced. In comparison to our previous calculations, the inclusion of spin-orbit interactions with the SO-MCQDPT2 method makes the simulated spectra more consistent with the results of the experiment.

Structure of a Premicellar Complex of Alkyl Sulfates with the Interfacial Binding Surfaces of 4 Subunits of Phospholipase A2✰

PubMed Central

Pan, Ying H.; Bahnson, Brian J.

2010-01-01

The properties of three discrete premicellar complexes (E1#, E2#, E3#) of pig pancreatic group-IB secreted phospholipase A2 (sPLA2) with monodisperse alkyl sulfates has been characterized [Berg, O. G., et al., Biochemistry 43, 7999–8013, 2004]. Here we have solved the 2.7 Å crystal structure of group-IB sPLA2 complexed with 12 molecules of octyl sulfate (C8S) in a form consistent with a tetrameric oligomeric that exists during the E1# phase of premicellar complexes. The alkyl tails of the C8S molecules are centered in the middle of the tetrameric cluster of sPLA2 subunits. Three of the four sPLA2 subunits also contain a C8S molecule in the active site pocket. The sulfate oxygen of a C8S ligand is complexed to the active site calcium in 3 of the 4 protein active sites. The interactions of the alkyl sulfate head group with Arg-6 and Lys-10, as well as the backbone amide of Met-20, are analogous to those observed in the previously solved sPLA2 crystal structures with bound phosphate and sulfate anions. The cluster of three anions found in the present structure is postulated to be the site for nucleating the binding of anionic amphiphiles to the interfacial surface of the protein, and therefore this binding interaction has implications for interfacial activation of the enzyme. PMID:20302975

Coordination Complexes of Titanium(IV) and Indium(III) Phthalocyanines with Carbonyl-Containing Dyes: The Formation of Singly Bonded Anionic Squarylium Dimers.

PubMed

Konarev, Dmitri V; Kuzmin, Alexey V; Khasanov, Salavat S; Fatalov, Alexey M; Yudanova, Evgenia I; Lyubovskaya, Rimma N

2018-04-14

Reduction methods for the preparation of coordination complexes of titanium(IV) and indium(III) phthalocyanines (Pc) with organic dyes such as indigo, thioindigo, and squarylium dye III (SQ) have been developed, which allow one to obtain crystalline {cryptand(K + )}{(cis-indigo-O,O) 2- Ti IV (Pc 2- )}(Cl - )⋅C 6 H 4 Cl 2 (1), {cryptand(K + )}{(cis-thioindigo-O,O) 2- In III (Pc 2- )} - ⋅C 6 H 4 Cl 2 (2), and {cryptand(K + )}{[(SQ) 2 -O,O] 2- In III (Pc 2- )} - ⋅3.5 C 6 H 4 Cl 2 (3) complexes. The formation of these complexes is accompanied by the reduction of the starting dyes to the anionic state. Transition of trans-indigo or trans-thioindigo to the cis conformation in 1 and 2 provides coordination of both carbonyl oxygen atoms of the dye to Ti IV Pc or In III Pc. SQ is reduced to the radical anion state and forms unusual diamagnetic singly bonded (SQ - ) 2 dimers in 3. These dimers have two closely positioned carbonyl oxygen atoms coordinated to In III Pc. Dianionic Pc 2- macrocycles have been found in 1-3. The complexes contain two chromophore molecules at one metal center. However, their optical spectra are defined mainly by absorption bands of the metal phthalocyanines. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of surface complexation models to anion adsorption by natural materials.

PubMed

Goldberg, Sabine

2014-10-01

Various chemical models of ion adsorption are presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model, are described in the present study. Characteristics common to all the surface complexation models are equilibrium constant expressions, mass and charge balances, and surface activity coefficient electrostatic potential terms. Methods for determining parameter values for surface site density, capacitances, and surface complexation constants also are discussed. Spectroscopic experimental methods of establishing ion adsorption mechanisms include vibrational spectroscopy, nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, X-ray absorption spectroscopy, and X-ray reflectivity. Experimental determinations of point of zero charge shifts and ionic strength dependence of adsorption results and molecular modeling calculations also can be used to deduce adsorption mechanisms. Applications of the surface complexation models to heterogeneous natural materials, such as soils, using the component additivity and the generalized composite approaches are described. Emphasis is on the generalized composite approach for predicting anion adsorption by soils. Continuing research is needed to develop consistent and realistic protocols for describing ion adsorption reactions on soil minerals and soils. The availability of standardized model parameter databases for use in chemical speciation-transport models is critical. Published 2014 Wiley Periodicals Inc. on behalf of SETAC. This article is a US Government work and as such, is in the public domain in the in the United States of America.

Biasing hydrogen bond donating host systems towards chemical warfare agent recognition.

PubMed

Hiscock, Jennifer R; Wells, Neil J; Ede, Jayne A; Gale, Philip A; Sambrook, Mark R

2016-10-12

A series of neutral ditopic and negatively charged, monotopic host molecules have been evaluated for their ability to bind chloride and dihydrogen phosphate anions, and neutral organophosphorus species dimethyl methylphosphonate (DMMP), pinacolyl methylphosphonate (PMP) and the chemical warfare agent (CWA) pinacolyl methylphosphonofluoridate (GD, soman) in organic solvent via hydrogen bonding. Urea, thiourea and boronic acid groups are shown to bind anions and neutral guests through the formation of hydrogen bonds, with the urea and thiourea groups typically exhibiting higher affinity interactions. The introduction of a negative charge on the host structure is shown to decrease anion affinity, whilst still allowing for high stability host-GD complex formation. Importantly, the affinity of the host for the neutral CWA GD is greater than for anionic guests, thus demonstrating the potential for selectivity reversal based on charge repulsion.

Radical anionic versus neutral 2,2'-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands.

PubMed

Diaconescu, Paula L; Cummins, Christopher C

2015-02-14

The synthesis and characterization of (bipy)(2)U(N[t-Bu]Ar)(2) (1-(bipy)(2), bipy = 2,2'-bipyridyl, Ar = 3,5-C(6)H(3)Me(2)), (bipy)U(N[(1)Ad]Ar)(3) (2-bipy), (bipy)(2)U(NC[t-Bu]Mes)(3) (3-(bipy)(2), Mes = 2,4,6-C(6)H(2)Me(3)), and IU(bipy)(NC[t-Bu]Mes)(3) (3-I-bipy) are reported. X-ray crystallography studies indicate that bipy coordinates as a radical anion in 1-(bipy)(2) and 2-bipy, and as a neutral ligand in 3-I-bipy. In 3-(bipy)(2), one of the bipy ligands is best viewed as a radical anion, the other as a neutral ligand. The electronic structure assignments are supported by NMR spectroscopy studies of exchange experiments with 4,4'-dimethyl-2,2'-bipyridyl and also by optical spectroscopy. In all complexes, uranium was assigned a +4 formal oxidation state.

Cellular Binding of Anionic Nanoparticles is Inhibited by Serum Proteins Independent of Nanoparticle Composition.

PubMed

Fleischer, Candace C; Kumar, Umesh; Payne, Christine K

2013-09-01

Nanoparticles used in biological applications encounter a complex mixture of extracellular proteins. Adsorption of these proteins on the nanoparticle surface results in the formation of a "protein corona," which can dominate the interaction of the nanoparticle with the cellular environment. The goal of this research was to determine how nanoparticle composition and surface modification affect the cellular binding of protein-nanoparticle complexes. We examined the cellular binding of a collection of commonly used anionic nanoparticles: quantum dots, colloidal gold nanoparticles, and low-density lipoprotein particles, in the presence and absence of extracellular proteins. These experiments have the advantage of comparing different nanoparticles under identical conditions. Using a combination of fluorescence and dark field microscopy, flow cytometry, and spectroscopy, we find that cellular binding of these anionic nanoparticles is inhibited by serum proteins independent of nanoparticle composition or surface modification. We expect these results will aid in the design of nanoparticles for in vivo applications.

A selective optical sensor based on [9]mercuracarborand-3, a new type of ionophore with a chloride complexing cavity

NASA Technical Reports Server (NTRS)

Badr, I. H.; Johnson, R. D.; Diaz, M.; Hawthorne, M. F.; Bachas, L. G.; Daunert, S. (Principal Investigator)

2000-01-01

A highly selective optical sensor for chloride, based on the multidentate Lewis acid ionophore [9]mercuracarborand-3, is described herein. This sensor is constructed by embedding the mercuracarborand ionophore, a suitable pH-sensitive lipophilic dye, and lipophilic cationic sites in a plasticized polymeric membrane. The multiple complementary interactions offered by the preorganized complexing cavity of [9]mercuracarborand-3 is shown to control the anion selectivity pattern of the optical film. The film exhibits a significantly enhanced selectivity for chloride over a variety of lipophilic anions such as perchlorate, nitrate, salicylate, and thiocyanate. Furthermore, the optical selectivity coefficients obtained for chloride over other biologically relevant anions are shown to meet the selectivity requirements for the determination of chloride in physiological fluids, unlike previously reported chloride optical sensors. In addition, the optical film responds to chloride reversibly over a wide dynamic range (16 microM-136 mM) with fast response and recovery times.

cis,cis,cis-(Acetato-κ(2) O,O')bis-[1,2-bis-(diphenyl-phosphan-yl)ethane-κ(2) P,P']ruthenium(II) 0.75-trifluoro-methane-sulfonate 0.25-chloride.

PubMed

Figueira, João; Rodrigues, João; Valkonen, Arto

2013-04-01

In the title Ru(II) carboxyl-ate compound, [Ru(C2H3O2)(C26H24P2)2](CF3O3S)0.75Cl0.25, the distorted tris-bidentate octa-hedral stereochemistry about the Ru(II) atom in the complex cation comprises four P-atom donors from two 1,2-bis-(diphenyl-phosphan-yl)ethane ligands [Ru-P = 2.2881 (13)-2.3791 (13) Å] and two O-atom donors from the acetate ligand [Ru-O = 2.191 (3) and 2.202 (3) Å]. The disordered counter-anions are located on the same site in the structure in a 3:1 ratio, the expanded formula comprising four complex cations, three trifluoro-methane-sulfonate anions and one chloride anion, with two such formula units in the unit cell.

Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands

DOE PAGES

Xie, Yan; Shaffer, David W.; Lewandowska-Andralojc, Anna; ...

2016-05-11

Here, we describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox-potential leveling through charge compensation and σ donation to allow facile access to high oxidation states. These complexes display unique pH-dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations.more » The unprecedented attack of water at a neutral six-coordinate [Ru IV] center to yield an anionic seven-coordinate [Ru IV–OH] – intermediate is one of the key steps of a single-site mechanism in which all species are anionic or neutral. These complexes are among the fastest single-site catalysts reported to date.« less

The N-terminal domain of the mammalian nucleoporin p62 interacts with other nucleoporins of the FXFG family during interphase

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

Stochaj, Ursula; Banski, Piotr; Kodiha, Mohamed

2006-08-01

Nuclear pore complexes (NPCs) provide the only sites for macromolecular transport between nucleus and cytoplasm. The nucleoporin p62, a component of higher eukaryotic NPCs, is located at the central gated channel and involved in nuclear trafficking of various cargos. p62 is organized into an N-terminal segment that contains FXFG repeats and binds the soluble transport factor NTF2, whereas the C-terminal portion associates with other nucleoporins and importin-{beta}1. We have now identified new components that interact specifically with the p62 N-terminal domain. Using the p62 N-terminal segment as bait, we affinity-purified nucleoporins Nup358, Nup214 and Nup153 from crude cell extracts. Inmore » ligand binding assays, the N-terminal p62 segment associated with Nup358 and p62, suggesting their direct binding to the p62 N-terminal portion. Furthermore, p62 was isolated in complex with Nup358, Nup214 and Nup153 from growing HeLa cells, indicating that the interactions Nup358/p62, Nup214/p62 and p62/Nup153 also occur in vivo. The formation of Nup358/p62 and p62/Nup153 complexes was restricted to interphase cells, whereas Nup214/p62 binding was detected in interphase as well as during mitosis. Our results support a model of complex interactions between FXFG containing nucleoporins, and we propose that some of these interactions may contribute to the movement of cargo across the NPC.« less

Mechanical properties of bulk graphene oxide/poly(acrylic acid)/poly(ethylenimine) ternary polyelectrolyte complex.

PubMed

Duan, Yipin; Wang, Chao; Zhao, Mengmeng; Vogt, Bryan D; Zacharia, Nicole S

2018-05-30

Ternary complexes formed in a single pot process through the mixing of cationic (branched polyethylenimine, BPEI) and anionic (graphene oxide, GO, and poly(acrylic acid), PAA) aqueous solutions exhibit superior mechanical performance in comparison to their binary analogs. The composition of the ternary complex can be simply tuned through the composition of the anionic solution, which influences the water content and mechanical properties of the complex. Increasing the PAA content in the complex decreases the overall water content due to improved charge compensation with the BPEI, but this change also significantly improves the toughness of the complex. Ternary complexes containing ≤32 wt% PAA were too brittle to generate samples for tensile measurements, while extension in excess of 250% could be reached with 57 wt% PAA. From this work, the influence of GO and PAA on the mechanical properties of GO/PAA/BPEI complexes were elucidated with GO sheets acting to restrain the viscous flow and improve the mechanical strength at low loading (<12.6 wt%) and PAA more efficiently complexes with BPEI than GO to generate a less swollen and stronger network. This combination overcomes the brittle nature of GO-BPEI complexes and viscous creep of PAA-BPEI complexes. Ternary nanocomposite complexes appear to provide an effective route to toughen and strengthen bulk polyelectrolyte complexes.

Hydrophilic Strong Anion Exchange (hSAX) Chromatography for Highly Orthogonal Peptide Separation of Complex Proteomes

PubMed Central

2013-01-01

Due to its compatibility and orthogonality to reversed phase (RP) liquid chromatography (LC) separation, ion exchange chromatography, and mainly strong cation exchange (SCX), has often been the first choice in multidimensional LC experiments in proteomics. Here, we have tested the ability of three strong anion exchanger (SAX) columns differing in their hydrophobicity to fractionate RAW264.7 macrophage cell lysate. IonPac AS24, a strong anion exchange material with ultralow hydrophobicity, demonstrated to be superior to other materials by fractionation and separation of tryptic peptides from both a mixture of 6 proteins as well as mouse cell lysate. The chromatography displayed very high orthogonality and high robustness depending on the hydrophilicity of column chemistry, which we termed hydrophilic strong anion exchange (hSAX). Mass spectrometry analysis of 34 SAX fractions from RAW264.7 macrophage cell lysate digest resulted in an identification of 9469 unique proteins and 126318 distinct peptides in one week of instrument time. Moreover, when compared to an optimized high pH/low pH RP separation approach, the method presented here raised the identification of proteins and peptides by 10 and 28%, respectively. This novel hSAX approach provides robust, reproducible, and highly orthogonal separation of complex protein digest samples for deep coverage proteome analysis. PMID:23294059

Chemistry of nitrile anions in the interstellar medium

NASA Astrophysics Data System (ADS)

Carles, S.; Le Garrec, J.-L.; Guillemin, J.-C.; Biennier, L.

2015-12-01

Despite the extreme conditions of temperature (down to 10K) and density (down to 100 molecules/cm3), the giant molecular clouds and the circumstellar envelopes present a rich and complex chemistry. To date, more than 180 molecules have been detected in the InterStellar Medium (ISM) with a large abundance of nitriles (RC≡N). In addition, several anions have been recently observed in this medium: C4H¯, C6H¯, C8H¯, CN¯, C3N¯ and C5N¯. These last species should play a key role in the molecular growth towards complexity. To explore this hypothesis, their reactivity must be studied in the laboratory. The FALP-MS and the CRESU experimental apparatuses of the Rennes University are able to measure absolute rate coefficient of various chemical reactions, including the ion - molecule reactions, in gas phase at low temperature (from 300K for the FALP-MS down to 15K for the CRESU). Therefore, these experimental tools are particularly adapted to the kinetic studies of reactions potentially involved in the Interstellar Medium. One of the difficulties encountered in experiments with anions is their generation. We describe here the formation of the CN¯ and C3N¯ anions by dissociative electron attachment on the molecular precursors BrCN and BrC3N.

Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragments

NASA Astrophysics Data System (ADS)

Schaugaard, Richard N.; Topolski, Josey E.; Ray, Manisha; Raghavachari, Krishnan; Jarrold, Caroline Chick

2018-02-01

Recent studies on reactions between MoxOy- cluster anions and H2O/C2H4 mixtures revealed a complex web of addition, hydrogen evolution, and chemifragmentation reactions, with chemifragments unambiguously connected to cluster reactions with C2H4. To gain insight into the molecular-scale interactions along the chemifragmentation pathways, the anion photoelectron (PE) spectra of MoC2H2-, MoC4H4-, MoOC2H2-, and MoO2C2H2- formed directly in MoxOy- + C2H4 (x > 1; y ≥ x) reactions, along with supporting CCSD(T) and density functional theory calculations, are presented and analyzed. The complexes have spectra that are all consistent with η2-acetylene complexes, though for all but MoC4H4-, the possibility that vinylidene complexes are also present cannot be definitively ruled out. Structures that are consistent with the PE spectrum of MoC2H2- differ from the lowest energy structure, suggesting that the fragment formation is under kinetic control. The PE spectrum of MoO2C2H2- additionally exhibits evidence that photodissociation to MoO2- + C2H2 may be occurring. The results suggest that oxidative dehydrogenation of ethylene is initiated by Lewis acid/base interactions between the Mo centers in larger clusters and the π orbitals in ethylene.

Solution Synthesis, Structure, and CO2 Reduction Reactivity of a Scandium(II) Complex, {Sc[N(SiMe3 )2 ]3 }.

PubMed

Woen, David H; Chen, Guo P; Ziller, Joseph W; Boyle, Timothy J; Furche, Filipp; Evans, William J

2017-02-13

The first crystallographically characterizable complex of Sc 2+ , [Sc(NR 2 ) 3 ] - (R=SiMe 3 ), has been obtained by LnA 3 /M reactions (Ln=rare earth metal; A=anionic ligand; M=alkali metal) involving reduction of Sc(NR 2 ) 3 with K in the presence of 2.2.2-cryptand (crypt) and 18-crown-6 (18-c-6) and with Cs in the presence of crypt. Dark maroon [K(crypt)] + , [K(18-c-6)] + , and [Cs(crypt)] + salts of the [Sc(NR 2 ) 3 ] - anion are formed, respectively. The formation of this oxidation state of Sc is also indicated by the eight-line EPR spectra arising from the I=7/2 45 Sc nucleus. The Sc(NR 2 ) 3 reduction differs from Ln(NR 2 ) 3 reactions (Ln=Y and lanthanides) in that it occurs under N 2 without formation of isolable reduced dinitrogen species. [K(18-c-6)][Sc(NR 2 ) 3 ] reacts with CO 2 to produce an oxalate complex, {K 2 (18-c-6) 3 }{[(R 2 N) 3 Sc] 2 (μ-C 2 O 4 -κ 1 O:κ 1 O'')}, and a CO 2 - radical anion complex, [(R 2 N) 3 Sc(μ-OCO-κ 1 O:κ 1 O')K(18-c-6)] n . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Twinned low-temperature structures of tris(ethylenediamine)zinc(II) sulfate and tris(ethylenediamine)copper(II) sulfate.

PubMed

Lutz, Martin

2010-11-01

Tris(ethylenediamine)zinc(II) sulfate, [Zn(C(2)H(8)N(2))(3)]SO(4), (I), undergoes a reversible solid-solid phase transition during cooling, accompanied by a lowering of the symmetry from high-trigonal P31c to low-trigonal P3 and by merohedral twinning. The molecular symmetries of the cation and anion change from 32 (D(3)) to 3 (C(3)). This lower symmetry allows an ordered sulfate anion and generates in the complex cation two independent N atoms with significantly different geometries. The twinning is the same as in the corresponding Ni complex [Jameson et al. (1982). Acta Cryst. B38, 3016-3020]. The low-temperature phase of tris(ethylenediamine)copper(II) sulfate, [Cu(C(2)H(8)N(2))(3)]SO(4), (II), has only triclinic symmetry and the unit-cell volume is doubled with respect to the room-temperature structure in P31c. (II) was refined as a nonmerohedral twin with five twin domains. The asymmetric unit contains two independent formula units, and all cations and anions are located on general positions with 1 (C(1)) symmetry. Both molecules of the Cu complex are in elongated octahedral geometries because of the Jahn-Teller effect. This is in contrast to an earlier publication, which describes the complex as a compressed octahedron [Bertini et al. (1979). J. Chem. Soc. Dalton Trans. pp. 1409-1414].

Controlled Neutralization of Anions in Cryogenic Matrices by Near-Threshold Photodetachment

NASA Astrophysics Data System (ADS)

Ludwig, Ryan M.; Moore, David T.

2014-06-01

Using matrix isolation FTIR, we have observed the formation of anionic copper carbonyl complexes [Cu(CO)n]- (n=1-3) following co-deposition of Cu- and counter-cations (Ar+ or Kr+) into argon matrices doped with CO. The infrared bands have been previously assigned in argon matrix studies employing laser ablation, however they were quite weak compared to the bands for the corresponding neutral species. In the current study, when the deposition is carried out in fully darkened conditions at 10 K with high CO concentrations (1-2%), only the bands for the anionic complexes are observed initially via FTIR. However, upon mild irradiation with broadband visible light, the anionic bands are rapidly depleted, with concomitant appearance of bands corresponding to neutral copper carbonyl complexes. This photo-triggered neutralization is attributed to photodetachment of electrons from the anions, which then "flow" through the solid argon matrix to recombine in the matrix with non-adjacent trapping sites. This mechanism is supported by the appearance of a new band near 1515 wn, assigned to the (CO)2- species in argon. The wavelength dependence of the photodetachment will be discussed in detail, although preliminary indications are that the thresholds for the copper carbonyls, which are normally in the infrared, are shifted into the visible region of the spectrum in argon matrices. This likely occurs because the conduction band of solid argon is known to lie about 1 eV above the vacuum level, and thus the electron must have at least this much energy in order to escape into the matrix and find a trapping site. Funding support from NSF CAREER Award CHE-0955637 is gratefully acknowledged Ryan M. Ludwig and David T. Moore, J. Chem. Phys. 139, 244202 (2013) Zhou, M.; Andrews, L., J. Chem. Phys. 111, 4548 (1999). Thompson, W.E.; Jacox, M.E.; J. Chem. Phys. 91, 735 (1991). Stanzel, J. et al.; Collect. Czech. Chem. Comm. 72, 1 (2007). Harbich, W. et al.; Phys. Rev. B. 76, 104306 (2007).

Functionalization of Bambusurils by thiol-ene click reaction and new, facile method for the preparation of anion-free Bambus[6]urils.

PubMed

Heck, Marie-Pierre; Azazna, Djamille; Lafosse, Marine; Wang, Jialan; Rivollier, Julie; Ben Cheikh, Imen; Meyer, Michel; Thuéry, Pierre; Dognon, Jean-Pierre; Huber, Gaspard

2018-05-03

New sulfide-functionalized bambus[4]urils ((RS)8BU[4]) and bambus[6]urils ((RS)12BU[6]) have been synthesized through thiol-ene click coupling reactions (TEC) of allylbambus[n]urils. Synthesis of BU[6] derivatives always requires the use of a template anion (iodide, chloride or bromide) which is enclosed in the cavity of BU[6]. We show that this anion influences the reactivity of bambus[6]urils. An encapsulated iodide makes allyl functions of allyl12BU[6] less reactive towards TEC and hydrogenation reactions in comparison to the corresponding chloride or bromide inclusion complexes. This is critical for the chemical reactivity of BU[6] and even more to determine their anion-binding properties. We report a new, facile and fast method using AgSbF6 to prepare anion-free BU[6]. NMR methods were used to estimate association constants of these new empty BU[6] with different anions. Quantum chemistry calculations were employed to rationalize the observed results. These new functionalized bambusuril scaffolds in alternate conformation could find applications as multivalent binders. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamics of Pseudomonas aeruginosa association with anionic hydrogel surfaces in the presence of aqueous divalent-cation salts

PubMed Central

Tran, Victoria B.; Sung, Ye Suel; Fleiszig, Suzanne M.J.; Evans, David J.; Radke, C.J.

2013-01-01

Binding of bacteria to solid surfaces is complex with many aspects incompletely understood. We investigate Pseudomonas aeruginosa uptake kinetics onto hydrogel surfaces representative of soft-contact lenses made of nonionic poly(2-hydroxyethylmethacrylate) (p-HEMA), anionic poly(methacrylic acid) (p-MAA), and anionic poly(acrylic acid) (p-AA). Using a parallel-plate flow cell under phase-contrast microscopy, we document a kinetic “burst” at the anionic hydrogel surface: dilute aqueous P. aeruginosa first rapidly accumulates and then rapidly depletes. Upon continuing flow, divalent cations in the suspending solution sorb into the hydrogel network causing the previously surface-accumulated bacteria to desorb. The number of bacteria eventually bound to the surface is low compared to the nonionic p-HEMA hydrogel. We propose that the kinetic burst is due to reversible divalent-cation bridging between the anionic bacteria and the negatively charged hydrogel surface. The number of surface bridging sites diminishes as divalent cations impregnate into and collapse the gel. P. aeruginosa association with the surface then falls. Low eventual binding of P. aeruginosa to the anionic hydrogel is ascribed to increased surface hydrophilicity compared to the counterpart nonionic p-HEMA hydrogel. PMID:21723562

Escape of anions from geminate recombination in THF due to charge delocalization

DOE PAGES

Chen, Hung -Cheng; Cook, Andrew R.; Asaoka, Sadayuki; ...

2017-11-24

Geminate recombination of 24 radical anions (M˙ –) with solvated protons (RH 2 +) was studied in tetrahydrofuran (THF) with pulse radiolysis. The recombination has two steps: (1) diffusion of M˙ – and RH 2 + together to form intimate (contact and solvent separated) ion pairs, driven by Coulomb attraction; (2) annihilation of anions due to proton transfer (PT) from RH 2 + to M˙ –. The non-exponential time-dependence of the geminate diffusion was determined. For all molecules protonated on O or N atoms the subsequent PT step is too fast (<0.2 ns) to measure, except for the anion ofmore » TCNE which did not undergo proton transfer. PT to C atoms was as slow as 70 ns and was always slow enough to be observable. A possible effect of charge delocalization on the PT rates could not be clearly separated from other factors. For 21 of the 24 molecules studied here, a free ion yield (71.6 ± 6.2 nmol J –1) comprising ~29% of the total, was formed. This yield of “Type I” free ions is independent of the PT rate because it arises entirely by escape from the initial distribution of ion pair distances without forming intimate ion pairs. Furthermore, three anions of oligo(9,9-dihexyl)fluorenes, F n˙ – (n = 2–4) were able to escape from intimate ion-pairs to form additional yields of “Type II” free ions with escape rate constants near 3 × 10 6 s –1. These experiments find no evidence for an inverted region for proton transfer.« less

Tuning of protein-surfactant interaction to modify the resultant structure.

PubMed

Mehan, Sumit; Aswal, Vinod K; Kohlbrecher, Joachim

2015-09-01

Small-angle neutron scattering and dynamic light scattering studies have been carried out to examine the interaction of bovine serum albumin (BSA) protein with different surfactants under varying solution conditions. We show that the interaction of anionic BSA protein (pH7) with surfactant and the resultant structure are strongly modified by the charge head group of the surfactant, ionic strength of the solution, and mixed surfactants. The protein-surfactant interaction is maximum when two components are oppositely charged, followed by components being similarly charged through the site-specific binding, and no interaction in the case of a nonionic surfactant. This interaction of protein with ionic surfactants is characterized by the fractal structure representing a bead-necklace structure of micellelike clusters adsorbed along the unfolded protein chain. The interaction is enhanced with ionic strength only in the case of site-specific binding of an anionic surfactant with an anionic protein, whereas it is almost unchanged for other complexes of cationic and nonionic surfactants with anionic proteins. Interestingly, the interaction of BSA protein with ionic surfactants is significantly suppressed in the presence of nonionic surfactant. These results with mixed surfactants thus can be used to fold back the unfolded protein as well as to prevent surfactant-induced protein unfolding. For different solution conditions, the results are interpreted in terms of a change in fractal dimension, the overall size of the protein-surfactant complex, and the number of micelles attached to the protein. The interplay of electrostatic and hydrophobic interactions is found to govern the resultant structure of complexes.

Tuning of protein-surfactant interaction to modify the resultant structure

NASA Astrophysics Data System (ADS)

Mehan, Sumit; Aswal, Vinod K.; Kohlbrecher, Joachim

2015-09-01

Small-angle neutron scattering and dynamic light scattering studies have been carried out to examine the interaction of bovine serum albumin (BSA) protein with different surfactants under varying solution conditions. We show that the interaction of anionic BSA protein (p H 7 ) with surfactant and the resultant structure are strongly modified by the charge head group of the surfactant, ionic strength of the solution, and mixed surfactants. The protein-surfactant interaction is maximum when two components are oppositely charged, followed by components being similarly charged through the site-specific binding, and no interaction in the case of a nonionic surfactant. This interaction of protein with ionic surfactants is characterized by the fractal structure representing a bead-necklace structure of micellelike clusters adsorbed along the unfolded protein chain. The interaction is enhanced with ionic strength only in the case of site-specific binding of an anionic surfactant with an anionic protein, whereas it is almost unchanged for other complexes of cationic and nonionic surfactants with anionic proteins. Interestingly, the interaction of BSA protein with ionic surfactants is significantly suppressed in the presence of nonionic surfactant. These results with mixed surfactants thus can be used to fold back the unfolded protein as well as to prevent surfactant-induced protein unfolding. For different solution conditions, the results are interpreted in terms of a change in fractal dimension, the overall size of the protein-surfactant complex, and the number of micelles attached to the protein. The interplay of electrostatic and hydrophobic interactions is found to govern the resultant structure of complexes.

Photoinduced electron transfer from rylenediimide radical anions and dianions to Re(bpy)(CO) 3 using red and near-infrared light

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

La Porte, Nathan T.; Martinez, Jose F.; Hedström, Svante

A major goal of artificial photosynthesis research is photosensitizing highly reducing metal centers using as much as possible of the solar spectrum reaching Earth's surface. The radical anions and dianions of rylenediimide (RDI) dyes, which absorb at wavelengths as long as 950 nm, are powerful photoreductants with excited state oxidation potentials that rival or exceed those of organometallic chromophores. These dyes have been previously incorporated into all-organic donor–acceptor systems, but have not yet been shown to reduce organometallic centers. This study describes a set of dyads in which perylenediimide (PDI) or naphthalenediimide (NDI) chromophores are attached to Re(bpy)(CO) 3 throughmore » either the bipyridine ligand or more directly to the Re center via a pyridine ligand. The chromophores are reduced with a mild reducing agent, after which excitation with long-wavelength red or near-infrared light leads to reduction of the Re complex. The kinetics of electron transfer from the photoexcited anions to the Re complex are monitored using transient visible/near-IR and mid-IR spectroscopy, complemented by theoretical spectroscopic assignments. The photo-driven charge shift from the reduced PDI or NDI to the complex occurs in picoseconds regardless of whether PDI or NDI is attached to the bipyridine or to the Re center, but back electron transfer is found to be three orders of magnitude slower with the chromophore attached to the Re center. These results will inform the design of future catalytic systems that incorporate RDI anions as chromophores.« less

Photoinduced electron transfer from rylenediimide radical anions and dianions to Re(bpy)(CO) 3 using red and near-infrared light

DOE PAGES

La Porte, Nathan T.; Martinez, Jose F.; Hedström, Svante; ...

2017-02-28

A major goal of artificial photosynthesis research is photosensitizing highly reducing metal centers using as much as possible of the solar spectrum reaching Earth's surface. The radical anions and dianions of rylenediimide (RDI) dyes, which absorb at wavelengths as long as 950 nm, are powerful photoreductants with excited state oxidation potentials that rival or exceed those of organometallic chromophores. These dyes have been previously incorporated into all-organic donor–acceptor systems, but have not yet been shown to reduce organometallic centers. This study describes a set of dyads in which perylenediimide (PDI) or naphthalenediimide (NDI) chromophores are attached to Re(bpy)(CO) 3 throughmore » either the bipyridine ligand or more directly to the Re center via a pyridine ligand. The chromophores are reduced with a mild reducing agent, after which excitation with long-wavelength red or near-infrared light leads to reduction of the Re complex. The kinetics of electron transfer from the photoexcited anions to the Re complex are monitored using transient visible/near-IR and mid-IR spectroscopy, complemented by theoretical spectroscopic assignments. The photo-driven charge shift from the reduced PDI or NDI to the complex occurs in picoseconds regardless of whether PDI or NDI is attached to the bipyridine or to the Re center, but back electron transfer is found to be three orders of magnitude slower with the chromophore attached to the Re center. These results will inform the design of future catalytic systems that incorporate RDI anions as chromophores.« less

A Web-Based Multidrug-Resistant Organisms Surveillance and Outbreak Detection System with Rule-Based Classification and Clustering

PubMed Central

Tseng, Yi-Ju; Wu, Jung-Hsuan; Ping, Xiao-Ou; Lin, Hui-Chi; Chen, Ying-Yu; Shang, Rung-Ji; Chen, Ming-Yuan; Lai, Feipei

2012-01-01

Background The emergence and spread of multidrug-resistant organisms (MDROs) are causing a global crisis. Combating antimicrobial resistance requires prevention of transmission of resistant organisms and improved use of antimicrobials. Objectives To develop a Web-based information system for automatic integration, analysis, and interpretation of the antimicrobial susceptibility of all clinical isolates that incorporates rule-based classification and cluster analysis of MDROs and implements control chart analysis to facilitate outbreak detection. Methods Electronic microbiological data from a 2200-bed teaching hospital in Taiwan were classified according to predefined criteria of MDROs. The numbers of organisms, patients, and incident patients in each MDRO pattern were presented graphically to describe spatial and time information in a Web-based user interface. Hierarchical clustering with 7 upper control limits (UCL) was used to detect suspicious outbreaks. The system’s performance in outbreak detection was evaluated based on vancomycin-resistant enterococcal outbreaks determined by a hospital-wide prospective active surveillance database compiled by infection control personnel. Results The optimal UCL for MDRO outbreak detection was the upper 90% confidence interval (CI) using germ criterion with clustering (area under ROC curve (AUC) 0.93, 95% CI 0.91 to 0.95), upper 85% CI using patient criterion (AUC 0.87, 95% CI 0.80 to 0.93), and one standard deviation using incident patient criterion (AUC 0.84, 95% CI 0.75 to 0.92). The performance indicators of each UCL were statistically significantly higher with clustering than those without clustering in germ criterion (P < .001), patient criterion (P = .04), and incident patient criterion (P < .001). Conclusion This system automatically identifies MDROs and accurately detects suspicious outbreaks of MDROs based on the antimicrobial susceptibility of all clinical isolates. PMID:23195868

Evidence-based hamstring injury prevention is not adopted by the majority of Champions League or Norwegian Premier League football teams: the Nordic Hamstring survey.

PubMed

Bahr, Roald; Thorborg, Kristian; Ekstrand, Jan

2015-11-01

The Nordic hamstring (NH) exercise programme was introduced in 2001 and has been shown to reduce the risk of acute hamstring injuries in football by at least 50%. Despite this, the rate of hamstring injuries has not decreased over the past decade in male elite football. To examine the implementation of the NH exercise programme at the highest level of male football in Europe, the UEFA Champions League (UCL), and to compare this to the Norwegian Premier League, Tippeligaen, where the pioneer research on the NH programme was conducted. Retrospective survey. 50 professional football teams, 32 from the UCL and 18 from Tippeligaen. A questionnaire, based on the Reach, Efficacy, Adoption, Implementation and Maintenance framework, addressing key issues related to the implementation of the NH programme during three seasons from 2012 through 2014, was distributed to team medical staff using electronic survey software. The response rate was 100%. Of the 150 club-seasons covered by the study, the NH programme was completed in full in 16 (10.7%) and in part in an additional 9 (6%) seasons. Consequently, 125 (83.3%) club-seasons were classified as non-compliant. There was no difference in compliance between the UCL and Tippeligaen in any season (χ(2): 0.41 to 0.52). Adoption and implementation of the NH exercise programme at the highest levels of male football in Europe is low; too low to expect any overall effect on acute hamstring injury rates. 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/

Estimation of process capability indices from the results of limit gauge inspection of dimensional parameters in machining industry

NASA Astrophysics Data System (ADS)

Masterenko, Dmitry A.; Metel, Alexander S.

2018-03-01

The process capability indices Cp, Cpk are widely used in the modern quality management as statistical measures of the ability of a process to produce output X within specification limits. The customer's requirement to ensure Cp ≥ 1.33 is often applied in contracts. Capability indices estimates may be calculated with the estimates of the mean µ and the variability 6σ, and for it, the quality characteristic in a sample of pieces should be measured. It requires, in turn, using advanced measuring devices and well-qualified staff. From the other hand, quality inspection by attributes, fulfilled with limit gauges (go/no-go) is much simpler and has a higher performance, but it does not give the numerical values of the quality characteristic. The described method allows estimating the mean and the variability of the process on the basis of the results of limit gauge inspection with certain lower limit LCL and upper limit UCL, which separates the pieces into three groups: where X < LCL, number of pieces is n1, where LCL ≤ X < UCL, n2 pieces, and where X ≥ UCL, n3 pieces. So-called Pittman-type estimates, developed by the author, are functions of n1, n2, n3 and allow calculation of the estimated µ and σ. Thus, Cp and Cpk also may be estimated without precise measurements. The estimates can be used in quality inspection of lots of pieces as well as in monitoring and control of the manufacturing process. It is very important for improving quality of articles in machining industry through their tolerance.

Control of C-H Bond Activation by Mo-Oxo Complexes: pKa or Bond Dissociation Free Energy (BDFE)?

PubMed

Nazemi, Azadeh; Cundari, Thomas R

2017-10-16

A density functional theory (DFT) study (BMK/6-31+G(d)) was initiated to investigate the activation of benzylic carbon-hydrogen bonds by a molybdenum-oxo complex with a potentially redox noninnocent supporting ligand-a simple mimic of the active species of the enzyme ethylbenzene dehydrogenase (EBDH)-through deprotonation (C-H bond heterolysis) or hydrogen atom abstraction (C-H bond homolysis) routes. Activation free-energy barriers for neutral and anionic Mo-oxo complexes were high, but lower for anionic complexes than neutral complexes. Interesting trends as a function of substituents were observed that indicated significant H δ+ character in the transition states (TS), which was further supported by the preference for [2 + 2] addition over HAA for most complexes. Hence, it was hypothesized that C-H activation by these EBDH mimics is controlled more by the pK a than by the bond dissociation free energy of the C-H bond being activated. Therefore, the results suggest promising pathways for designing more efficient and selective catalysts for hydrocarbon oxidation based on EBDH active-site mimics.

Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example

DOE PAGES

Jin, Geng Bang; Lin, Jian; Estes, Shanna L.; ...

2017-11-17

Here, the influence of countercations (A n+) in directing the composition of monomeric metal–ligand (ML) complexes that precipitate from solution are often overlooked despite the wide usage of A n+ in materials synthesis. Herein, we describe a correlation between the composition of ML complexes and A + hydration enthalpies found for two related series of thorium (Th)–nitrate molecular compounds obtained by evaporating acidic aqueous Th–nitrate solutions in the presence of A + counterions. Analyses of their chemical composition and solid-state structures demonstrate that A + not only affects the overall solid-state packing of the Th–nitrato complexes but also influences themore » composition of the Th–nitrato monomeric anions themselves. Trends in composition and structure are found to correlate with A + hydration enthalpies, such that the A + with smaller hydration enthalpies associate with less hydrated and more anionic Th–nitrato complexes. This perspective, broader than the general assumption of size and charge as the dominant influence of A n+, opens a new avenue for the design and synthesis of targeted metal–ligand complexes.« less

Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example

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

Jin, Geng Bang; Lin, Jian; Estes, Shanna L.

Here, the influence of countercations (A n+) in directing the composition of monomeric metal–ligand (ML) complexes that precipitate from solution are often overlooked despite the wide usage of A n+ in materials synthesis. Herein, we describe a correlation between the composition of ML complexes and A + hydration enthalpies found for two related series of thorium (Th)–nitrate molecular compounds obtained by evaporating acidic aqueous Th–nitrate solutions in the presence of A + counterions. Analyses of their chemical composition and solid-state structures demonstrate that A + not only affects the overall solid-state packing of the Th–nitrato complexes but also influences themore » composition of the Th–nitrato monomeric anions themselves. Trends in composition and structure are found to correlate with A + hydration enthalpies, such that the A + with smaller hydration enthalpies associate with less hydrated and more anionic Th–nitrato complexes. This perspective, broader than the general assumption of size and charge as the dominant influence of A n+, opens a new avenue for the design and synthesis of targeted metal–ligand complexes.« less

Cytotoxicity of Triorganophosphinegold(I) Complexes of Thiobenzoate

PubMed Central

Vincent, Beverly R.; Clarke, David J.; Smyth, Douglas R.; de Vos, Dick

2001-01-01

The preparation and characterization of two triorganophosphinegold(I) complexes containing the anion derived from thiobenzoic acid are described. The cytotoxicity of these complexes has been investigated along with that of triphenylphosphinegold(I) mercaptopurinate, a known anti-tumor compound, against a variety of human cell lines. The complexes showed moderate to high cytotoxicity (ID50 250 – 2500 ng/ml). PMID:18475979

Autophagic degradation of the androgen receptor mediated by increased phosphorylation of p62 suppresses apoptosis in hypoxia.

PubMed

Mitani, Takakazu; Minami, Masato; Harada, Naoki; Ashida, Hitoshi; Yamaji, Ryoichi

2015-10-01

Prostate cancer grows under hypoxic conditions. Hypoxia decreases androgen receptor (AR) protein levels. However, the molecular mechanism remains unclear. Here, we report that p62-mediated autophagy degrades AR protein and suppresses apoptosis in prostate cancer LNCaP cells in hypoxia. In LNCaP cells, hypoxia decreased AR at the protein level, but not at the mRNA level. Hypoxia-induced AR degradation was inhibited not only by knockdown of LC3, a key component of the autophagy machinery, but also by knockdown of p62. Depletion of p62 enhanced hypoxia-induced poly(ADP-ribose) polymerase cleavage and caspase-3 cleavage, markers of apoptosis, whereas simultaneous knockdown of p62 and AR suppressed hypoxia-induced apoptosis. Hypoxia increased the formation of a cytosolic p62-AR complex and enhanced sequestration of AR from the nucleus. Formation of this complex was promoted by the increased phosphorylation of serine 403 in the ubiquitin-associated domain of p62 during hypoxia. An antioxidant and an AMP-activated protein kinase (AMPK) inhibitor reduced hypoxia-induced p62 phosphorylation at serine 403 and suppressed hypoxia-induced complex formation between AR and p62. These results demonstrate that hypoxia enhances the complex formation between p62 and AR by promoting phosphorylation of p62 at serine 403, probably through activating AMPK, and that p62-mediated autophagy degrades AR protein for cell survival in hypoxia. Copyright © 2015 Elsevier Inc. All rights reserved.

Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph)

DOE PAGES

Pagano, Justin K.; Erickson, Karla A.; Scott, Brian L.; ...

2016-10-22

A new uranium metallacyclocumulene, (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph), was synthesized by both reaction of (C 5Me 5) 2UCl 2 with 1,4-diphenylbutadiyne in the presence of KC 8 and by ligand exchange between (C 5Me 5) 2U(η 2-Me 3SiC 2SiMe 3) and 1,4-diphenylbutadiyne. Lastly, full characterization of (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph) is reported, including the solid-state structure. (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph) displays an unusually detailed UV–visible spectrum, which is rare for uranium(IV) metallocene complexes.

Synthesis and characterization of a new and electronically unusual uranium metallacyclocumulene, (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph)

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

Pagano, Justin K.; Erickson, Karla A.; Scott, Brian L.

A new uranium metallacyclocumulene, (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph), was synthesized by both reaction of (C 5Me 5) 2UCl 2 with 1,4-diphenylbutadiyne in the presence of KC 8 and by ligand exchange between (C 5Me 5) 2U(η 2-Me 3SiC 2SiMe 3) and 1,4-diphenylbutadiyne. Lastly, full characterization of (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph) is reported, including the solid-state structure. (C 5Me 5) 2U(η 4-1,2,3,4-PhC 4Ph) displays an unusually detailed UV–visible spectrum, which is rare for uranium(IV) metallocene complexes.

Yb3+ can be much better than Dy3+: SMM properties and controllable self-assembly of novel lanthanide 3,5-dinitrobenzoate-acetylacetonate complexes.

PubMed

Gavrikov, Andrey V; Efimov, Nikolay N; Ilyukhin, Andrey B; Dobrokhotova, Zhanna V; Novotortsev, Vladimir M

2018-05-01

The first representatives of the binuclear lanthanide 3,5-dinitrobenzoate-acetylacetonate complexes, namely isostructural compounds [Ln(dnbz)(acac)2(H2O)(EtOH)]2 (Ln = Eu (1), Gd (2), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), and Yb (8); dnbz - 3,5-dinitrobenzoate anion; acac - acetylacetonate (pentane-2,4-dionate) anion) were prepared and characterized. The SMM behavior of the Yb compound 8 was shown to be surprisingly less sensitive to the composition of the Yb3+ coordination environment in comparison with that of the Dy derivative. For Yb compound 8, the anisotropy barrier is Δeff/kB = 26 K under the dc field of 2000 Oe. This value is the highest one currently known for binuclear Yb complexes.

The selectivity of water-based pyrophosphate recognition is tuned by metal substitution in dimetallic receptors.

PubMed

Svane, Simon; Kjeldsen, Frank; McKee, Vickie; McKenzie, Christine J

2015-07-14

The three dimetallic compounds [Ga2(bpbp)(OH)2(H2O)2](ClO4)3, [In2(bpbp)(CH3CO2)2](ClO4)3 and [Zn2(bpbp)(HCO2)2](ClO4) (bpbp(-) = 2,6-bis((N,N'-bis(2-picolyl)amino)methyl)-4-tertbutylphenolate) were evaluated as stable solid state precursors for reactive solution state receptors to use for the recognition of the biologically important anion pyrophosphate in water at neutral pH. Indicator displacement assays using in situ generated complex-pyrocatechol violet adducts, {M2(bpbp)(HxPV)}(n+) M = Ga(3+), In(3+), Zn(2+), were tested for selectivity in their reactions with a series of common anions: pyrophosphate, phosphate, ATP, arsenate, nitrate, perchlorate, chloride, sulfate, formate, carbonate and acetate. The receptor employing Ga(3+) showed a slow but visually detectable response (blue to yellow) in the presence of one equivalent of pyrophosphate but no response to any other anion, even when they were present in much higher concentrations. The systems based on In(3+) or Zn(2+) show less selectivity in accord with visibly discernible responses to several of the anions. These results demonstrate a facile method for increasing anion selectivity without modification of an organic dinucleating ligand scaffold. The comfortable supramolecular recognition of pyrophosphate by the dimetallic complexes is demonstrated by the single crystal X-ray structure of [Ga2(bpbp)(HP2O7)](ClO4)2 in which the pyrophosphate is coordinated to the two gallium ions via four of its oxygen atoms.

Localized rosuvastatin via implantable bioerodible sponge and its potential role in augmenting bone healing and regeneration.

PubMed

Ibrahim, Howida Kamal; Fahmy, Rania Hassan

2016-11-01

Statins proved potential bone healing properties. Rosuvastatin is a synthetic, hydrophilic, potent and highly efficacious statin. In the current work, an attempt was investigated to develop, evaluate various bioerodible composite sponges enclosing rosuvastatin and explore their potential in augmenting bone healing and regeneration. Twelve lyophilized sponge formulae were prepared adapting a 4 1 .3 1 full factorial design. Xanthan gum, polycarbophil, Carbopol® and sodium alginate were investigated as anionic polymers, each at three chitosan:anionic polymer ratios (1:3, 1:1, 3:1). The formula of choice was implanted in fractured rat femora. Visual and microscopic examination showed flexible homogenous porous structures with considerable bending ability. Polyelectrolyte complex formation was proved by DSC and FT-IR for all chitosan/anionic combinations except with xanthan gum where chitosan probably bound to the drug rather than xanthan gum. Statistical analysis proved that anionic polymer type and chitosan: polymer ratio, as well as, their interactions, exhibited significant effects on the release parameters at p ≤ 0.05. The optimum chitosan/anionic polymer complexation ratios were 3:1 for polycarbophil and 1:1 for Carbopol and alginate. The release at these ratios followed Fiction diffusion while other ratios had anomalous diffusion. Imwitor® 900K and HPMC K100M were added as release retarardants for further release optimization. The formula of choice was implanted in fractured rat femora. Histopathological examination revealed advanced stages of healing in treated femora compared to control ones. Biodegradable sponges for local rosuvastatin delivery proved significantly enhanced wound healing and regeneration properties to fractured bones.

Synergistic effect of dicarbollide anions in liquid-liquid extraction: a molecular dynamics study at the octanol-water interface.

PubMed

Chevrot, G; Schurhammer, R; Wipff, G

2007-04-28

We report a molecular dynamics study of chlorinated cobalt bis(dicarbollide) anions [(B(9)C(2)H(8)Cl(3))(2)Co](-)"CCD(-)" in octanol and at the octanol-water interface, with the main aim to understand why these hydrophobic species act as strong synergists in assisted liquid-liquid cation extraction. Neat octanol is quite heterogeneous and is found to display dual solvation properties, allowing to well solubilize CCD(-), Cs(+) salts in the form of diluted pairs or oligomers, without displaying aggregation. At the aqueous interface, octanol behaves as an amphiphile, forming either monolayers or bilayers, depending on the initial state and confinement conditions. In biphasic octanol-water systems, CCD(-) anions are found to mainly partition to the organic phase, thus attracting Cs(+) or even more hydrophilic counterions like Eu(3+) into that phase. The remaining CCD(-) anions adsorb at the interface, but are less surface active than at the chloroform interface. Finally, we compare the interfacial behavior of the Eu(BTP)(3)(3+) complex in the absence and in the presence of CCD(-) anions and extractant molecules. It is found that when the CCD(-)'s are concentrated enough, the complex is extracted to the octanol phase. Otherwise, it is trapped at the interface, attracted by water. These results are compared to those obtained with chloroform as organic phase and discussed in the context of synergistic effect of CCD(-) in liquid-liquid extraction, pointing to the importance of dual solvation properties of octanol and of the hydrophobic character of CCD(-) for synergistic extraction of cations.

Theory after experiment on sensing mechanism of a newly developed sensor molecule: Converging or diverging?

NASA Astrophysics Data System (ADS)

Paul, Suvendu; Karar, Monaj; Das, Biswajit; Mallick, Arabinda; Majumdar, Tapas

2017-12-01

Fluoride ion sensing mechanism of 3,3‧-bis(indolyl)-4-chlorophenylmethane has been analyzed with density functional and time-dependent density functional theories. Extensive theoretical calculations on molecular geometry & energy, charge distribution, orbital energies & electronic distribution, minima on potential energy surface confirmed strong hydrogen bonded sensor-anion complex with incomplete proton transfer in S0. In S1, strong hydrogen bonding extended towards complete ESDPT. The distinct and single minima on the PES of the sensor-anion complex for both ground and first singlet excited states confirmed the concerted proton transfer mechanism. Present study well reproduced the experimental spectroscopic data and provided ESDPT as probable fluoride sensing mechanism.

Preparation and characterization of ligand types intermediate in the metal catalyzed conversion of coal to methane, methanol, and higher alkanes and alcohols. Second technical progress report, September 1, 1979-February 28, 1981

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

Gladysz, J. A.

1980-11-10

Mechanistic studies of anionic formyl complexes were made. The rate of decomposition of the formyl (CO)/sub 4/Mn(COC/sub 6/H/sub 5/)(CHO)/sup -/ anion as a function of counter-ion and trialkylborane present was examined. The deuterated formyl (CO)/sub 4/Mn(COC/sub 6/H/sub 5/)(CDO)/sup -/ was prepared and its decomposition was monitored by H/sup 2/ NMR. The data obtained indicate that the formyl decomposes by a disproportionative pathway not by initial CO loss, as commonly noted for formyl complexes.

Radiation creation of cation defects in alkali halide crystals: Review and today's concept (Review Article)

NASA Astrophysics Data System (ADS)

Lushchik, A.; Lushchik, Ch.; Vasil'chenko, E.; Popov, A. I.

2018-04-01

Irradiation of alkali halide crystals creates pairs of Frenkel defects both in anion and cation sublattices. However, the particular nonimpact creation mechanisms (related to the decay of different electronic excitations) of cation Frenkel pairs are still unclear. At helium temperatures, there is yet no direct evidences of the creation of stable (long-lived) elemental cation defects. On the other hand, a number of complex structural defects containing cation vacancies and/or interstitials, were detected after irradiation of alkali halides at higher temperatures. Besides already proved mechanism related to the association of H and VK centers into trihalide molecules, the following possibilities of cation interstitial-vacancy pair creation are analyzed as well: (i) a direct decay of cation or anion excitons, (ii) the transformation of anion Frenkel pairs, formed at the decay of anion excitons or e-h recombination, into cation ones.

Slow Photoelectron Velocity-Map Imaging of Cryogenically Cooled Anions

NASA Astrophysics Data System (ADS)

Weichman, Marissa L.; Neumark, Daniel M.

2018-04-01

Slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled anions (cryo-SEVI) is a powerful technique for elucidating the vibrational and electronic structure of neutral radicals, clusters, and reaction transition states. SEVI is a high-resolution variant of anion photoelectron spectroscopy based on photoelectron imaging that yields spectra with energy resolution as high as 1-2 cm‑1. The preparation of cryogenically cold anions largely eliminates hot bands and dramatically narrows the rotational envelopes of spectral features, enabling the acquisition of well-resolved photoelectron spectra for complex and spectroscopically challenging species. We review the basis and history of the SEVI method, including recent experimental developments that have improved its resolution and versatility. We then survey recent SEVI studies to demonstrate the utility of this technique in the spectroscopy of aromatic radicals, metal and metal oxide clusters, nonadiabatic interactions between excited states of small molecules, and transition states of benchmark bimolecular reactions.

Photoelectron spectroscopic study of the anionic transition metalorganic complexes [Fe(1,2)(COT)](-) and [Co(COT)](-).

PubMed

Li, Xiang; Eustis, Soren N; Bowen, Kit H; Kandalam, Anil

2008-09-28

The gas-phase, iron and cobalt cyclooctatetraene cluster anions, [Fe(1,2)(COT)](-) and [Co(COT)](-), were generated using a laser vaporization source and studied using mass spectrometry and anion photoelectron spectroscopy. Density functional theory was employed to compute the structures and spin multiplicities of these cluster anions as well as those of their corresponding neutrals. Both experimental and theoretically predicted electron affinities and photodetachment transition energies are in good agreement, authenticating the structures and spin multiplicities predicted by theory. The implied spin magnetic moments of these systems suggest that [Fe(COT)], [Fe(2)(COT)], and [Co(COT)] retain the magnetic moments of the Fe atom, the Fe(2) dimer, and the Co atom, respectively. Thus, the interaction of these transition metal, atomic and dimeric moieties with a COT molecule does not quench their magnetic moments, leading to the possibility that these combinations may be useful in forming novel magnetic materials.

Anion Binding of One-, Two-, and Three-Armed Thiourea Receptors Examined via Photoelectron Spectroscopy and Quantum Computations.

PubMed

Beletskiy, Evgeny V; Wang, Xue-Bin; Kass, Steven Robert

2016-10-05

A benzene ring substituted with 1-3 thiourea containing arms (1-3) were examined by photoelectron spectroscopy and density functional theory computations. Their conjugate bases and chloride, acetate and dihydrogen phosphate anion clusters are reported. The resulting vertical and adiabatic detachment energies span from 3.93 - 5.82 eV (VDE) and 3.65 - 5.10 (ADE) for the deprotonated species and 4.88 - 5.97 eV (VDE) and 4.45 - 5.60 eV (ADE) for the anion complexes. These results reveal the stabilizing effects of multiple hydrogen bonds and anionic host-guest interactions in the gas phase. Previously measured equilibrium binding constants in aqueous dimethyl sulfoxide for all three thioureas are compared to the present results and cooperative binding is uniformly observed in the gas phase but only for one case (i.e., 3 • H2PO4-) in solution.

Natural lipid extracts and biomembrane-mimicking lipid compositions are disposed to form nonlamellar phases, and they release DNA from lipoplexes most efficiently

PubMed Central

Koynova, Rumiana; MacDonald, Robert C.

2007-01-01

A viewpoint now emerging is that a critical factor in lipid-mediated transfection (lipofection) is the structural evolution of lipoplexes upon interacting and mixing with cellular lipids. Here we report our finding that lipid mixtures mimicking biomembrane lipid compositions are superior to pure anionic liposomes in their ability to release DNA from lipoplexes (cationic lipid/DNA complexes), even though they have a much lower negative charge density (and thus lower capacity to neutralize the positive charge of the lipoplex lipids). Flow fluorometry revealed that the portion of DNA released after a 30 min incubation of the cationic O-ethylphosphatidylcholine lipoplexes with the anionic phosphatidylserine or phosphatidylglycerol was 19% and 37%, respectively, whereas a mixture mimicking biomembranes (MM: phosphatidylcholine/phosphatidylethanolamine/ phosphatidylserine/cholesterol 45:20:20:15 w/w) and polar lipid extract from bovine liver released 62% and 74%, respectively, of the DNA content. A possible reason for this superior power in releasing DNA by the natural lipid mixtures was suggested by structural experiments: while pure anionic lipids typically form lamellae, the natural lipid mixtures exhibited a surprising predilection to form nonlamellar phases. Thus, the MM mixture arranged into lamellar arrays at physiological temperature, but began to convert to the hexagonal phase at a slightly higher temperature, ∼40-45°C. A propensity to form nonlamellar phases (hexagonal, cubic, micellar) at close to physiological temperatures was also found with the lipid extracts from natural tissues (from bovine liver, brain, and heart). This result reveals that electrostatic interactions are only one of the factors involved in lipid-mediated DNA delivery. The tendency of lipid bilayers to form nonlamellar phases has been described in terms of bilayer “frustration” which imposes a nonzero intrinsic curvature of the two opposing monolayers. Because the stored curvature elastic energy in a “frustrated” bilayer seems to be comparable to the binding energy between cationic lipid and DNA, the balance between these two energies could play a significant role in the lipoplex-membrane interactions and DNA release energetics. PMID:17559800

Natural lipid extracts and biomembrane-mimicking lipid compositions are disposed to form nonlamellar phases, and they release DNA from lipoplexes most efficiently

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

Koynova, Rumiana; MacDonald, Robert C.

2010-01-18

A viewpoint now emerging is that a critical factor in lipid-mediated transfection (lipofection) is the structural evolution of lipoplexes upon interacting and mixing with cellular lipids. Here we report our finding that lipid mixtures mimicking biomembrane lipid compositions are superior to pure anionic liposomes in their ability to release DNA from lipoplexes (cationic lipid/DNA complexes), even though they have a much lower negative charge density (and thus lower capacity to neutralize the positive charge of the lipoplex lipids). Flow fluorometry revealed that the portion of DNA released after a 30-min incubation of the cationic O-ethylphosphatidylcholine lipoplexes with the anionic phosphatidylserinemore » or phosphatidylglycerol was 19% and 37%, respectively, whereas a mixture mimicking biomembranes (MM: phosphatidylcholine/phosphatidylethanolamine/phosphatidylserine /cholesterol 45:20:20:15 w/w) and polar lipid extract from bovine liver released 62% and 74%, respectively, of the DNA content. A possible reason for this superior power in releasing DNA by the natural lipid mixtures was suggested by structural experiments: while pure anionic lipids typically form lamellae, the natural lipid mixtures exhibited a surprising predilection to form nonlamellar phases. Thus, the MM mixture arranged into lamellar arrays at physiological temperature, but began to convert to the hexagonal phase at a slightly higher temperature, {approx} 40-45 C. A propensity to form nonlamellar phases (hexagonal, cubic, micellar) at close to physiological temperatures was also found with the lipid extracts from natural tissues (from bovine liver, brain, and heart). This result reveals that electrostatic interactions are only one of the factors involved in lipid-mediated DNA delivery. The tendency of lipid bilayers to form nonlamellar phases has been described in terms of bilayer 'frustration' which imposes a nonzero intrinsic curvature of the two opposing monolayers. Because the stored curvature elastic energy in a 'frustrated' bilayer seems to be comparable to the binding energy between cationic lipid and DNA, the balance between these two energies could play a significant role in the lipoplex-membrane interactions and DNA release energetics.« less

Dyscalculia in Harrow

ERIC Educational Resources Information Center

Messenger, Chris; Emerson, Jane; Bird, Ronit

2007-01-01

In this article, the authors offer three definitions of dyscalculia, then describe the background and initial progress of the Harrow Dyscalculia Project. Their project in Harrow is associated with ongoing research into numeracy and brain development led by Brian Butterworth, Professor of Cognitive Neuropsychology at UCL. Pupils from Harrow schools…

Upconversion luminescence of CsScF4 crystals doped with erbium and ytterbium

NASA Astrophysics Data System (ADS)

Ikonnikov, D. A.; Voronov, V. N.; Molokeev, M. S.; Aleksandrovsky, A. S.

2016-10-01

Tetragonal CsScF4 crystals doped with (5 at.%) Er and Er/Yb (0.5 at.%/5 at.%) are grown and their crystal structure is determined to belong to Pmmn space group. Er and Yb ions are shown to occupy distorted octahedral Sc sites with the center of inversion. Bright visible upconversion luminescence was observed under 970-980 nm pumping with red (4F9/2), yellow (4S3/2) and green (2H11/2) bands of comparable intensity. UCL tuning curves maximize at 972 nm (CSF:Er) and at 969.7 nm (CSF:Er,Yb) pumping wavelengths. Different ratios between yellow-green and red luminescence intensities in CSF:Er and CSF:Er, Yb are explained by contribution of cross-relaxation in CSF:Er UCL. UC in CSF:Er is a three stage process while UC in CSF:Er, Yb is a two stage process. The peculiarities of power dependences are explained by the power-dependent repopulation between starting levels of UC.

Dianion diagnostics in DESIREE: High-sensitivity detection of Cn2 - from a sputter ion source

NASA Astrophysics Data System (ADS)

Chartkunchand, K. C.; Stockett, M. H.; Anderson, E. K.; Eklund, G.; Kristiansson, M. K.; Kamińska, M.; de Ruette, N.; Blom, M.; Björkhage, M.; Källberg, A.; Löfgren, P.; Reinhed, P.; Rosén, S.; Simonsson, A.; Zettergren, H.; Schmidt, H. T.; Cederquist, H.

2018-03-01

A sputter ion source with a solid graphite target has been used to produce dianions with a focus on carbon cluster dianions, Cn2 -, with n = 7-24. Singly and doubly charged anions from the source were accelerated together to kinetic energies of 10 keV per atomic unit of charge and injected into one of the cryogenic (13 K) ion-beam storage rings of the Double ElectroStatic Ion Ring Experiment facility at Stockholm University. Spontaneous decay of internally hot Cn2 - dianions injected into the ring yielded Cn- anions with kinetic energies of 20 keV, which were counted with a microchannel plate detector. Mass spectra produced by scanning the magnetic field of a 90° analyzing magnet on the ion injection line reflect the production of internally hot C72 - - C242 - dianions with lifetimes in the range of tens of microseconds to milliseconds. In spite of the high sensitivity of this method, no conclusive evidence of C62 - was found while there was a clear C72 - signal with the expected isotopic distribution. This is consistent with earlier experimental studies and with theoretical predictions. An upper limit is deduced for a C62 - signal that is two orders-of-magnitude smaller than that for C72 -. In addition, CnO2- and CnCu2- dianions were detected.

Interaction of inorganic anions with iron-mineral adsorbents in aqueous media--a review.

PubMed

Kumar, Eva; Bhatnagar, Amit; Hogland, William; Marques, Marcia; Sillanpää, Mika

2014-01-01

A number of inorganic anions (e.g., nitrate, fluoride, bromate, phosphate, and perchlorate) have been reported in alarming concentrations in numerous drinking water sources around the world. Their presence even in very low concentrations may cause serious environmental and health related problems. Due to the presence and significance of iron minerals in the natural aquatic environment and increasing application of iron in water treatment, the knowledge of the structure of iron and iron minerals and their interactions with aquatic pollutants, especially inorganic anions in water are of great importance. Iron minerals have been known since long as potential adsorbents for the removal of inorganic anions from aqueous phase. The chemistry of iron and iron minerals reactions in water is complex. The adsorption ability of iron and iron minerals towards inorganic anions is influenced by several factors such as, surface characteristics of the adsorbent (surface area, density, pore volume, porosity, pore size distribution, pHpzc, purity), pH of the solution, and ionic strength. Furthermore, the physico-chemical properties of inorganic anions (pore size, ionic radius, bulk diffusion coefficient) also significantly influence the adsorption process. The aim of this paper is to provide an overview of the properties of iron and iron minerals and their reactivity with some important inorganic anionic contaminants present in water. It also summarizes the usage of iron and iron minerals in water treatment technology. © 2013.

Mechanism of Action of Sulforaphane as a Superoxide Radical Anion and Hydrogen Peroxide Scavenger by Double Hydrogen Transfer: A Model for Iron Superoxide Dismutase.

PubMed

Prasad, Ajit Kumar; Mishra, P C

2015-06-25

The mechanism of action of sulforaphane as a scavenger of superoxide radical anion (O2(•-)) and hydrogen peroxide (H2O2) was investigated using density functional theory (DFT) in both gas phase and aqueous media. Iron superoxide dismutase (Fe-SOD) involved in scavenging superoxide radical anion from biological media was modeled by a complex consisting of the ferric ion (Fe(3+)) attached to three histidine rings. Reactions related to scavenging of superoxide radical anion by sulforaphane were studied using DFT in the presence and absence of Fe-SOD represented by this model in both gas phase and aqueous media. The scavenging action of sulforaphane toward both superoxide radical anion and hydrogen peroxide was found to involve the unusual mechanism of double hydrogen transfer. It was found that sulforaphane alone, without Fe-SOD, cannot scavenge superoxide radical anion in gas phase or aqueous media efficiently as the corresponding reaction barriers are very high. However, in the presence of Fe-SOD represented by the above-mentioned model, the scavenging reactions become barrierless, and so sulforaphane scavenges superoxide radical anion by converting it to hydrogen peroxide efficiently. Further, sulforaphane was found to scavenge hydrogen peroxide also very efficiently by converting it into water. Thus, the mechanism of action of sulforaphane as an excellent antioxidant has been unravelled.

Understanding Anionic "Ligandless" Palladium Species in the Mizoroki-Heck Reaction.

PubMed

Schroeter, Felix; Strassner, Thomas

2018-05-07

The anionic complex [NBu 4 ][Pd(DMSO)Cl 3 ], as a "ligandless" system, was shown to be an active catalyst in the Mizoroki-Heck coupling of aryl chlorides in the absence of strongly σ-donating ligands. To investigate the experimentally observed influence of halides and the amount of water on the catalytic activity, we employed a combination of experiments and theoretical calculations. The presence of water was shown to be critical for the formation of the active palladium(0) species by oxidation of in situ generated tributylamine. Oxidative addition to an anionic palladium(0) species was found to be the rate-determining step of the catalytic cycle. For the ensuing steps, both neutral and anionic pathways were considered. It was shown that, in the absence of strongly σ-donating neutral ligands, chloride ions stabilize the catalytic intermediates. Therefore, an anionic pathway is preferred, which explains the need for tetrabutylammonium chloride as an additive. The study of the influence of bromide ions on the catalytic activity revealed that the strongly exergonic displacement of the neutral substrates by bromide ions lowers the catalytic activity.

Fluoride-selective colorimetric sensor based on thiourea binding site and anthraquinone reporter.

PubMed

Wu, Fang-ying; Hu, Mei-hua; Wu, Yu-mei; Tan, Xiao-fang; Zhao, Yong-qiang; Ji, Zhao-jun

2006-11-01

A structurally simple colorimetric sensor, N-4-nitrobenzene-N'-1'-anthraquinone-thiourea (1), for anions was synthesized and characterized by (1)H NMR, ESI mass and IR methods. In acetonitrile, the addition of F(-) changed 1 solution from colorless to yellow. In the presence of other anions such as CH(3)CO(2)(-), H(2)PO(4)(-), HSO(4)(-) and Cl(-), however, the absorption spectrum of 1 was slightly red shifted with no obvious color changes observed. The association constants of anionic complexes followed the order of F(-)>CH(3)CO(2)(-)>H(2)PO(4)(-)>HSO(4)(-)>Cl(-)>Br(-), which was different from the order of anion basicity. AM1 calculation results indicated that the most stable configuration of 1 existed in the Z-E-conformation with a six-membered ring via intramolecular hydrogen bond. This made thiourea moiety of 1 in an unfavorable conformation to bond with oxygen-anionic substrates such as CH(3)CO(2)(-) and H(2)PO(4)(-), thus leading to a high selectivity and sensitivity for the detection of F(-).

High-Resolution 3T MR Imaging of the Triangular Fibrocartilage Complex

PubMed Central

von Borstel, Donald; Wang, Michael; Small, Kirstin; Nozaki, Taiki; Yoshioka, Hiroshi

2017-01-01

This study is intended as a review of 3Tesla (T) magnetic resonance (MR) imaging of the triangular fibrocartilage complex (TFCC). The recent advances in MR imaging, which includes high field strength magnets, multi-channel coils, and isotropic 3-dimensional (3D) sequences have enabled the visualization of precise TFCC anatomy with high spatial and contrast resolution. In addition to the routine wrist protocol, there are specific techniques used to optimize 3T imaging of the wrist; including driven equilibrium sequence (DRIVE), parallel imaging, and 3D imaging. The coil choice for 3T imaging of the wrist depends on a number of variables, and the proper coil design selection is critical for high-resolution wrist imaging with high signal and contrast-to-noise ratio. The TFCC is a complex structure and is composed of the articular disc (disc proper), the triangular ligament, the dorsal and volar radioulnar ligaments, the meniscus homologue, the ulnar collateral ligament (UCL), the extensor carpi ulnaris (ECU) tendon sheath, and the ulnolunate and ulnotriquetral ligaments. The Palmer classification categorizes TFCC lesions as traumatic (type 1) or degenerative (type 2). In this review article, we present clinical high-resolution MR images of normal TFCC anatomy and TFCC injuries with this classification system. PMID:27535592

High-Resolution 3T MR Imaging of the Triangular Fibrocartilage Complex.

PubMed

von Borstel, Donald; Wang, Michael; Small, Kirstin; Nozaki, Taiki; Yoshioka, Hiroshi

2017-01-10

This study is intended as a review of 3Tesla (T) magnetic resonance (MR) imaging of the triangular fibrocartilage complex (TFCC). The recent advances in MR imaging, which includes high field strength magnets, multi-channel coils, and isotropic 3-dimensional (3D) sequences have enabled the visualization of precise TFCC anatomy with high spatial and contrast resolution. In addition to the routine wrist protocol, there are specific techniques used to optimize 3T imaging of the wrist; including driven equilibrium sequence (DRIVE), parallel imaging, and 3D imaging. The coil choice for 3T imaging of the wrist depends on a number of variables, and the proper coil design selection is critical for high-resolution wrist imaging with high signal and contrast-to-noise ratio. The TFCC is a complex structure and is composed of the articular disc (disc proper), the triangular ligament, the dorsal and volar radioulnar ligaments, the meniscus homologue, the ulnar collateral ligament (UCL), the extensor carpi ulnaris (ECU) tendon sheath, and the ulnolunate and ulnotriquetral ligaments. The Palmer classification categorizes TFCC lesions as traumatic (type 1) or degenerative (type 2). In this review article, we present clinical high-resolution MR images of normal TFCC anatomy and TFCC injuries with this classification system.

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.

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

Polyakova, I. N., E-mail: polyakova@igic.ras.ru; Baulin, V. E.; Ivanova, I. S.

The coordination compounds of Er{sup 3+} with 1-(methoxydiphenylphosphoryl)-2-diphenylphosphorylbenzene [ErL{sub 2}{sup 1}(NO{sub 3}){sub 2}]{sub 2}[Er(NO{sub 3}){sub 2}(H{sub 2}O){sub 5}]{sub 0.333}(NO{sub 3}){sub 2.333} · 2.833H{sub 2}O (I) and its ethyl substituted derivative [ErL{sub 2}{sup 2}(NO{sub 3}){sub 2}][Er(NO{sub 3}){sub 5}]{sub 0.5} · 0.5H{sub 2}O (II) are synthesized and their crystal structures are studied. I and II contain [ErL{sub 2}(NO{sub 3}){sub 2}]{sup +} complex cations of identical composition and close structure. The eight-vertex polyhedron of the Er atom in the shape of a distorted octahedron with two split trans vertices is formed by the O atoms of the phosphoryl groups of L ligands andmore » nitrate anions. L ligands close nine-membered metallocycles. The structures contain spacious channels which are populated differently, namely, by disordered [Er(NO{sub 3}){sub 2}(H{sub 2}O){sub 5}]{sup +} complex cations, NO{sub 3}{sup −} anions, and crystallization water molecules in I and disordered [Er(NO{sub 3}){sub 5}]{sup 2−} complex anions and crystallization water molecules in II. The IR spectra of I and II are studied.« less

Structure of a premicellar complex of alkyl sulfates with the interfacial binding surfaces of four subunits of phospholipase A2.

PubMed

Pan, Ying H; Bahnson, Brian J

2010-07-01

The properties of three discrete premicellar complexes (E1#, E2#, E3#) of pig pancreatic group-IB secreted phospholipase A2 (sPLA2) with monodisperse alkyl sulfates have been characterized [Berg, O. G. et al., Biochemistry 43, 7999-8013, 2004]. Here we have solved the 2.7 A crystal structure of group-IB sPLA2 complexed with 12 molecules of octyl sulfate (C8S) in a form consistent with a tetrameric oligomeric that exists during the E1# phase of premicellar complexes. The alkyl tails of the C8S molecules are centered in the middle of the tetrameric cluster of sPLA2 subunits. Three of the four sPLA2 subunits also contain a C8S molecule in the active site pocket. The sulfate oxygen of a C8S ligand is complexed to the active site calcium in three of the four protein active sites. The interactions of the alkyl sulfate head group with Arg-6 and Lys-10, as well as the backbone amide of Met-20, are analogous to those observed in the previously solved sPLA2 crystal structures with bound phosphate and sulfate anions. The cluster of three anions found in the present structure is postulated to be the site for nucleating the binding of anionic amphiphiles to the interfacial surface of the protein, and therefore this binding interaction has implications for interfacial activation of the enzyme. Copyright (c) 2010 Elsevier B.V. All rights reserved.

A comparative study of the biosorption of iron(III)-cyanide complex anions to Rhizopus arrhizus and Chlorella vulgaris

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

Aksu, Z.; Calik, A.

1999-03-01

In this study a comparative biosorption of iron(III)-cyanide complex anions from aqueous solutions to Rhizopus arrhizus and Chlorella vulgaris was investigated. The iron(III)-cyanide complex ion-binding capacities of the biosorbents were shown as a function of initial pH, initial iron(III)-cyanide complex ion, and biosorbent concentrations. The results indicated that a significant reduction of iron(III)-cyanide complex ions was achieved at pH 13, a highly alkaline condition for both the biosorbents. The maximum loading capacities of the biosorbents were found to be 612.2 mg/g for R.arrhizus at 1,996.2 mg/L initial iron(III)-cyanide complex ion concentration and 387.0 mg/g for C. vulgaris at 845.4 mg/Lmore » initial iron(III)-cyanide complex ion concentration at this pH. The Freundlich, Langmuir, and Redlich-Peterson adsorption models were fitted to the equilibrium data at pH 3, 7, and 13. The equilibrium data of the biosorbents could be best fitted by all the adsorption models over the entire concentration range at pH 13.« less

Dramatic Influence of an Anionic Donor on the Oxygen-Atom Transfer Reactivity of a MnV–Oxo Complex

PubMed Central

Neu, Heather M; Quesne, Matthew G; Yang, Tzuhsiung; Prokop-Prigge, Katharine A; Lancaster, Kyle M; Donohoe, James; DeBeer, Serena; de Visser, Sam P; Goldberg, David P

2014-01-01

Addition of an anionic donor to an MnV(O) porphyrinoid complex causes a dramatic increase in 2-electron oxygen-atom-transfer (OAT) chemistry. The 6-coordinate [MnV(O)(TBP8Cz)(CN)]− was generated from addition of Bu4N+CN− to the 5-coordinate MnV(O) precursor. The cyanide-ligated complex was characterized for the first time by Mn K-edge X-ray absorption spectroscopy (XAS) and gives Mn–O=1.53 Å, Mn–CN=2.21 Å. In combination with computational studies these distances were shown to correlate with a singlet ground state. Reaction of the CN− complex with thioethers results in OAT to give the corresponding sulfoxide and a 2e−-reduced MnIII(CN)− complex. Kinetic measurements reveal a dramatic rate enhancement for OAT of approximately 24 000-fold versus the same reaction for the parent 5-coordinate complex. An Eyring analysis gives ΔH≠=14 kcal mol−1, ΔS≠=−10 cal mol−1 K−1. Computational studies fully support the structures, spin states, and relative reactivity of the 5- and 6-coordinate MnV(O) complexes. PMID:25256417

Interactions between Hofmeister anions and the binding pocket of a protein.

PubMed

Fox, Jerome M; Kang, Kyungtae; Sherman, Woody; Héroux, Annie; Sastry, G Madhavi; Baghbanzadeh, Mostafa; Lockett, Matthew R; Whitesides, George M

2015-03-25

This paper uses the binding pocket of human carbonic anhydrase II (HCAII, EC 4.2.1.1) as a tool to examine the properties of Hofmeister anions that determine (i) where, and how strongly, they associate with concavities on the surfaces of proteins and (ii) how, upon binding, they alter the structure of water within those concavities. Results from X-ray crystallography and isothermal titration calorimetry show that most anions associate with the binding pocket of HCAII by forming inner-sphere ion pairs with the Zn(2+) cofactor. In these ion pairs, the free energy of anion-Zn(2+) association is inversely proportional to the free energetic cost of anion dehydration; this relationship is consistent with the mechanism of ion pair formation suggested by the "law of matching water affinities". Iodide and bromide anions also associate with a hydrophobic declivity in the wall of the binding pocket. Molecular dynamics simulations suggest that anions, upon associating with Zn(2+), trigger rearrangements of water that extend up to 8 Å away from their surfaces. These findings expand the range of interactions previously thought to occur between ions and proteins by suggesting that (i) weakly hydrated anions can bind complementarily shaped hydrophobic declivities, and that (ii) ion-induced rearrangements of water within protein concavities can (in contrast with similar rearrangements in bulk water) extend well beyond the first hydration shells of the ions that trigger them. This study paints a picture of Hofmeister anions as a set of structurally varied ligands that differ in size, shape, and affinity for water and, thus, in their ability to bind to—and to alter the charge and hydration structure of—polar, nonpolar, and topographically complex concavities on the surfaces of proteins.

Ammonium boranes for the selective complexation of cyanide or fluoride ions in water.

PubMed

Hudnall, Todd W; Gabbaï, François P

2007-10-03

With the recognition of aqueous fluoride and cyanide ions as an objective, we have investigated the anion binding properties of two isomeric ammonium boranes, namely [p-(Mes2B)C6H4(NMe3)]+ ([1]+) and [o-(Mes2B)C6H4(NMe3)]+ ([2]+). These cationic boranes, which could be obtained by reaction of the known 4- and 2-dimesitylboryl-N,N-dimethylaniline with MeOTf, have been investigated both experimentally and computationally. They both react with fluoride and cyanide ions in organic solvents to afford the corresponding fluoroborate/ or cyanoborate/ammonium zwitterions 1F, 1CN, 2F, and 2CN. In aqueous solution, however, these cationic boranes behave as remarkably selective receptors. Indeed, [1]+ only complexes cyanide ions while [2]+ only complexes fluoride ions. In H2O/DMSO 60:40 vol (HEPES 6 mM, pH 7), the cyanide binding constant of [1]+ and the fluoride binding constant of [2]+ are respectively equal to 3.9 (+/-0.1) x 108 and 910 (+/-50) M-1. Structural and computational studies indicate that both steric and electronic effects contribute to the unusual selectivity displayed by these cationic boranes. Owing to favorable Coulombic effects, the para-derivative [1]+ has a very high affinity for cyanide; yet these effects are not sufficiently intense to allow complexation of the more efficiently hydrated and less basic fluoride anion. In the case of the ortho-derivative [2]+, the proximity of the ammonium moiety leads to an increase in the Lewis acidity of the boron center thus making fluoride binding possible. However, steric effects prevent cyanide coordination to the boron center of [2]+. Finally, cation [1]+ and [2]+ bind their dedicated anions reversibly and show a negligible response in the presence of other common anions including Cl-, Br-, I-, NO3-, OAc-, H2PO4-, and HSO4-.

Outcomes and Return to Sport After Ulnar Collateral Ligament Reconstruction in Adolescent Baseball Players

PubMed Central

Saper, Michael; Shung, Joseph; Pearce, Stephanie; Bompadre, Viviana; Andrews, James R.

2018-01-01

Background: The number of ulnar collateral ligament (UCL) reconstructions in adolescent athletes has increased over the past 2 decades. Clinical results in this population have not been well studied. Purpose/Hypothesis: The purpose of this study was to evaluate the outcomes and return to sport after UCL reconstruction in a large group of adolescent baseball players. We hypothesized that excellent clinical outcomes and high rates of return to sport would be observed in this population at a minimum 2-year follow-up. Study Design: Case series; Level of evidence, 4. Methods: We reviewed 140 adolescent (aged ≤19 years) baseball players who underwent UCL reconstruction with the American Sports Medicine Institute (ASMI) technique by a single surgeon. Medical records were reviewed for patient demographics, injury characteristics, operative details, and surgical complications. Patient-reported outcomes were assessed using the Conway scale, the Andrews-Timmerman (A-T) score, the Kerlan-Jobe Orthopaedic Clinic (KJOC) score, and a 0- to 100-point subjective scale for elbow function and satisfaction. Return to sporting activity was assessed using a custom-designed questionnaire. Results: The mean age at the time of surgery was 18.0 years (range, 13-19 years), and the mean follow-up was 57.9 months (range, 32.4-115.4 months). Over half (60%) of patients were high school athletes. The mean duration of symptoms before surgery was 6.9 months (range, 0.5-60.0 months). Partial tears were identified in 57.9% of patients, and 41.3% of patients had preoperative ulnar nerve symptoms. Graft type included the ipsilateral palmaris in 77.1% of patients. Concomitant procedures were performed in 25% of patients. Outcomes on the Conway scale were “excellent” in 86.4% of patients. The mean A-T and KJOC scores were 97.3 ± 6.1 and 85.2 ± 14.6, respectively. Mean patient satisfaction was 94.4. Overall, 97.8% of patients reported returning to sport at a mean of 11.6 months (range, 5-24 months), and 89.9% of patients returned to sport at the same level of competition or higher. A total of 11.6% of patients went on to play professional baseball. Conclusion: UCL reconstruction with the ASMI technique is an effective surgical option in adolescents, with excellent outcome scores. At a minimum of 2-year follow-up, nearly 90% of patients returned to their preinjury level of sport. PMID:29780844

Caution regarding the choice of standard deviations to guide sample size calculations in clinical trials.

PubMed

Chen, Henian; Zhang, Nanhua; Lu, Xiaosun; Chen, Sophie

2013-08-01

The method used to determine choice of standard deviation (SD) is inadequately reported in clinical trials. Underestimations of the population SD may result in underpowered clinical trials. This study demonstrates how using the wrong method to determine population SD can lead to inaccurate sample sizes and underpowered studies, and offers recommendations to maximize the likelihood of achieving adequate statistical power. We review the practice of reporting sample size and its effect on the power of trials published in major journals. Simulated clinical trials were used to compare the effects of different methods of determining SD on power and sample size calculations. Prior to 1996, sample size calculations were reported in just 1%-42% of clinical trials. This proportion increased from 38% to 54% after the initial Consolidated Standards of Reporting Trials (CONSORT) was published in 1996, and from 64% to 95% after the revised CONSORT was published in 2001. Nevertheless, underpowered clinical trials are still common. Our simulated data showed that all minimal and 25th-percentile SDs fell below 44 (the population SD), regardless of sample size (from 5 to 50). For sample sizes 5 and 50, the minimum sample SDs underestimated the population SD by 90.7% and 29.3%, respectively. If only one sample was available, there was less than 50% chance that the actual power equaled or exceeded the planned power of 80% for detecting a median effect size (Cohen's d = 0.5) when using the sample SD to calculate the sample size. The proportions of studies with actual power of at least 80% were about 95%, 90%, 85%, and 80% when we used the larger SD, 80% upper confidence limit (UCL) of SD, 70% UCL of SD, and 60% UCL of SD to calculate the sample size, respectively. When more than one sample was available, the weighted average SD resulted in about 50% of trials being underpowered; the proportion of trials with power of 80% increased from 90% to 100% when the 75th percentile and the maximum SD from 10 samples were used. Greater sample size is needed to achieve a higher proportion of studies having actual power of 80%. This study only addressed sample size calculation for continuous outcome variables. We recommend using the 60% UCL of SD, maximum SD, 80th-percentile SD, and 75th-percentile SD to calculate sample size when 1 or 2 samples, 3 samples, 4-5 samples, and more than 5 samples of data are available, respectively. Using the sample SD or average SD to calculate sample size should be avoided.

Outpatient versus inpatient treatment for patients with acute pulmonary embolism: an international, open-label, randomised, non-inferiority trial.

PubMed

Aujesky, Drahomir; Roy, Pierre-Marie; Verschuren, Franck; Righini, Marc; Osterwalder, Joseph; Egloff, Michael; Renaud, Bertrand; Verhamme, Peter; Stone, Roslyn A; Legall, Catherine; Sanchez, Olivier; Pugh, Nathan A; N'gako, Alfred; Cornuz, Jacques; Hugli, Olivier; Beer, Hans-Jürg; Perrier, Arnaud; Fine, Michael J; Yealy, Donald M

2011-07-02

Although practice guidelines recommend outpatient care for selected, haemodynamically stable patients with pulmonary embolism, most treatment is presently inpatient based. We aimed to assess non-inferiority of outpatient care compared with inpatient care. We undertook an open-label, randomised non-inferiority trial at 19 emergency departments in Switzerland, France, Belgium, and the USA. We randomly assigned patients with acute, symptomatic pulmonary embolism and a low risk of death (pulmonary embolism severity index risk classes I or II) with a computer-generated randomisation sequence (blocks of 2-4) in a 1:1 ratio to initial outpatient (ie, discharged from hospital ≤24 h after randomisation) or inpatient treatment with subcutaneous enoxaparin (≥5 days) followed by oral anticoagulation (≥90 days). The primary outcome was symptomatic, recurrent venous thromboembolism within 90 days; safety outcomes included major bleeding within 14 or 90 days and mortality within 90 days. We used a non-inferiority margin of 4% for a difference between inpatient and outpatient groups. We included all enrolled patients in the primary analysis, excluding those lost to follow-up. This trial is registered with ClinicalTrials.gov, number NCT00425542. Between February, 2007, and June, 2010, we enrolled 344 eligible patients. In the primary analysis, one (0·6%) of 171 outpatients developed recurrent venous thromboembolism within 90 days compared with none of 168 inpatients (95% upper confidence limit [UCL] 2·7%; p=0·011). Only one (0·6%) patient in each treatment group died within 90 days (95% UCL 2·1%; p=0·005), and two (1·2%) of 171 outpatients and no inpatients had major bleeding within 14 days (95% UCL 3·6%; p=0·031). By 90 days, three (1·8%) outpatients but no inpatients had developed major bleeding (95% UCL 4·5%; p=0·086). Mean length of stay was 0·5 days (SD 1·0) for outpatients and 3·9 days (SD 3·1) for inpatients. In selected low-risk patients with pulmonary embolism, outpatient care can safely and effectively be used in place of inpatient care. Swiss National Science Foundation, Programme Hospitalier de Recherche Clinique, and the US National Heart, Lung, and Blood Institute. Sanofi-Aventis provided free drug supply in the participating European centres. Copyright © 2011 Elsevier Ltd. All rights reserved.

Influence of ionic strength and OH(-) ion concentration on the Cu(II) complex formation with EDTA in alkaline solutions.

PubMed

Norkus, E; Vaskelis, A; Zakaite, I

1996-03-01

D.c. polarographic data show that the complex formation of copper ions with EDTA depends markedly on the ionic strength of the solution at pH 8-10. This is primarily associated with the dependence of the fourth deprotonization constant of EDTA on the solution ionic strength: when it increases from 0.4 to 3.4, the pK(a4) value decreases from 9.5 to 8.2. According to polarographic and spectrophotometric data the degree of Cu(II) complexation increases at pH>10 due to transformation of the complex CuY(2-) to the more stable CuY(OH)(3-) (Y(4-), a fully deprotonized anion of EDTA), but it decreases with increase in alkalinity in a highly alkaline solution (pH>13.5). The latter result could be explained by the decrease in the EDTA anion activity. The calculated values of the activity coefficient are lower than 0.05 at pH>14.

Linear trichromium complexes with the anion of 2,6-di(phenylimino)piperidine.

PubMed

Clérac, R; Cotton, F A; Daniels, L M; Dunbar, K R; Murillo, C A; Zhou, H C

2000-07-24

The anion of 2,6-di(phenylimino)piperidine (DPhIP) has been found to support linear chains of three metal atoms. Three new compounds, [Cr3(DPhIP)4Cl]Cl.(1).5CH2Cl2.0.5H2O (1.1.5CH2Cl2.0.5H2O), [Cr3(DPhIP)4(CH3CN)]- (PF6)2.H2O.4CH3CN (2.H2O.4CH3CN), and [Cr3(DPhIP)4(F)(CH3CN)](BF4)2.5CH3CN (3.5CH3CN), have been synthesized and characterized by X-ray crystallography. Compound 1 has a linear chain of three chromium atoms arranged in an unsymmetrical fashion, with two of them forming a quadruply bonded unit (Cr-Cr distance 1.932(2) A) and the third being a non-metal-metal-bound 5-coordinate unit (Cr...Cr distance 2.659(2) A). The fifth coordination site is occupied by a chloride ion, and another chloride ion is located in the interstices of the crystal. The trimetal unit in compound 2 is structurally similar to that in compound 1 except that the axial ligand in 2 is a CH3CN molecule. Compound 3 is an oxidation product prepared by reaction of 1 with AgBF4. Here, a square pyramidal CrIII unit, FCrN4, and a Cr-Cr quadruply bonded (Cr-Cr distance 1.968(2) A) unit, with an axially coordinated acetonitrile molecule, form the trichromium chain. The CrIII...CrII separation of 2.594(2) A in 3 is too long to be considered a bonding interaction.

Six uranyl-organic frameworks with naphthalene-dicarboxylic acid and bipyridyl-based spacers: syntheses, structures, and properties.

PubMed

Xu, Wei; Ren, Ya-Nan; Xie, Miao; Zhou, Lin-Xia; Zheng, Yue-Qing

2018-03-28

A new series of uranium coordination polymers have been hydrothermally synthesized by using 1,4-naphthalene dicarboxylic acid (H 2 NDC), namely, (H 3 O) 2 [(UO 2 ) 2 (NDC) 3 ]·H 2 O (1), (H 2 -bpp)[(UO 2 ) 2 (NDC) 3 ]·EtOH·5H 2 O (2), (H 2 -bpe) 2/2 [(UO 2 ) 2 (NDC) 3 ]·EtOH (3), (H 2 -bpp)[(UO 2 ) 2 (NDC) 3 ]·5H 2 O (4), (H 2 -bpp)[(UO 2 )(HNDC)(NDC)] 2 ·2H 2 O (5), and (H 2 -bpy)[(UO 2 )(NDC) 2 ] (6) [bpp = 1,3-di(4-pyridyl) propane, bpe = 4,4'-vinylenedipyridine, bpy = 4,4'-bipyridine]. Single-crystal X-ray diffraction demonstrates that complex 1 represents the uranyl-organic polycatenated framework derived from a simple two-dimensional honeycomb grid network structure via a H 2 NDC linker. Complexes 2-4 contain the dinuclear motifs of the two UO 7 pentagonal and one UO 8 hexagonal bipyramids which are linked by NDC 2- anions creating a (UO 2 ) 4 (NDC) 2 unit, and further extend to a 2D layer through NDC 2- anions. Complex 5 displays a 1D zigzag double chain structure, in which the carboxylate groups of the NDC 2- anions adopt a chelate mode and further extends to a 2D framework via hydrogen bonds. The 1D structure of complex 6 is similar to the zigzag chain of complex 5. In addition, powder X-ray diffraction, elemental analysis, IR, thermal stability and luminescence properties of all complexes have also been investigated in this paper. The photocatalytic properties of the six complexes for the degradation of tetracycline hydrochloride (TC) under UV irradiation have been examined. Moreover, density functional theory (DFT) calculations were carried out to explore the electronic structural and bonding properties of the uranyl complexes 1-6.

Tetraammine(carbonato-κ(2) O,O')cobalt(III) perchlorate.

PubMed

Mohan, Singaravelu Chandra; Jenniefer, Samson Jegan; Muthiah, Packianathan Thomas; Jothivenkatachalam, Kandasamy

2013-01-01

In the title complex, [Co(CO3)(NH3)4]ClO4, both the cation and anion lie on a mirror plane. The Co(III) ion is coordinated by two NH3 ligands and a chelating carbonato ligand in the equatorial sites and by two NH3 groups in the axial sites, forming a distorted octa-hedral geometry. In the crystal, N-H⋯O hydrogen bonds connect the anions and cations, forming a three-dimensional network.

Oxygen anion (O- ) and hydroxide anion (HO- ) reactivity with a series of old and new refrigerants.

PubMed

Le Vot, Clotilde; Lemaire, Joël; Pernot, Pascal; Heninger, Michel; Mestdagh, Hélène; Louarn, Essyllt

2018-04-01

The reactivity of a series of commonly used halogenated compounds (trihalomethanes, chlorofluorocarbon, hydrochlorofluorocarbon, fluorocarbons, and hydrofluoroolefin) with hydroxide and oxygen anion is studied in a compact Fourier transform ion cyclotron resonance. O - is formed by dissociative electron attachment to N 2 O and HO - by a further ion-molecule reaction with ammonia. Kinetic experiments are performed by increasing duration of introduction of the studied molecule at a constant pressure. Hydroxide anion reactions mainly proceed by proton transfer for all the acidic compounds. However, nucleophilic substitution is observed for chlorinated and brominated compounds. For fluorinated compounds, a specific elimination of a neutral fluorinated alkene is observed in our results in parallel with the proton transfer reaction. Oxygen anion reacts rapidly and extensively with all compounds. Main reaction channels result from nucleophilic substitution, proton transfer, and formal H 2 + transfer. We highlight the importance of transfer processes (atom or ion) in the intermediate ion-neutral complex, explaining part of the observed reactivity and formed ions. In this paper, we present the first reactivity study of anions with HFO 1234yf. Finally, the potential of O - and HO - as chemical ionization reagents for trace analysis is discussed. Copyright © 2017 John Wiley & Sons, Ltd.

Crystal structure of octa-kis-(4-meth-oxy-pyridinium) bis-(4-meth-oxy-pyridine-κN)tetra-kis-(thio-cyanato-κN)ferrate(III) bis-[(4-meth-oxypyri-dine-κN)pentakis-(thio-cyanato-κN)ferrate(III)] hexa-kis-(thio-cyanato-κN)ferrate(III) with iron in three different octa-hedral coordination environments.

PubMed

Jochim, Aleksej; Jess, Inke; Näther, Christian

2018-03-01

The crystal structure of the title salt, (C 6 H 8 NO) 8 [Fe(NCS) 4 (C 6 H 7 NO) 2 ][Fe(NCS) 5 (C 6 H 7 NO)] 2 [Fe(NCS) 6 ], comprises three negatively charged octa-hedral Fe III complexes with different coordination environments in which the Fe III atoms are coordinated by a different number of thio-cyanate anions and 4-meth-oxy-pyridine ligands. Charge balance is achieved by 4-meth-oxy-pyridinium cations. The asymmetric unit consists of three Fe III cations, one of which is located on a centre of inversion, one on a twofold rotation axis and one in a general position, and ten thio-cyanate anions, two 4-meth-oxy-pyridine ligands and 4-meth-oxy-pyridinium cations (one of which is disordered over two sets of sites). Beside to Coulombic inter-actions between organic cations and the ferrate(III) anions, weak N-H⋯S hydrogen-bonding inter-actions involving the pyridinium N-H groups of the cations and the thio-cyanate S atoms of the complex anions are mainly responsible for the cohesion of the crystal structure.

Antibacterial effect of cationic porphyrazines and anionic phthalocyanine and their interaction with plasmid DNA

NASA Astrophysics Data System (ADS)

Hassani, Leila; Hakimian, Fatemeh; Safaei, Elham; Fazeli, Zahra

2013-11-01

Resistance to antibiotics is a public health issue and identification of new antibacterial agents is one of the most important goals of pharmacological research. Among the novel developed antibacterial agents, porphyrin complexes and their derivatives are ideal candidates for use in medical applications. Phthalocyanines differ from porphyrins by having nitrogen atoms link the individual pyrrol units. The aza analogues of the phthalocyanines (azaPcs) such as tetramethylmetalloporphyrazines are heterocyclic Pc analogues. In this investigation, interaction of an anionic phthalocyanine (Cu(PcTs)) and two cationic tetrapyridinoporphyrazines including [Cu(2,3-tmtppa)]4+ and [Cu(3,4-tmtppa)]4+ complexes with plasmid DNA was studied using spectroscopic and gel electrophoresis methods. In addition, antibacterial effect of the complexes against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria was investigated using dilution test method. The results indicated that both porphyrazines have significant antibacterial properties, but Cu(PcTs) has weak antibacterial effect. Compairing the binding of the phthalocyanine and the porphyrazines to DNA demonstrated that the interaction of cationic porphyrazines is stronger than the anionic phthalocyanine remarkably. The extent of hypochromicity and red shift of absorption spectra indicated preferential intercalation of the two porphyrazine into the base pairs of DNA helix. Gel electrophoresis result implied Cu(2,3-tmtppa) and Cu(3,4-tmtppa) are able to perform cleavage of the plasmid DNA. Consequently, DNA binding and cleavage might be one of the antibacterial mechanisms of the complexes.

Microhydration Effects on the Intermediates of the SN2 Reacation of Iodide Anion with Methyl Iodine

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

Doi, Keisuke; Togano, Eijiro; Xantheas, Sotiris S.

2013-04-15

Reactions of halide anions with methyl halides (X- + CH3Y → XCH3 + Y-) are bimolecular nucleophilic substitution (SN2) reactions that have been well investigated in the last few decades.[1] Figure 1 shows typical potential energy surfaces (PESs) proposed for symmetric (X- + CH3X → XCH3 + X-) SN2 reactions along the reaction coordinate. In the gas phase, the PES has two minima corresponding to the stable X-(CH3X) complexes.[2] The PES is substantially distorted by the solvation. Since the negative charge is delocalized over the [X•••CH3•••X]- moiety at the transition state the stabilization energy gained by the solvation is smallermore » for the transition state than that for the (X- + CH3X) reactants or the X- (CH3X) complexes. In solution, a large potential barrier exists between the reactants and products. The rate constants of these reactions in protic solvents were reported to be a few orders of magnitude smaller than those in aprotic solvents; this trend was explained by the formation of solvation shells of protic molecules around the halide anions.[1,3] Morokuma has previously reported a theoretical study on the PES of the (Cl- + CH3Cl → ClCH3 + Cl-) SN2 reaction with a few H2O molecules. The attachment of H2O molecules to the Cl-(CH3Cl) reactive system produces metastable isomers, which affect the reaction mechanism.[4] Johnson and coworkers extensively investigated the structure and reactions of halide anion complexes in the gas phase using photodissociation spectroscopy.« less

Interactions in ion pairs of protic ionic liquids: Comparison with aprotic ionic liquids

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

Tsuzuki, Seiji, E-mail: s.tsuzuki@aist.go.jp; Shinoda, Wataru; Miran, Md. Shah

2013-11-07

The stabilization energies for the formation (E{sub form}) of 11 ion pairs of protic and aprotic ionic liquids were studied by MP2/6-311G{sup **} level ab initio calculations to elucidate the difference between the interactions of ions in protic ionic liquids and those in aprotic ionic liquids. The interactions in the ion pairs of protic ionic liquids (diethylmethylammonium [dema] and dimethylpropylammonium [dmpa] based ionic liquids) are stronger than those of aprotic ionic liquids (ethyltrimethylammonium [etma] based ionic liquids). The E{sub form} for the [dema][CF{sub 3}SO{sub 3}] and [dmpa][CF{sub 3}SO{sub 3}] complexes (−95.6 and −96.4 kcal/mol, respectively) are significantly larger (more negative)more » than that for the [etma][CF{sub 3}SO{sub 3}] complex (−81.0 kcal/mol). The same trend was observed for the calculations of ion pairs of the three cations with the Cl{sup −}, BF{sub 4}{sup −}, TFSA{sup −} anions. The anion has contact with the N–H bond of the dema{sup +} or dmpa{sup +} cations in the most stable geometries of the dema{sup +} and dmpa{sup +} complexes. The optimized geometries, in which the anions locate on the counter side of the cations, are 11.0–18.0 kcal/mol less stable, which shows that the interactions in the ions pairs of protic ionic liquids have strong directionality. The E{sub form} for the less stable geometries for the dema{sup +} and dmpa{sup +} complexes are close to those for the most stable etma{sup +} complexes. The electrostatic interaction, which is the major source of the attraction in the ion pairs, is responsible for the directionality of the interactions and determining the magnitude of the interaction energy. Molecular dynamic simulations of the [dema][TFSA] and [dmpa][TFSA] ionic liquids show that the N–H bonds of the cations have contact with the negatively charged (oxygen and nitrogen) atoms of TFSA{sup −} anion, while the strong directionality of the interactions was not suggested from the simulation of the [etma][CF{sub 3}SO{sub 3}] ionic liquid.« less

Bimetallic poly- and oligo-nuclear complexes based on a rhodium(III) metalloligand

NASA Astrophysics Data System (ADS)

Vasilchenko, Danila B.; Venediktov, Anatoliy B.; Korenev, Sergey V.; Filatov, Evgeniy Yu.; Baidina, Iraida A.; Nadolinnyi, Vladimir A.

2012-10-01

Interaction of trans-[Rh(i-Nic)4Cl2]3- anions (i-Nic- - isonicotinate anion) with Cuaq2+ and Coaq2+ cations in water has afforded complex salts Co3[Rh(i-Nic)4Cl2]2·17H2O (1) and Cu3[Rh(i-Nic)4Cl2]2·14H2O (2). Oligonuclear character of 1 and 2 has been established. A coordination polymer Cu5[Rh(i-Nic)4Cl2]2(i-Nic)2(OH)2·2H2O (3) has been crystallized by hydrothermal treatment of 2 at 160 °C, and its structure was determined by X-ray structural analysis. EPR data for the complexes has been collected and interpreted. Thermal decomposition of the salts was studied by c-DTA. Bimetallic alloys rhodium-copper and rhodium-cobalt have been obtained as final products of thermal decomposition.

Amplification of hofmeister effect by alcohols.

PubMed

Xu, Yun; Liu, Guangming

2014-07-03

We have demonstrated that Hofmeister effect can be amplified by adding alcohols to aqueous solutions. The lower critical solution temperature behavior of poly(N-isopropylacrylamide) has been employed as the model system to study the amplification of Hofmeister effect. The alcohols can more effectively amplify the Hofmeister effect following the series methanol < ethanol < 1-propanol < 2-propanol for the monohydric alcohols and following the series d-sorbitol ≈ xylitol ≈ meso-erythritol < glycerol < ethylene glycol < methanol for the polyhydric alcohols. Our study reveals that the relative extent of amplification of Hofmeister effect is determined by the stability of the water/alcohol complex, which is strongly dependent on the chemical structure of alcohols. The more stable solvent complex formed via stronger hydrogen bonds can more effectively differentiate the anions through the anion-solvent complex interactions, resulting in a stronger amplification of Hofmeister effect. This study provides an alternative method to tune the relative strength of Hofmeister effect besides salt concentration.

Mulliken Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical

NASA Astrophysics Data System (ADS)

Rosokha, S. V.; Newton, M. D.; Head-Gordon, M.; Kochi, J. K.

2006-05-01

The paramagnetic [1:1] encounter complex (TCNE)2-rad is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor ( TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE)2-rad by its intervalence absorption band at the solvent-dependent wavelength of λIV ˜ 1500 nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of HDA = 1000 cm -1. The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of HDA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy ( λ) and the electronic coupling element ( HDA) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes.

Structural elucidation, EPR and magnetic property of a Co(III) complex salt incorporating 4,4‧-bipyridine and 5-sulfoisophthalate

NASA Astrophysics Data System (ADS)

Das, Kuheli; Datta, Amitabha; Pevec, Andrej; Mane, Sandeep B.; Rameez, Mohammad; Garribba, Eugenio; Akitsu, Takashiro; Tanka, Shinnosuke

2018-01-01

The cobalt(III) derivative [Co3(sip)4(bipy)2(H2O)10][Co(bipy)2(H2O)4]3(sip)2·20H2O (1) has been hydro(solvo) thermally synthesized by combining sodium 5-sulfoisophthalate (sipH2Na) as organic linker, divalent cobalt nitrate hexahydrate as metal salt and the flexible N-donor ancillary ligand bipy (4,4‧-bipyridine). Compound 1 is an ionic solid consisting of both cobalt containing cations and anions and also in addition 5-sulfoisophthalate anions. Cobalt containing cations in the crystal structure are mononuclear complex while cobalt containing anion is a discrete trinuclear species. The π-π interaction present in 1 results in chain supramolecular structure. The encapsulation of the cobalt compound displays a moderate luminescent property. On temperature dependent magnetic study, it is revealed that the corresponding effective magnetic moment is 5.27 B.M. at 300 K, which suggests isolated Co(III) species with S = 2 (theoretical value is 4.90 B M.) and thus 1 shows a rare paramagnetic behavior.

Combined experimental and theoretical studies on selective sensing of zinc and pyrophosphate ions by rational design of compartmental chemosensor probe: Dual sensing behaviour via secondary recognition approach and cell imaging studies.

PubMed

Mawai, Kiran; Nathani, Sandip; Roy, Partha; Singh, U P; Ghosh, Kaushik

2018-05-08

A compartmental chemosensor probe HL has been designed and synthesized for the selective recognition of zinc ions over other transition metal ions via fluorescence "ON" strategy. The chemosensing behaviour of HL was demonstrated through fluorescence, absorption and NMR spectroscopic techniques. The molecular structure of the zinc complex derived from HL was determined by X-ray crystallography. A probable mechanism of this selective sensing behavior was described on the basis of spectroscopic results and theoretical studies by density functional theory (DFT). The biological applicability of the chemosensor HL was examined via cell imaging on HeLa cells. The HL-zinc complex served as a secondary fluorescent probe responding to the pyrophosphate anion specifically over other anions. The fluorescence enhancement of HL in association with Zn2+ ions was quenched in the presence of pyrophosphate (PPi). Thus, a dual response was established based on "OFF-ON-OFF" strategy for detection of both cation and anion. This phenomenon was utilized in the construction of a "INHIBIT" logic gate.

Neutral and anionic duality of 1,2,4-triazole α-amino acid scaffold in 1D coordination polymers

NASA Astrophysics Data System (ADS)

Naik, Anil D.; Dîrtu, Marinela M.; Garcia, Yann

2012-03-01

A tiny supramolecular synthon, 4H-1,2,4-triazol-4-yl acetic acid (HGlytrz) which is bifunctional by design having an electronic asymmetry and conformational flexibility has been introduced to synthesize iron(II) complexes. Having 1,2,4-triazole or carboxylic extremities on the same framework HGlytrz could display dual functionality by acting as a neutral as well as anionic ligand based on the possibility of deprotonation of carboxylic group. Four new iron(II) HGlytrz complexes with ClO4- ( 1), NO3- ( 2), BF4- ( 3) and CF3SO3- ( 4) anions were prepared. Formulation of their composition which is complicated due to ligand deprotonation is discussed. Unlike its ester protected counterpart ethyl-4H-1,2,4-triazol-4-yl-acetate ( αGlytrz) which show hysteretic room temperature spin crossover, 1- 4 remain in the high-spin state as revealed by 57Mössbauer spectroscopy. Prospects of such 1D coordination polymers with dangling unbounded carboxylic entities in the realm of self-assembled monolayer (SAM) are discussed.

Tellurite‐Squarate Driven Assembly of a New Family of Nanoscale Clusters Based on (Mo2O2S2)2+

PubMed Central

Purcell, Jamie W.; Miras, Haralampos N.; Long, De‐Liang; Markopoulou, Panagiota

2017-01-01

Abstract The preparation and characterization of a new family of four polyoxothiometalate (POTM) clusters are reported, with varying size and complexity, based upon the dimeric [Mo2O2S2(H2O)6]2+ cation with the general formula (NMe4)aKb[(Mo2O2S2)c(TeO4)d(C4O4)e(OH)f] where a,b,c,d,e,f={1,7,14,2,4,10}=1, {Mo28Te2}; {2,26,36,12,10,48}=2, {Mo72Te12}; {0,11,15,3,3,21}=3, {Mo30Te3}; {2,6,12,2,4,16}=4, {Mo24Te2}. The incorporation of tellurite anions allowed the fine tuning of the templating and bridging of the available building blocks, leading to new topologies of increased complexity. The structural diversity of this family of compounds ranges from the highly symmetrical cross‐shaped {Mo24Te2} to the stacked ring structure of {Mo72Te12}, which is the largest tellurium‐containing POTM cluster reported so far. Also a detailed experimental analysis revealed that the pH isolation window extends from acidic to basic values. ESI‐MS analyses not only confirmed the stability of this family in solution but also revealed the stability of the observed virtual building blocks. PMID:28548217

46 CFR 54.01-35 - Corrosion (modifies UG- 25).

Code of Federal Regulations, 2012 CFR

2012-10-01

... 46 Shipping 2 2012-10-01 2012-10-01 false Corrosion (modifies UG- 25). 54.01-35 Section 54.01-35 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PRESSURE VESSELS... weather or mechanical damage are not acceptable. Note: No applied linings except as provided in Part UCL...

46 CFR 54.01-35 - Corrosion (modifies UG- 25).

Code of Federal Regulations, 2011 CFR

2011-10-01

... 46 Shipping 2 2011-10-01 2011-10-01 false Corrosion (modifies UG- 25). 54.01-35 Section 54.01-35 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PRESSURE VESSELS... weather or mechanical damage are not acceptable. Note: No applied linings except as provided in Part UCL...

46 CFR 54.01-35 - Corrosion (modifies UG- 25).

Code of Federal Regulations, 2014 CFR

2014-10-01

... 46 Shipping 2 2014-10-01 2014-10-01 false Corrosion (modifies UG- 25). 54.01-35 Section 54.01-35 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PRESSURE VESSELS... weather or mechanical damage are not acceptable. Note: No applied linings except as provided in part UCL...

46 CFR 54.01-35 - Corrosion (modifies UG- 25).

Code of Federal Regulations, 2010 CFR

2010-10-01

... 46 Shipping 2 2010-10-01 2010-10-01 false Corrosion (modifies UG- 25). 54.01-35 Section 54.01-35 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PRESSURE VESSELS... weather or mechanical damage are not acceptable. Note: No applied linings except as provided in Part UCL...

46 CFR 54.01-35 - Corrosion (modifies UG- 25).

Code of Federal Regulations, 2013 CFR

2013-10-01

... 46 Shipping 2 2013-10-01 2013-10-01 false Corrosion (modifies UG- 25). 54.01-35 Section 54.01-35 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING PRESSURE VESSELS... weather or mechanical damage are not acceptable. Note: No applied linings except as provided in part UCL...

Comparing International Curriculum Systems: The International Instructional Systems Study

ERIC Educational Resources Information Center

Creese, Brian; Gonzalez, Alvaro; Isaacs, Tina

2016-01-01

This paper sets out the main findings of the International Instructional Systems Study (IISS), conducted by the UCL Institute of Education and funded by the Center on International Education Benchmarking (CIEB). The study examined the instructional systems and intended curricula of six "high performing" countries and two US states. The…

Queer Inroads: Two Queer Higher Education Symposia Reviews Written Otherwise

ERIC Educational Resources Information Center

Burford, James; Henderson, Emily F.

2015-01-01

This article is a review approached by the authors as a writing experiment of two recent gatherings where queer theory and Higher Education (HE) Studies met: "The Queerly Theorising Higher Education and Academia: Interdisciplinary Conversations" symposium held at the University College London (UCL), Institute of Education (IOE), (London,…

ESTIMATING THE EXPOSURE POINT CONCENTRATION TERM USING PROUCL, VERSION 3.0

EPA Science Inventory

In superfund and RCRA Projects of the U.S. EPA, cleanup, exposure, and risk assessment decisions are often made based upon the mean concentrations of the contaminants of potential concern (COPC). A 95% upper confidence limit (UCL) of the population mean is used to estimate the e...

Chloridobis(ethyl­enediamine-κ2 N,N′)(n-pentyl­amine-κN)cobalt(III) dichloride monhydrate

PubMed Central

Anbalagan, K.; Tamilselvan, M.; Nirmala, S.; Sudha, L.

2009-01-01

The title complex, [CoCl(C5H13N)(C2H8N2)2]Cl2·H2O, comprises one chloridobis(ethyl­enediamine)(n-pentyl­amine)cobalt(III) cation, two chloride counter-anions and a water mol­ecule. The CoIII atom of the complex is hexa­coordinated by five N and one Cl atoms. The five N atoms are from two chelating ethyl­enediamine and one n-pentyl­amine ligands. Neighbouring cations and anions are connected by N—H⋯Cl and N—H⋯O hydrogen bonds to each other and also to the water mol­ecule. PMID:21582753

Ethylenediammonium dication: H-bonded complexes with terephthalate, chloroacetate, phosphite, selenite and sulfamate anions. Detailed vibrational spectroscopic and theoretical studies of ethylenediammonium terephthalate

NASA Astrophysics Data System (ADS)

Marchewka, M. K.; Drozd, M.

2012-12-01

Crystalline complexes between ethylenediammonium dication and terephthalate, chloroacetate, phosphite, selenite and sulfamate anions were obtained by slow evaporation from water solution method. Room temperature powder infrared and Raman measurements were carried out. For ethylenediammonium terephthalate theoretical calculations of structure were performed by two ways: ab-initio HF and semiempirical PM3. In this case the PM3 method gave more accurate structure (closer to X-ray results). The additional PM3 calculations of vibrational spectra were performed. On the basis theoretical approach and earlier vibrational studies of similar compounds the vibrational assignments for observed bands have been proposed. All compounds were checked for second harmonic generation (SHG).

4-(Di­methyl­amino)­pyridinium trichlorido[4-(di­methyl­amino)­pyridine-κN]cobaltate(II)

PubMed Central

Guenifa, Fatiha; Hadjadj, Nasreddine; Zeghouan, Ouahida; Bendjeddou, Lamia; Merazig, Hocine

2013-01-01

In the anion of the title compound, (C7H11N2)[CoCl3(C7H10N2)], the CoII ion is coordinated by one N atom from a 4-(di­methyl­amino)­pyridine (DMAP) ligand and three Cl atoms, forming a CoNCl3 polyhedron with a distorted tetra­hedral geometry. In the crystal, cations and anions are linked via weak N—H⋯Cl and C—H⋯Cl hydrogen bonds. Double layers of complex anions stack along the b- axis direction, which alternate with double layers of 4-(di­methyl­amino)-pyridinium cations. PMID:24046560

Cesium Platinide Hydride 4Cs 2 Pt-CsH: An Intermetallic Double Salt Featuring Metal Anions

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

Smetana, Volodymyr; Mudring, Anja-Verena

2016-10-24

With Cs9Pt4H a new representative of ionic compounds featuring metal anions can be added to this rare-membered family. Cs 9Pt 4H exhibits a complex crystal structure containing Cs + cations, Pt 2- and H - anions. Being a red, transparent compound its band gap is in the visible range of the electromagnetic spectrum and the ionic type of bonding is confirmed by quantum chemical calculations. This cesium platinide hydride can formally be considered as a double salt of the “alloy” cesium–platinum, or better cesium platinide, Cs2Pt, and the salt cesium hydride CsH according to Cs 9Pt 4H≡4 Cs 2Pt∙CsH.

Super-pnicogen bonding in the radical anion of the fluorophosphine dimer

NASA Astrophysics Data System (ADS)

Setiawan, Dani; Cremer, Dieter

2016-10-01

The LUMO of the pnicogen-bonded fluoro-phosphine dimer has PP bonding character. Radical anion and dianion form relatively strong pnicogen bonds with some covalent character where however the dianion turns out to be a second order transition state. The binding energy of (FPH 2)2- is 30.4 kcal/mol (CCSD(T)/aug-cc-pVTZ; CASPT2(5,8): 30.7 kcal/mol) and the bond strength order measured with the local PP bond stretching force constant increases from 0.055 for the neutral dimer to 0.187 thus revealing that the stabilization of the radical anion is to a large extend a result of one-electron six-center delocalization. Pnicogen-bonded complexes have a stabilizing electron affinity.

Superoxide radical anion scavenging and dismutation by some Cu2+ and Mn2+ complexes: A pulse radiolysis study

NASA Astrophysics Data System (ADS)

Joshi, Ravi

2017-10-01

Copper (Cu) and manganese (Mn) ions are catalytic centers, in complexed form, in scavenging and dismutation process of superoxide radicals anion (O2.-) by superoxide dismutase enzyme. In the present work, fast reaction kinetics and mechanism of scavenging and dismutation of O2.- by Cu2+, Mn2+ and their complexes formed with some natural ligands have been studied using pulse radiolysis technique. Catechol, gentisic acid, tetrahydroxyquinone, tyrosine, tryptophan, embelin and bilirubin have been used as low molecular weight natural ligands for Cu2+ and Mn2+ to understand superoxide radical scavenging and dismutation reactions. These complexes have been found to be efficient scavengers of O2.- (k 107-109 M-1 s-1). The effects of nature of metal ion and ligand, and stoichiometry of complex on scavenging reaction rate constants are reported. Higher scavenging rate constants have been observed with complexes of: (1) Cu2+ as compared to Mn2+, and (2) at [ligand]/[metal] ratio of one as compared to two. A clear evidence of O2.- dismutation by free metal ions and some of the complexes has been observed. The study suggests that complexes of Cu2+ and Mn2+ with small natural ligands can also act as SOD mimics.

A New Bis(aquated) High Relaxivity Mn(II) Complex as an Alternative to Gd(III)-Based MRI Contrast Agent.

PubMed

Phukan, Bedika; Mukherjee, Chandan; Goswami, Upashi; Sarmah, Amrit; Mukherjee, Subhajit; Sahoo, Suban K; Moi, Sankar Ch

2018-03-05

Disclosed here are a piperazine, a pyridine, and two carboxylate groups containing pentadentate ligand H 2 pmpa and its corresponding water-soluble Mn(II) complex (1). DFT-based structural optimization implied that the complex had pentagonal bipyramidal geometry where the axial positions were occupied by two water molecules, and the equatorial plane was constituted by the ligand ON 3 O donor set. Thus, a bis(aquated) disc-like Mn(II) complex has been synthesized. The complex showed higher stability compared with Mn(II)-EDTA complex [log K MnL = 14.29(3)] and showed a very high r 1 relaxivity value of 5.88 mM -1 s -1 at 1.41 T, 25 °C, and pH = 7.4. The relaxivity value remained almost unaffected by the pH of the medium in the range of 6-10. Although the presence of 200 equiv of fluoride and bicarbonate anions did not affect the relaxivity value appreciably, an increase in the value was noticed in the presence of phosphate anion due to slow tumbling of the complex. Cell viability measurements, as well as phantom MR images using clinical MRI imager, consolidated the possible candidature of complex 1 as a positive contrast agent.

Sorption behavior of the Pt(II) complex anion on manganese dioxide (δ-MnO2): a model reaction to elucidate the mechanism by which Pt is concentrated into a marine ferromanganese crust

NASA Astrophysics Data System (ADS)

Maeno, Mamiko Yamashita; Ohashi, Hironori; Yonezu, Kotaro; Miyazaki, Akane; Okaue, Yoshihiro; Watanabe, Koichiro; Ishida, Tamao; Tokunaga, Makoto; Yokoyama, Takushi

2016-02-01

It is difficult to directly investigate the chemical state of Pt in marine ferromanganese crusts (a mixture of hydrous iron(III) oxide and manganese dioxide (δ-MnO2)) because it is present at extremely low concentration levels. This paper attempts to elucidate the mechanism by which Pt is concentrated into marine ferromanganese crust from the Earth's continental crust through ocean water. In this investigation, the sorption behavior of the Pt(II) complex ions on the surface of the δ-MnO2 that is a host of Pt was examined as a model reaction. The δ-MnO2 sorbing Pt was characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) to determine the chemical state of the Pt. Hydrolytic Pt(II) complex ions were specifically sorbed above pH 6 by the formation of a Mn-O-Pt bond. XPS spectra and XANES spectra for δ-MnO2 sorbing Pt showed that the sorbed Pt(II) was oxidized to Pt(IV) on δ-MnO2. The extended X-ray absorption fine structure (EXAFS) analysis showed that the coordination structure of Pt sorbed on δ-MnO2 is almost the same as that of the [Pt(OH)6]2- complex ion used as a standard. Therefore, the mechanism for the concentration of Pt in marine ferromanganese crust may be an oxidative substitution (penetration of Pt(IV) into structure of δ-MnO2) by a reduction-oxidation reaction between Pt(II) in [PtCl4-n(OH)n]2- and Mn(IV) in δ-MnO2 through a Mn-O-Pt bond.

Tetraammine(carbonato-κ2 O,O′)cobalt(III) perchlorate

PubMed Central

Mohan, Singaravelu Chandra; Jenniefer, Samson Jegan; Muthiah, Packianathan Thomas; Jothivenkatachalam, Kandasamy

2013-01-01

In the title complex, [Co(CO3)(NH3)4]ClO4, both the cation and anion lie on a mirror plane. The CoIII ion is coordinated by two NH3 ligands and a chelating carbonato ligand in the equatorial sites and by two NH3 groups in the axial sites, forming a distorted octa­hedral geometry. In the crystal, N—H⋯O hydrogen bonds connect the anions and cations, forming a three-dimensional network. PMID:24109252

Poly(vinyl alcohol) composite films with high percent elongation prepared from amylose-fatty ammonium salt inclusion complexes

USDA-ARS?s Scientific Manuscript database

Amylose inclusion complexes prepared from cationic fatty ammonium salts and jet-cooked high amylose starch were combined with poly(vinyl alcohol) (PVOH) to form glycerol-plasticized films. Their tensile properties were compared with similar films prepared previously with analogous anionic fatty acid...

Unusual bridging of three nitrates with two bridgehead protons in an octaprotonated azacryptand

PubMed Central

Saeed, Musabbir A.; Fronczek, Frank R.; Huang, Ming-Ju; Hossain, Md. Alamgir

2010-01-01

Structural analysis of the nitrate complex of a thiophene-based azacryptand suggests that three nitrates are bridged with two bridgehead protons which play the topological role of two transition metal ions in a classical Werner type coordination complex bridging three anions. PMID:20066306

Structures of M2(SO2)6B12F12 (M = Ag or K) and Ag2(H2O)4B12F12: Comparison of the Coordination of SO2 versus H2O and of B12F122- versus Other Weakly Coordinating Anions to Metal Ions in the Solid State.

PubMed

Malischewski, Moritz; Peryshkov, Dmitry V; Bukovsky, Eric V; Seppelt, Konrad; Strauss, Steven H

2016-12-05

The structures of three solvated monovalent cation salts of the superweak anion B 12 F 12 2- (Y 2- ), K 2 (SO 2 ) 6 Y, Ag 2 (SO 2 ) 6 Y, and Ag 2 (H 2 O) 4 Y, are reported and discussed with respect to previously reported structures of Ag + and K + with other weakly coordinating anions. The structures of K 2 (SO 2 ) 6 Y and Ag 2 (SO 2 ) 6 Y are isomorphous and are based on expanded cubic close-packed arrays of Y 2- anions with M(OSO) 6 + complexes centered in the trigonal holes of one expanded close-packed layer of B 12 centroids (⊙). The K + and Ag + ions have virtually identical bicapped trigonal prism MO 6 F 2 coordination spheres, with M-O distances of 2.735(1)-3.032(2) Å for the potassium salt and 2.526(5)-2.790(5) Å for the silver salt. Each M(OSO) 6 + complex is connected to three other cationic complexes through their six μ-SO 2 -κ 1 O,κ 2 O' ligands. The structure of Ag 2 (H 2 O) 4 Y is unique [different from that of K 2 (H 2 O) 4 Y]. Planes of close-packed arrays of anions are offset from neighboring planes along only one of the linear ⊙···⊙···⊙ directions of the close-packed arrays, with [Ag(μ-H 2 O) 2 Ag(μ-H 2 O) 2 )] ∞ infinite chains between the planes of anions. There are two nearly identical AgO 4 F 2 coordination spheres, with Ag-O distances of 2.371(5)-2.524(5) Å and Ag-F distances of 2.734(4)-2.751(4) Å. This is only the second structurally characterized compound with four H 2 O molecules coordinated to a Ag + ion in the solid state. Comparisons with crystalline H 2 O and SO 2 solvates of other Ag + and K + salts of weakly coordinating anions show that (i) N[(SO 2 ) 2 (1,2-C 6 H 4 )] - , BF 4 - , SbF 6 - , and Al(OC(CF 3 ) 3 ) 4 - coordinate much more strongly to Ag + than does Y 2- , (ii) SnF 6 2- coordinates somewhat more strongly to K + than does Y 2- , and (iii) B 12 Cl 12 2- coordinates to K + about the same as, if not slightly weaker than, Y 2- .

Influence of Structure, Charge, and Concentration on the Pectin-Calcium-Surfactant Complexes.

PubMed

Joshi, Nidhi; Rawat, Kamla; Bohidar, H B

2016-05-12

Polymer-surfactant complex formation of pectin with different types of surfactants, cationic (cetyltrimethylammonium bromide, CTAB and dodecyl trimethylammonium bromide, DTAB), anionic (sodium dodecyl sulfate, SDS), and neutral (Triton X-100, TX-100), was investigated at room temperature in the presence and absence of cross-linker calcium chloride using light scattering, zeta potential, rheology, and UV-vis spectroscopic measurements where the surfactant concentration was maintained below their critical micellar concentration (CMC). Results indicated that the interaction of cationic surfactant with pectin in the presence and absence of calcium chloride was much stronger compared to anionic and neutral surfactants. The neutral surfactant showed identifiable interaction despite the absence of any charged headgroup, while anionic surfactant showed feeble or very weak interaction with the polymer. The pectin-CTAB or DTAB complex formation was attributed to associative electrostatic and hydrophobic interactions. On comparison between the cationic surfactants, it was found that CTAB interacts strongly with pectin because of its long hydrocarbon chain. The morphology of complexes formed exhibited random coil structures while at higher concentration of surfactant, rod-like or extended random coil structures were noticed. Thus, functional characteristics of the complex could be tuned by varying the type of surfactant (charge and structure) and its concentration. The differential network rigidity (pectin-CTAB versus pectin-DTAB gels) obtained from rheology measurements showed that addition of a very small amount of surfactant (concentration ≪ CMC) was required for enhancing network strength, while the presence of a large amount of surfactant resulted in the formation of fragile gels. No gel formation occurred when the surfactant concentration was close to their CMC values. Considering the importance of pectin in food and pharmaceutical industry, this study is relevant.

Unsaturated Mn complex decorated hybrid thioarsenates: Syntheses, crystal structures and physical properties

NASA Astrophysics Data System (ADS)

Yue, Cheng-Yang; Lei, Xiao-Wu; Tian, Ya-Wei; Xu, Jing; Bai, Yi-Qun; Wang, Fei; Zhou, Peng-Fei; Liu, Xiao-Fan; Yi, Fei-Yan

2016-03-01

The incorporation of unsaturated [Mn(1,2-dap)]2+, [Mn(1,2-dap)2]2+, [Mn(2,2-bipy)]2+ (1,2-dap=1,2-diaminopropane) complex cations with thioarsenate anions of [AsIIIS3]3- and [AsVS4]3- led to three new hybrid manganese thioarsenates, namely, [Mn(1,2-dap)]2MnAs2S6 (1), [Mn(1,2-dap)2]{[Mn(1,2-dap)]2As2S8} (2) and (NH4)[Mn(2,2-bipy)2]AsS4 (3). In compound 1, the unsaturated [Mn(1,2-dap)]2+ complexes, [MnS4]6- tetrahedra and [AsIIIS3]3- trigonal-pyramids are condensed to form the 1D [Mn(1,2-dap)]2MnAs2S6 chain, whereas compound 2 features 2D layer composed of [Mn(1,2-dap)]2+ and [Mn(1,2-dap)2]2+ complexes as well as [AsVS4]3- tetrahedral units. For compound 3, two [AsVS4]3- anions bridge two [Mn(2,2-bipy)]2+ complex cations into a butterfly like {[Mn(2,2-bipy)]2As2S8}2- anionic unit. Magnetic measurements indicate the ferrimagnetic behavior for compound 1 and antiferromagnetic (AF) behaviors for compounds 2-3. The UV-vis diffuse-reflectance measurements and electronic structural calculations based on density functional theory (DFT) revealed the title compounds belong to semiconductors with band gaps of 2.63, 2.21, and 1.97 eV, respectively. The narrow band-gap of compound 3 led to the efficient and stable photocatalytic degradation activity over organic pollutant than N-doped P25 under visible light irradiation.

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

Zhou, Yan; Dyck, Jeffrey; Graham, Todd

Oil-soluble phosphonium-based ionic liquids (ILs) have recently been reported as potential ashless lubricant additives. This study is to expand the IL chemistry envelope and to achieve fundamental correlations between the ion structures and ILs’ physiochemical and tribological properties. Here we present eight ILs containing two different phosphonium cations and seven different anions from three groups: organophosphate, carboxylate, and sulfonate. The oil solubility of ILs seems largely governed by the IL molecule size and structure complexity. When used as oil additives, the ranking of effectiveness in wear protection for the anions are: organophosphate > carboxylate > sulfonate. All selected ILs outperformedmore » a commercial ashless anti-wear additive. Surface characterization from the top and the cross-section revealed the nanostructures and compositions of the tribo-films formed by the ILs. Some fundamental insights were achieved: branched and long alkyls improve the IL’s oil solubility, anions of a phosphonium-phosphate IL contribute most phosphorus in the tribofilm, and carboxylate anions, though free of P, S, N, or halogen, can promote the formation of an anti-wear tribofilm.« less

Enhanced liquid-liquid anion exchange using macrocyclic anion receptors: effect of receptor structure on sulphate-nitrate exchange selectivity

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

Moyer, Bruce A; Sloop Jr, Frederick; Fowler, Christopher J

2010-01-01

When certain macrocyclic anion receptors are added to a chloroform solution of the nitrate form of a lipophilic quaternary ammonium salt (methyltri-C8,10-ammonium nitrate, Aliquat 336N), the extraction of sulphate from an aqueous sodium nitrate solution via exchange with the organic-phase nitrate is significantly enhanced. Eight macrocycles were surveyed, including two derivatives of a tetraamide macrocycle, five derivatives of calix[4]pyrrole and -decafluorocalix[5]pyrrole. Under the hypothesis that the enhancement originates from sulphate binding by the anion receptors in the chloroform phase, it was possible to obtain reasonable fits to the sulphate distribution survey data based on the formation of 1:1 and 2:1more » receptor:sulphate complexes in the chloroform phase. Apparent 1:1 sulphate-binding constants obtained from the model in this system fell in the range . Comparison of the results for the various anion receptors included in this study reveals that sulphate binding is sensitive to the nature of the substituents on the parent macrocycle scaffolds in a way that does not follow straightforwardly from simple chemical expectations, such as electron-withdrawing effects on hydrogen-bond donor strength.« less

Can collision-induced negative-ion fragmentations of [M-H](-) anions be used to identify phosphorylation sites in peptides?

PubMed

Tran, T T Nha; Wang, Tianfang; Hack, Sandra; Hoffmann, Peter; Bowie, John H

2011-12-15

A joint experimental and theoretical investigation of the fragmentation behaviour of energised [M-H](-) anions from selected phosphorylated peptides has confirmed some of the most complex rearrangement processes yet to be reported for peptide negative ions. In particular: pSer and pThr (like pTyr) may transfer phosphate groups to C-terminal carboxyl anions and to the carboxyl anion side chains of Asp and Glu, and characteristic nucleophilic/cleavage reactions accompany or follow these rearrangements. pTyr may transfer phosphate to the side chains of Ser and Thr. The reverse reaction, namely transfer of a phosphate group from pSer or pThr to Tyr, is energetically unfavourable in comparison. pSer can transfer phosphate to a non-phosphorylated Ser. The non-rearranged [M-H](-) species yields more abundant product anions than its rearranged counterpart. If a peptide containing any or all of Ser, Thr and Tyr is not completely phosphorylated, negative-ion cleavages can determine the number of phosphated residues, and normally the positions of Ser, Thr and Tyr, but not which specific residues are phosphorylated. This is in accord with comments made earlier by Lehmann and coworkers. Copyright © 2011 John Wiley & Sons, Ltd.

Tandem mass spectrometry characteristics of polyester anions and cations formed by electrospray ionization.

PubMed

Arnould, Mark A; Buehner, Rita W; Wesdemiotis, Chrys; Vargas, Rafael

2005-01-01

Electrospray ionization of polyesters composed of isophthalic acid and neopentyl glycol produces carboxylate anions in negative mode and mainly sodium ion adducts in positive mode. A tandem mass spectrometry (MS/MS) study of these ions in a quadrupole ion trap shows that the collisionally activated dissociation pathways of the anions are simpler than those of the corresponding cations. Charge-remote fragmentations predominate in both cases, but the spectra obtained in negative mode are devoid of the complicating cation exchange observed in positive mode. MS/MS of the Na(+) adducts gives rise to a greater number of fragments but not necessarily more structural information. In either positive or negative mode, polyester oligomers with different end groups fragment by similar mechanisms. The observed fragments are consistent with rearrangements initiated by the end groups. Single-stage ESI mass spectra also are more complex in positive mode because of extensive H/Na substitutions; this is also true for matrix-assisted laser desorption ionization (MALDI) mass spectra. Hence, formation and analysis of anions might be the method of choice for determining block length, end group structure and copolymer sequence, provided the polyester contains at least one carboxylic acid end group that is ionizable to anions.

Effects of microsolvation on uracil and its radical anion: Uracil.(H2O)n (n=1-5)

NASA Astrophysics Data System (ADS)

Kim, Sunghwan; Schaefer, Henry F.

2006-10-01

Microsolvation effects on the stabilities of uracil and its anion have been investigated by explicitly considering the structures of complexes of uracil with up to five water molecules at the B3LYP /DZP++ level of theory. For all five systems, the global minimum of the neutral cluster has a different equilibrium geometry from that of the radical anion. Both the vertical detachment energy (VDE) and adiabatic electron affinity (AEA) of uracil are predicted to increase gradually with the number of hydrating molecules, qualitatively consistent with experimental results from a photodetachment-photoelectron spectroscopy study [J. Schiedt et al., Chem. Phys. 239, 511 (1998)]. The trend in the AEAs implies that while the conventional valence radical anion of uracil is only marginally bound in the gas phase, it will form a stable anion in aqueous solution. The gas-phase AEA of uracil (0.24eV) was higher than that of thymine by 0.04eV and this gap was not significantly affected by microsolvation. The largest AEA is that predicted for uracil•(H2O)5, namely, 0.96eV. The VDEs range from 0.76to1.78eV.

Effects of microsolvation on uracil and its radical anion: uracil(H2O)n (n = 1-5).

PubMed

Kim, Sunghwan; Schaefer, Henry F

2006-10-14

Microsolvation effects on the stabilities of uracil and its anion have been investigated by explicitly considering the structures of complexes of uracil with up to five water molecules at the B3LYPDZP++ level of theory. For all five systems, the global minimum of the neutral cluster has a different equilibrium geometry from that of the radical anion. Both the vertical detachment energy (VDE) and adiabatic electron affinity (AEA) of uracil are predicted to increase gradually with the number of hydrating molecules, qualitatively consistent with experimental results from a photodetachment-photoelectron spectroscopy study [J. Schiedt et al., Chem. Phys. 239, 511 (1998)]. The trend in the AEAs implies that while the conventional valence radical anion of uracil is only marginally bound in the gas phase, it will form a stable anion in aqueous solution. The gas-phase AEA of uracil (0.24 eV) was higher than that of thymine by 0.04 eV and this gap was not significantly affected by microsolvation. The largest AEA is that predicted for uracil(H2O)5, namely, 0.96 eV. The VDEs range from 0.76 to 1.78 eV.