Theoretical investigation of M@Pb122- and M@Sn122- Zintl clusters (M = Lrn+, Lun+, La3+, Ac3+ and n = 0, 1, 2, 3).

PubMed

Joshi, Meenakshi; Chandrasekar, Aditi; Ghanty, Tapan K

2018-06-06

The positions of lawrencium (Lr), lutetium (Lu), actinium (Ac) and lanthanum (La) in the periodic table have been a controversial topic for quite some time. According to studies carried out by different groups with their justifications, these elements may potentially be placed in the d-block, p-block or all four in a 15 element f-block. The present work looks into this issue from a new perspective, which involves encapsulation of these four elements into Zintl ion clusters, Pb122- and Sn122-, followed by the determination of the structural, thermodynamic and electronic properties of these endohedral M@Pb122- and M@Sn122- clusters (M = Lrn+, Lun+ with n = 0, 1, 2, 3) using first principles based density functional theory (DFT). These parameters are compared with similar clusters encapsulated La3+ and Ac3+ ions in order to seek out similarities and differences to draw conclusions about their placement in the periodic table. For the first time the structural, energetic, and electronic properties of these metal atom/ion encapsulated Pb122- and Sn122- clusters have been investigated thoroughly. Structural parameters such as bond distances, geometry and symmetry, electronic properties viz. the density of states, the molecular orbital ordering, the electron localization function, bond critical point properties and charge distributions have been analyzed. Additionally, the thermodynamic property of the binding energy during the encapsulation process has also been calculated. All M@Pb12+ and M@Sn12+ (M = Lr and Lu) clusters form stable 18 bonding electron magic number systems with shell closing. They show negative values of binding energy and relatively large HOMO-LUMO energy gaps indicating the stability of such clusters. All the calculated parameters for Lr encapsulated clusters closely match with the corresponding calculated parameters of Lu encapsulated clusters, confirming the similarity between Lr and Lu metal atoms in various oxidation states, though their atomic

Structurally complex Zintl compounds for high temperature thermoelectric power generation

NASA Astrophysics Data System (ADS)

Zevalkink, Alexandra; Pomrehn, Gregory; Gibbs, Zachary; Snyder, Jeffrey

2014-03-01

Zintl phases, characterized by covalently-bonded substructures surrounded by highly electropositive cations, exhibit many of the characteristics desired for thermoelectric applications. Recently, we demonstrated promising thermoelectric performance (zT values between 0.4 and 0.9) in a class of Zintl antimonides that share a common structural motif: anionic moieties resembling infinite chains of linked tetrahedra. These compounds (A5M2 Sb6 and A3 M Sb3 compounds where A = Ca or Sr and M = Al, Ga and In) crystallize as four distinct, but closely related chain-forming structure types. Their large unit cells lead to exceptionally low lattice thermal conductivity due to the containment of heat in low velocity optical phonon modes. Here, we show that chemical substitutions on the A and M sites can be used to control the electronic and thermal transport properties and optimize the thermoelectric figure of merit. Doping with alio-valent elements allows for rational control of the carrier concentration, while isoelectronic substitutions can be used to fine-tune the intrinsic properties. A combination of Density Functional calculations and classical transport models was used to explain the experimentally observed transport properties of these compounds.

Lithiation-induced zinc clustering of Zn 3, Zn 12, and Zn 18 units in Zintl-like Ca ~30Li 3+xZn 60-x (x=0.44-1.38)

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

Lin, Qisheng

2014-11-14

Zinc clusters are not common for binary intermetallics with relatively low zinc content, but this work shows that zinc clustering can be triggered by lithiation, as exemplified by Ca ~30Li 3+xZn 60-x, P6/mmm, Z = 1, which can be directly converted from CaZn 2. Two end members of the solid solution (x = 0.44 and 1.38) were established and structurally characterized by single-crystal X-ray diffraction analyses: Ca 30Li 3.44(6)Zn59.56(6), a = 15.4651(9) Å, c = 9.3898(3) Å; Ca 30.45(2)Li 4.38(6)Zn 58.62(6), a = 15.524(3) Å, c = 9.413(2) Å. The structures of Ca ~30Li 3+xZn 60-x feature a condensed anionicmore » network of Zn3 triangles, lithium-centered Zn12 icosahedra, and arachno-(Zn,Li)18 tubular clusters that are surrounded respectively by Ca 14, Ca 20, and Ca 30 polyhedra. These polyhedra share faces and form a clathrate-like cationic framework. The specific occupation of lithium in the structure is consistent with theoretical “coloring” analyses. Analysis by the linear muffin-tin orbital (LMTO) method within the atomic sphere approximation reveals that Ca ~30Li 3+xZn 60-x is a metallic, Zintl-like phase with an open-shell electronic structure. The contribution of Ca–Zn polar covalent interactions is about 41%.« less

Electron-induced chemistry in imidazole clusters embedded in helium nanodroplets

NASA Astrophysics Data System (ADS)

Kuhn, Martin; Raggl, Stefan; Martini, Paul; Gitzl, Norbert; Darian, Masoomeh Mahmoodi; Goulart, Marcelo; Postler, Johannes; Feketeová, Linda; Scheier, Paul

2018-02-01

Electron-induced chemistry in imidazole (IMI) clusters embedded in helium nanodroplets (with an average size of 2 × 105 He atoms) has been investigated with high-resolution time-of-flight mass spectrometry. The formation of both, negative and positive, ions was monitored as a function of the cluster size n. In both ion spectra a clear series of peaks with IMI cluster sizes up to at least 25 are observed. While the anions are formed by collisions of IMI n with He*-, the cations are formed through ionization of IMI n by He+ as the measured onset for the cation formation is observed at 24.6 eV (ionization energy of He). The most abundant series of anions are dehydrogenated anions IMI n-1(IMI-H)-, while other anion series are IMI clusters involving CN and C2H4 moieties. The formation of cations is dominated by the protonated cluster ions IMI n H+, while the intensity of parent cluster cations IMI n + is also observed preferentially for the small cluster size n. The observation of series of cluster cations [IMI n CH3]+ suggests either CH3+ cation to be solvated by n neutral IMI molecules, or the electron-induced chemistry has led to the formation of protonated methyl-imidazole solvated by ( n - 1) neutral IMI molecules.

Revealing the optoelectronic and thermoelectric properties of the Zintl quaternary arsenides ACdGeAs{sub 2} (A = K, Rb)

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

Azam, Sikander; Khan, Saleem Ayaz; Goumri-Said, Souraya, E-mail: Souraya.Goumri-Said@chemistry.gatech.edu

Highlights: • Zintl tetragonal phase ACdGeAs{sub 2} (A = K, Rb) are chalcopyrite and semiconductors. • Their direct band gap is suitable for PV, optolectronic and thermoelectric applications. • Combination of DFT and Boltzmann transport theory is employed. • The present arsenides are found to be covalent materials. - Abstract: Chalcopyrite semiconductors have attracted much attention due to their potential implications in photovoltaic and thermoelectric applications. First principle calculations were performed to investigate the electronic, optical and thermoelectric properties of the Zintl tetragonal phase ACdGeAs{sub 2} (A = K, Rb) using the full potential linear augmented plane wave method andmore » the Engle–Vosko GGA (EV–GGA) approximation. The present compounds are found semiconductors with direct band gap and covalent bonding character. The optical transitions are investigated via the dielectric function (real and imaginary parts) along with other related optical constants including refractive index, reflectivity and energy-loss spectrum. Combining results from DFT and Boltzmann transport theory, we reported the thermoelectric properties such as the Seebeck’s coefficient, electrical and thermal conductivity, figure of merit and power factor as function of temperatures. The present chalcopyrite Zintl quaternary arsenides deserve to be explored for their potential applications as thermoelectric materials and for photovoltaic devices.« less

Globular cluster chemistry in fast-rotating dwarf stars belonging to intermediate-age open clusters

NASA Astrophysics Data System (ADS)

Pancino, Elena

2018-06-01

The peculiar chemistry observed in multiple populations of Galactic globular clusters is not generally found in other systems such as dwarf galaxies and open clusters, and no model can currently fully explain it. Exploring the boundaries of the multiple-population phenomenon and the variation of its extent in the space of cluster mass, age, metallicity, and compactness has proven to be a fruitful line of investigation. In the framework of a larger project to search for multiple populations in open clusters that is based on literature and survey data, I found peculiar chemical abundance patterns in a sample of intermediate-age open clusters with publicly available data. More specifically, fast-rotating dwarf stars (v sin i ≥ 50 km s-1) that belong to four clusters (Pleiades, Ursa Major, Come Berenices, and Hyades) display a bimodality in either [Na/Fe] or [O/Fe], or both, with the low-Na and high-O peak more populated than the high-Na and low-O peak. Additionally, two clusters show a Na-O anti-correlation in the fast-rotating stars, and one cluster shows a large [Mg/Fe] variation in stars with high [Na/Fe], reaching the extreme Mg depletion observed in NGC 2808. Even considering that the sample sizes are small, these patterns call for attention in the light of a possible connection with the multiple population phenomenon of globular clusters. The specific chemistry observed in these fast-rotating dwarf stars is thought to be produced by a complex interplay of different diffusion and mixing mechanisms, such as rotational mixing and mass loss, which in turn are influenced by metallicity, binarity, mass, age, variability, and so on. However, with the sample in hand, it was not possible to identify which stellar parameters cause the observed Na and O bimodality and Na-O anti-correlation. This suggests that other stellar properties might be important in addition to stellar rotation. Stellar binarity might influence the rotational properties and enhance rotational

Contribution of radiation chemistry to the study of metal clusters.

PubMed

Belloni, J

1998-11-01

Radiation chemistry dates from the discovery of radioactivity one century ago by H. Becquerel and P. and M. Curie. The complex phenomena induced by ionizing radiation have been explained progressively. At present, the methodology of radiation chemistry, particularly in the pulsed mode, provides a powerful means to study not only the early processes after the energy absorption, but more generally a broad diversity of chemical and biochemical reaction mechanisms. Among them, the new area of metal cluster chemistry illustrates how radiation chemistry contributed to this field in suggesting fruitful original concepts, in guiding and controlling specific syntheses, and in the detailed elaboration of the mechanisms of complex and long-unsolved processes, such as the dynamics of nucleation, electron transfer catalysis and photographic development.

Synthetic modeling chemistry of iron-sulfur clusters in nitric oxide signaling.

PubMed

Fitzpatrick, Jessica; Kim, Eunsuk

2015-08-18

Nitric oxide (NO) is an important signaling molecule that is involved in many physiological and pathological functions. Iron-sulfur proteins are one of the main reaction targets for NO, and the [Fe-S] clusters within these proteins are converted to various iron nitrosyl species upon reaction with NO, of which dinitrosyl iron complexes (DNICs) are the most prevalent. Much progress has been made in identifying the origin of cellular DNIC generation. However, it is not well-understood which other products besides DNICs may form during [Fe-S] cluster degradation nor what effects DNICs and other degradation products can have once they are generated in cells. Even more elusive is an understanding of the manner by which cells cope with unwanted [Fe-S] modifications by NO. This Account describes our synthetic modeling efforts to identify cluster degradation products derived from the [2Fe-2S]/NO reaction in order to establish their chemical reactivity and repair chemistry. Our intent is to use the chemical knowledge that we generate to provide insight into the unknown biological consequences of cluster modification. Our recent advances in three different areas are described. First, new reaction conditions that lead to the formation of previously unrecognized products during the reaction of [Fe-S] clusters with NO are identified. Hydrogen sulfide (H2S), a gaseous signaling molecule, can be generated from the reaction between [2Fe-2S] clusters and NO in the presence of acid or formal H• (e(-)/H(+)) donors. In the presence of acid, a mononitrosyl iron complex (MNIC) can be produced as the major iron-containing product. Second, cysteine analogues can efficiently convert MNICs back to [2Fe-2S] clusters without the need for any other reagents. This reaction is possible for cysteine analogues because of their ability to labilize NO from MNICs and their capacity to undergo C-S bond cleavage, providing the necessary sulfide for [2Fe-2S] cluster formation. Lastly, unique dioxygen

A cluster ion chemistry for the mesospheric sodium layer

NASA Technical Reports Server (NTRS)

Richter, E. S.; Sechrist, C. F., Jr.

1979-01-01

A cluster ion chemistry for sodium is developed which relates the Na(+) profile to the Na profile using reactions involving Na(+).N2, Na(+).CO2, and Na(+).H2O. Removal of sodium from the mesosphere is accomplished by the formation of higher order clusters of the form Na(+).(H2O)n which presumably precipitate to the lower atmosphere. This sink is most effective in the 80-85 km altitude range. The chemical equilibrium model is applied to experimental observations of the Na and Na(+) layers.

Identifying At-Risk Students in General Chemistry via Cluster Analysis of Affective Characteristics

ERIC Educational Resources Information Center

Chan, Julia Y. K.; Bauer, Christopher F.

2014-01-01

The purpose of this study is to identify academically at-risk students in first-semester general chemistry using affective characteristics via cluster analysis. Through the clustering of six preselected affective variables, three distinct affective groups were identified: low (at-risk), medium, and high. Students in the low affective group…

Electron-induced chemistry in microhydrated sulfuric acid clusters

NASA Astrophysics Data System (ADS)

Lengyel, Jozef; Pysanenko, Andriy; Fárník, Michal

2017-11-01

We investigate the mixed sulfuric acid-water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT) calculations. The microhydration of (H2SO4)m(H2O)n clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4)m(H2O)nHSO4- and (H2O)nH2SO4-. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4- ṡ ṡ ṡ H3O+) formation in the neutral H2SO4(H2O)n clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO4)2(H2O)n this process starts as early as n ≥ 2 water molecules. The (H2SO4)m(H2O)nHSO4- clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4- ṡ ṡ ṡ H3O+) ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2O)nH2SO4- cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid-water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid-water aerosols are discussed.

Higher thermoelectric performance of Zintl phases (Eu0.5Yb0.5)1-xCaxMg2Bi2 by band engineering and strain fluctuation.

PubMed

Shuai, Jing; Geng, Huiyuan; Lan, Yucheng; Zhu, Zhuan; Wang, Chao; Liu, Zihang; Bao, Jiming; Chu, Ching-Wu; Sui, Jiehe; Ren, Zhifeng

2016-07-19

Complex Zintl phases, especially antimony (Sb)-based YbZn0.4Cd1.6Sb2 with figure-of-merit (ZT) of ∼1.2 at 700 K, are good candidates as thermoelectric materials because of their intrinsic "electron-crystal, phonon-glass" nature. Here, we report the rarely studied p-type bismuth (Bi)-based Zintl phases (Ca,Yb,Eu)Mg2Bi2 with a record thermoelectric performance. Phase-pure EuMg2Bi2 is successfully prepared with suppressed bipolar effect to reach ZT ∼ 1. Further partial substitution of Eu by Ca and Yb enhanced ZT to ∼1.3 for Eu0.2Yb0.2Ca0.6Mg2Bi2 at 873 K. Density-functional theory (DFT) simulation indicates the alloying has no effect on the valence band, but does affect the conduction band. Such band engineering results in good p-type thermoelectric properties with high carrier mobility. Using transmission electron microscopy, various types of strains are observed and are believed to be due to atomic mass and size fluctuations. Point defects, strain, dislocations, and nanostructures jointly contribute to phonon scattering, confirmed by the semiclassical theoretical calculations based on a modified Debye-Callaway model of lattice thermal conductivity. This work indicates Bi-based (Ca,Yb,Eu)Mg2Bi2 is better than the Sb-based Zintl phases.

Structural and thermoelectric properties of zintl-phase CaLiPn (Pn=As, Sb, Bi)

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

Chandran, Anoop K.; Gudelli, Vijay Kumar; Sreeparvathy, P.C.

First-principles calculations were carried out to study the structural, mechanical, dynamical and transport properties of zintl phase materials CaLiPn (Pn=As, Sb and Bi). We have used two different approaches to solve the system based on density functional theory. The plane wave pseudopotential approach has been used to study the structural and dynamical properties whereas, full potential linear augment plane wave method is used to examine the electronic structure, mechanical and thermoelectric properties. The calculated ground-state properties agree quite well with experimental values. The computed electronic structure shows the investigated compounds to be direct band gap semiconductors. Further, we have calculatedmore » the thermoelectric properties of all the investigated compounds for both the carriers at various temperatures. We found a high thermopower for both the carriers, especially n-type doping to be more favourable, which enabled us to predict that CaLiPn might have promising applications as a good thermoelectric material. Further, the phonon dispersion curves of the investigated compounds showed flat phonon modes and we also find lower optical and acoustic modes to cut each other at the lower frequency range, which further indicate the investigated compounds to possess reasonably low thermal conductivity. We have also analysed the low value of the thermal conductivity through the empirical relations and discussions are presented here. - Highlights: • Electronic band structure and chemical bonding. • Single crystalline elastic constants and poly crystalline elastic moduli. • Thermoelectric properties of zintl phase. • Lattice dynamics and phonon density of states.« less

Bonding in Some Zintl Phases: A Study by Tin-119 Mössbauer Spectroscopy

NASA Astrophysics Data System (ADS)

Asbrand, M.; Berry, F. J.; Eisenmann, B.; Kniep, R.; Smart, L. E.; Thied, R. C.

1995-09-01

The 119Sn Mössbauer parameters for a range of Zintl phase compounds are reported. The compounds containing tetrahedrally coordinated tin of composition M5SnX3 (M = Na, K; X = P, As, Sb) have chemical isomer shifts close to that of grey-tin and can be considered to be covalently bonded species. The layer structures of composition KSnX (X = As, Sb) and double-layer compounds M Sn2X2 (M = Na, Sr; X = As, Sb) have tin in a distorted octahedral environment. The chemical isomer shifts are closer to that of white-tin and can be interpreted in terms of metallic bonding.

On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

NASA Astrophysics Data System (ADS)

Turi, László

2016-04-01

We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.

On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

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

Turi, László, E-mail: turi@chem.elte.hu

2016-04-21

We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions withmore » n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.« less

Na(23)K(9)Tl(15.3): An Unusual Zintl Compound Containing Apparent Tl(5)(7)(-), Tl(4)(8)(-), Tl(3)(7)(-), and Tl(5)(-) Anions.

PubMed

Dong, Zhen-Chao; Corbett, John D.

1996-05-22

Reaction of the neat elements in tantalum containers at 400 degrees C and then 150 degrees C gives the pure title phase. X-ray crystallography shows that the hexagonal structure (P6(3)/mmc, Z = 2, a = 11.235(1) Å, b = 30.133(5) Å) contains relatively high symmetry clusters Tl(5)(7)(-) (D(3)(h)()), Tl(4)(8)(-) (C(3)(v)(), approximately T(d)), and the new Tl(3)(7)(-) (D(infinity)(h)()) plus Tl(5)(-), the last two disordered over the same elongated site in 1:2 proportions. Cation solvation of these anions is tight and specific, providing good Coulombic trapping of weakly bound electrons on the isolated cluster anions. The observed disorder makes the compound structurally a Zintl phase with a closed shell electron count. EHMO calculations on the novel Tl(3)(7)(-) reveal some bonding similarities with the isoelectronic CO(2), with two good sigma(s,p) bonding and two weakly bonding pi MO's. The Tl-Tl bond lengths therein (3.14 Å) are evidently consistent with multiple bonding. The weak temperature-independent paramagnetism and metallic conductivity (rho(293) approximately 90 &mgr;Omega.cm) of the phase are discussed.

Acetonitrile cluster solvation in a cryogenic ethane-methane-propane liquid: Implications for Titan lake chemistry.

PubMed

Corrales, L René; Yi, Thomas D; Trumbo, Samantha K; Shalloway, David; Lunine, Jonathan I; Usher, David A

2017-03-14

The atmosphere of Titan, Saturn's largest moon, exhibits interesting UV- and radiation-driven chemistry between nitrogen and methane, resulting in dipolar, nitrile-containing molecules. The assembly and subsequent solvation of such molecules in the alkane lakes and seas found on the moon's surface are of particular interest for investigating the possibility of prebiotic chemistry in Titan's hydrophobic seas. Here we characterize the solvation of acetonitrile, a product of Titan's atmospheric radiation chemistry tentatively detected on Titan's surface [H. B. Niemann et al., Nature 438, 779-784 (2005)], in an alkane mixture estimated to match a postulated composition of the smaller lakes during cycles of active drying and rewetting. Molecular dynamics simulations are employed to determine the potential of mean force of acetonitrile (CH 3 CN) clusters moving from the alkane vapor into the bulk liquid. We find that the clusters prefer the alkane liquid to the vapor and do not dissociate in the bulk liquid. This opens up the possibility that acetonitrile-based microscopic polar chemistry may be possible in the otherwise nonpolar Titan lakes.

Hydrogenation properties of KSi and NaSi Zintl phases.

PubMed

Tang, Wan Si; Chotard, Jean-Noël; Raybaud, Pascal; Janot, Raphaël

2012-10-14

The recently reported KSi-KSiH(3) system can store 4.3 wt% of hydrogen reversibly with slow kinetics of several hours for complete absorption at 373 K and complete desorption at 473 K. From the kinetics measured at different temperatures, the Arrhenius plots give activation energies (E(a)) of 56.0 ± 5.7 kJ mol(-1) and 121 ± 17 kJ mol(-1) for the absorption and desorption processes, respectively. Ball-milling with 10 wt% of carbon strongly improves the kinetics of the system, i.e. specifically the initial rate of absorption becomes about one order of magnitude faster than that of pristine KSi. However, this fast absorption causes a disproportionation into KH and K(8)Si(46), instead of forming the KSiH(3) hydride from a slow absorption. This disproportionation, due to the formation of stable KH, leads to a total loss of reversibility. In a similar situation, when the pristine Zintl NaSi phase absorbs hydrogen, it likewise disproportionates into NaH and Na(8)Si(46), indicating a very poorly reversible reaction.

Simultaneous clustering of gene expression data with clinical chemistry and pathological evaluations reveals phenotypic prototypes

PubMed Central

Bushel, Pierre R; Wolfinger, Russell D; Gibson, Greg

2007-01-01

Background Commonly employed clustering methods for analysis of gene expression data do not directly incorporate phenotypic data about the samples. Furthermore, clustering of samples with known phenotypes is typically performed in an informal fashion. The inability of clustering algorithms to incorporate biological data in the grouping process can limit proper interpretation of the data and its underlying biology. Results We present a more formal approach, the modk-prototypes algorithm, for clustering biological samples based on simultaneously considering microarray gene expression data and classes of known phenotypic variables such as clinical chemistry evaluations and histopathologic observations. The strategy involves constructing an objective function with the sum of the squared Euclidean distances for numeric microarray and clinical chemistry data and simple matching for histopathology categorical values in order to measure dissimilarity of the samples. Separate weighting terms are used for microarray, clinical chemistry and histopathology measurements to control the influence of each data domain on the clustering of the samples. The dynamic validity index for numeric data was modified with a category utility measure for determining the number of clusters in the data sets. A cluster's prototype, formed from the mean of the values for numeric features and the mode of the categorical values of all the samples in the group, is representative of the phenotype of the cluster members. The approach is shown to work well with a simulated mixed data set and two real data examples containing numeric and categorical data types. One from a heart disease study and another from acetaminophen (an analgesic) exposure in rat liver that causes centrilobular necrosis. Conclusion The modk-prototypes algorithm partitioned the simulated data into clusters with samples in their respective class group and the heart disease samples into two groups (sick and buff denoting samples

Isolation and Versatile Derivatization of an Unsaturated Anionic Silicon Cluster (Siliconoid)

PubMed Central

Willmes, Philipp; Leszczyńska, Kinga; Heider, Yannic; Abersfelder, Kai; Zimmer, Michael; Huch, Volker

2016-01-01

Abstract The characteristic features of bulk silicon surfaces are echoed in the related partially substituted—and thus unsaturated—neutral silicon clusters (siliconoids). The incorporation of siliconoids into more‐extended frameworks is promising owing to their unique electronic features, but further developments in this regard are limited by the notable absence of functionalized siliconoid derivatives until now. Herein we report the isolation and full characterization of the lithium salt of an anionic R5Si6‐siliconoid, thus providing the missing link between silicon‐based Zintl anions and siliconoid clusters. Proof‐of‐principle for the high potential of this species for the efficient transfer of the intact unsaturated R5Si6 moiety is demonstrated by clean reactions with representative electrophiles of Groups 13, 14, and 15. PMID:26800440

Clustering in analytical chemistry.

PubMed

Drab, Klaudia; Daszykowski, Michal

2014-01-01

Data clustering plays an important role in the exploratory analysis of analytical data, and the use of clustering methods has been acknowledged in different fields of science. In this paper, principles of data clustering are presented with a direct focus on clustering of analytical data. The role of the clustering process in the analytical workflow is underlined, and its potential impact on the analytical workflow is emphasized.

Novel size-dependent chemistry within ionized van der Waals clusters of 1,1-difluoroethane

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

Coolbaugh, M.T.; Peifer, W.R.; Garvey, J.F.

1990-02-22

The authors present in this paper evidence for size-dependent cluster chemistry occurring in van der Waals clusters of 1,1-difluoroethane. Clusters of C{sub 2}H{sub 4}F{sub 2} are produced from a neat adiabatic expansion and are ionized via electron impact. In addition to the anticipated fragment ions, we observe ions with the general empirical formula of M{sub n}H{sup +} (where n {ge} 4). The reactive process that generates this species cannot be rationalized in terms of intramolecular analogues of known gas-phase bimolecular ion-molecular reactions. Hence, we fell the production of this product cluster ion represents an additional example of a brand newmore » class of ion-molecule reactions that can only occur within the unique solvated environment of the cluster.« less

Solid State Chemistry of Clathrate Phases: Crystal Structure, Chemical Bonding and Preparation Routes

NASA Astrophysics Data System (ADS)

Baitinger, Michael; Böhme, Bodo; Ormeci, Alim; Grin, Yuri

Clathrates represent a family of inorganic materials called cage compounds. The key feature of their crystal structures is a three-dimensional (host) framework bearing large cavities (cages) with 20-28 vertices. These polyhedral cages bear—as a rule—guest species. Depending on the formal charge of the framework, clathrates are grouped in anionic, cationic and neutral. While the bonding in the framework is of (polar) covalent nature, the guest-host interaction can be ionic, covalent or even van-der Waals, depending on the chemical composition of the clathrates. The chemical composition and structural features of the cationic clathrates can be described by the enhanced Zintl concept, whereas the composition of the anionic clathrates deviates often from the Zintl counts, indicating additional atomic interactions in comparison with the ionic-covalent Zintl model. These interactions can be visualized and studied by applying modern quantum chemical approaches such as electron localizability.

Chemistry Within Molecular Clusters

DTIC Science & Technology

1992-06-01

reactions, and only occur within van der Waals clusters. 23 They include the generation of (C2H4F2),>4H+ ions from 1,1- difluoroethane clusters, 4 the...of fragment ions, and identification of the molecule must be made by the characteristic fragmentation pattern. The mass spectrum of 1,1- difluoroethane

Chemistry within Molecular Clusters

DTIC Science & Technology

1992-05-29

within van der Waals clusters. 23 They include the generation of (C2H4F 2),,>4H+ ions from 1,1- difluoroethane clusters, 24 the generation of (CH 3...fragment ions, and identification of the molecule must be made by the characteristic fragmentation pattern. The mass spectrum of 1,1- difluoroethane (DFE

The new Zintl phases Eu{sub 21}Cd{sub 4}Sb{sub 18} and Eu{sub 21}Mn{sub 4}Sb{sub 18}

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

Wang, Yi; Darone, Gregory M.; Bobev, Svilen, E-mail: bobev@udel.edu

Crystals of two new Zintl compounds, Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} have been synthesized using the molten metal flux method, and their structures have been established by single-crystal X-ray diffraction. Both compounds are isotypic and crystallize in the monoclinic space group C2/m (No. 12, Z=4). The structures are based on edge- and corner-shared MnSb{sub 4} or CdSb{sub 4} tetrahedra, which make octameric [Mn{sub 8}Sb{sub 22}] or [Cd{sub 8}Sb{sub 22}] polyanions. Homoatomic Sb–Sb bonds are present in both structures. The Eu atoms take the role of Eu{sup 2+}cations with seven unpaired 4f electrons, as suggested by themore » temperature-dependent magnetization measurements. The magnetic susceptibilities of Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} indicate that both phases order anti-ferromagnetically with Néel temperatures of ca. 7 K and ca. 10 K, respectively. The unpaired 3d electrons of the Mn atoms in Eu{sub 21}Mn{sub 4}Sb{sub 18} do contribute to the magnetic response, however, the bulk magnetization measurements do not provide evidence for long-range ordering of the Mn spins down to 5 K. Electrical resistivity measurements suggest that both compounds are narrow band gap semiconductors. - Graphical abstract: Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} have complex monoclinic structures, based on MnSb{sub 4} and CdSb{sub 4} tetrahedra, both edge- and corner-shared. A perspective of the crystal structure is shown, as viewed along the b axis. Display Omitted - Highlights: • Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} are novel compounds in the respective ternary phase diagrams. • For both structures, the Zintl-Klemm rules are followed, and both are small gap semiconductors. • Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} are air-stable Zintl phases and could be new thermoelectric materials.« less

Fabrication of Lanthanum Telluride 14-1-11 Zintl High-Temperature Thermoelectric Couple

NASA Technical Reports Server (NTRS)

Ravi, Vilupanur A.; Li, Billy Chun-Yip; Fleurial, Pierre; Star, Kurt

2010-01-01

The development of more efficient thermoelectric couple technology capable of operating with high-grade heat sources up to 1,275 K is key to improving the performance of radioisotope thermoelectric generators. Lanthanum telluride La3-xTe4 and 14-1-11 Zintls (Yb14MnSb11) have been identified as very promising materials. The fabrication of advanced high-temperature thermoelectric couples requires the joining of several dissimilar materials, typically including a number of diffusion bonding and brazing steps, to achieve a device capable of operating at elevated temperatures across a large temperature differential (up to 900 K). A thermoelectric couple typically comprises a heat collector/ exchanger, metallic interconnects on both hot and cold sides, n-type and ptype conductivity thermoelectric elements, and cold-side hardware to connect to the cold-side heat rejection and provide electrical connections. Differences in the physical, mechanical, and chemical properties of the materials that make up the thermoelectric couple, especially differences in the coefficients of thermal expansion (CTE), result in undesirable interfacial stresses that can lead to mechanical failure of the device. The problem is further complicated by the fact that the thermoelectric materials under consideration have large CTE values, are brittle, and cracks can propagate through them with minimal resistance. The inherent challenge of bonding brittle, high-thermal-expansion thermoelectric materials to a hot shoe material that is thick enough to carry the requisite electrical current was overcome. A critical advantage over prior art is that this device was constructed using all diffusion bonds and a minimum number of assembly steps. The fabrication process and the materials used are described in the following steps: (1) Applying a thin refractory metal foil to both sides of lanthanum telluride. To fabricate the n-type leg of the advanced thermoelectric couple, the pre-synthesized lanthanum

Role of protein-glutathione contacts in defining glutaredoxin-3 [2Fe-2S] cluster chirality, ligand exchange and transfer chemistry.

PubMed

Sen, Sambuddha; Cowan, J A

2017-10-01

Monothiol glutaredoxins (Grx) serve as intermediate cluster carriers in iron-sulfur cluster trafficking. The [2Fe-2S]-bound holo forms of Grx proteins display cysteinyl coordination from exogenous glutathione (GSH), in addition to contact from protein-derived Cys. Herein, we report mechanistic studies that investigate the role of exogenous glutathione in defining cluster chirality, ligand exchange, and the cluster transfer chemistry of Saccharomyces cerevisiae Grx3. Systematic perturbations were introduced to the glutathione-binding site by substitution of conserved charged amino acids that form crucial electrostatic contacts with the glutathione molecule. Native Grx3 could also be reconstituted in the absence of glutathione, with either DTT, BME or free L-cysteine as the source of the exogenous Fe-S ligand contact, while retaining full functional reactivity. The delivery of the [2Fe-2S] cluster to Grx3 from cluster donor proteins such as Isa, Nfu, and a [2Fe-2S](GS) 4 complex, revealed that electrostatic contacts are of key importance for positioning the exogenous glutathione that in turn influences the chiral environment of the cluster. All Grx3 derivatives were reconstituted by standard chemical reconstitution protocols and found to transfer cluster to apo ferredoxin 1 (Fdx1) at rates comparable to native protein, even when using DTT, BME or free L-cysteine as a thiol source in place of GSH during reconstitution. Kinetic analysis of cluster transfer from holo derivatives to apo Fdx1 has led to a mechanistic model for cluster transfer chemistry of native holo Grx3, and identification of the likely rate-limiting step for the reaction.

Ab initio computational study on the lattice thermal conductivity of Zintl clathrates [Si19P4] Cl4 and Na4[Al4Si19

NASA Astrophysics Data System (ADS)

Härkönen, Ville J.; Karttunen, Antti J.

2016-08-01

The lattice thermal conductivity of silicon clathrate framework Si23 and two Zintl clathrates, [Si19P4] Cl4 and Na4[Al4Si19] , is investigated by using an iterative solution of the linearized Boltzmann transport equation in conjunction with ab initio lattice dynamical techniques. At 300 K, the lattice thermal conductivities for Si23, [Si19P4] Cl4 , and Na4[Al4Si19] were found to be 43 W/(m K), 25 W/(m K), and 2 W/(m K), respectively. In the case of Na4[Al4Si19] , the order-of-magnitude reduction in the lattice thermal conductivity was found to be mostly due to relaxation times and group velocities differing from Si23 and [Si19P4] Cl4 . The difference in the relaxation times and group velocities arises primarily due to the phonon spectrum at low frequencies, resulting eventually from the differences in the second-order interatomic force constants (IFCs). The obtained third-order IFCs were rather similar for all materials considered here. The present findings are similar to those obtained earlier for some skutterudites. The predicted lattice thermal conductivity of Na4[Al4Si19] is in line with the experimentally measured thermal conductivity of recently synthesized type-I Zintl clathrate Na8[Al8Si38] (polycrystalline samples).

Combining research in physical chemistry and chemical education: Part A. The femtosecond molecular dynamics of small gas-phase anion clusters. Part B. Surveying student beliefs about chemistry and the development of physical chemistry learning tutorials

NASA Astrophysics Data System (ADS)

Barbera, Jack

2007-12-01

This dissertation combines work in the areas of experimental physical chemistry and chemical education. In the area of physical chemistry, femtosecond pump-probe spectroscopy is used to interrogate the time-dependence for energy redistribution, solvent reorientation, and dissociation dynamics in small gas-phase anion clusters. The chemical education research addressed in this manuscript include the development and validation of a survey to measure students' beliefs about chemistry and the learning of chemistry and the development and testing of learning tutorials for use in undergraduate physical chemistry courses in thermodynamics and kinetics. In the first part of this dissertation, the Cu(CD3OD) dynamics are investigated using a combination of femtosecond pump-probe experiments and ab initio calculations. Dissociation of this complex into Cu and CD3OD occurs on two distinct time scales: 3 and 30 ps, which arise, respectively, from the coupling of intermolecular solvent rotations and excited methyl rotor rotation into the Cu-O dissociation component upon electron photodetachment of the precursor anion. In the second part of this dissertation, the time-resolved recombination of photodissociated IBr-(CO2)n (n = 5 - 10) cluster anions is investigated. Upon excitation to the A' 2pi 1/2 state of the chromophore, the bare anion results in I- and Br products, upon solvation with CO2, the IBr- chromophore regains near-IR absorption after recombination and vibrational relaxation on the ground electronic state. The recombination times vary with the number of solvent molecules from 12 ps for n = 5 to 900 ps for n = 10. Extensive electronic structure and non-adiabatic molecular dynamic simulations provide a framework to understand this behavior. In the third part of this dissertation, the modification and validation of the Colorado Learning Attitudes about Science Survey (CLASS) for use in chemistry is presented in detail. The CLASS survey is designed to measure student

Formation rates, stability and reactivity of sulfuric acid - amine clusters predicted by computational chemistry

NASA Astrophysics Data System (ADS)

Kurtén, Theo; Ortega, Ismael; Kupiainen, Oona; Olenius, Tinja; Loukonen, Ville; Reiman, Heidi; McGrath, Matthew; Vehkamäki, Hanna

2013-04-01

Despite the importance of atmospheric particle formation for both climate and air quality, both experiments and non-empirical models using e.g. sulfuric acid, ammonia and water as condensing vapors have so far been unable to reproduce atmospheric observations using realistic trace gas concentrations. Recent experimental and theoretical evidence has shown that this mystery is likely resolved by amines. Combining first-principles evaporation rates for sulfuric acid - dimethylamine clusters with cluster kinetic modeling, we show that even sub-ppt concentrations of amines, together with atmospherically realistic concentrations of sulfuric acid, result in formation rates close to those observed in the atmosphere. Our simulated cluster formation rates are also close to, though somewhat larger than, those measured at the CLOUD experiment in CERN for both sulfuric acid - ammonia and sulfuric acid - dimethylamine systems. A sensitivity analysis indicates that the remaining discrepancy for the sulfuric acid - amine particle formation rates is likely caused by steric hindrances to cluster formation (due to alkyl groups of the amine molecules) rather than by significant errors in the evaporation rates. First-principles molecular dynamic and reaction kinetic modeling shed further light on the microscopic physics and chemistry of sulfuric acid - amine clusters. For example, while the number and type of hydrogen bonds in the clusters typically reach their equilibrium values on a picosecond timescale, and the overall bonding patterns predicted by traditional "static" quantum chemical calculations seem to be stable, the individual atoms participating in the hydrogen bonds continuously change at atmospherically realistic temperatures. From a chemical reactivity perspective, we have also discovered a surprising phenomenon: clustering with sulfuric acid molecules slightly increases the activation energy required for the abstraction of alkyl hydrogens from amine molecules. This implies

Chemistry within Molecular van der Waals Clusters

DTIC Science & Technology

1990-07-18

and Discussion 1) Stabilizing an Unstable Reagent within a Cluster a) 1, 1- Difluoroethane Clusters 2) Providing New Chemical Pathways a) Ammonia...1- difluoroethane clusters 24, the generation of (CH3 OCH 3 )nH3 O+ & (CH3 OCH 3 )nCH3 OH2 + ions from dimethyl ether dusters25 ,26, the generation of...Stabilizing an Unstable Reagent within a Cluster a) 1.1- Difluoroethane Clusters 24 The dominant reactive process which occurs within the majority of cluster

The unusual chemical bonding and thermoelectric properties of a new type Zintl phase compounds Ba3Al2As4

NASA Astrophysics Data System (ADS)

Yang, Gui; Zhang, Guangbiao; Wang, Chao; Wang, Yuanxu

2016-07-01

Ba3Al2As4 exhibits an unusual anisotropic electrical conductivity, that is, the electrical conductivity along the chain is smaller than those along other two directions. The results is conflict with previous conclusion for Ca5M2Pn6. Earlier studies on Ca5M2Pn6 showed that a higher electrical conductivity could be obtained along the chain. The band decomposed charge density is used to explain such unusual behavior. Our calculations indicate the existence of a conductive pathway near the Fermi level is responsible for the electrons transport. Further, the Ba-As bonding of Ba3Al2As4 has some degree covalency which is novel for the Zintl compounds.

Effect of Rubber Polarity on Cluster Formation in Rubbers Cross-Linked with Diels–Alder Chemistry

PubMed Central

2017-01-01

Diels–Alder chemistry has been used for the thermoreversible cross-linking of furan-functionalized ethylene/propylene (EPM) and ethylene/vinyl acetate (EVM) rubbers. Both furan-functionalized elastomers were successfully cross-linked with bismaleimide to yield products with a similar cross-link density. NMR relaxometry and SAXS measurements both show that the apolar EPM-g-furan precursor contains phase-separated polar clusters and that cross-linking with polar bismaleimide occurs in these clusters. The heterogeneously cross-linked network of EPM-g-furan contrasts with the homogeneous network in the polar EVM-g-furan. The heterogeneous character of the cross-links in EPM-g-furan results in a relatively high Young’s modulus, whereas the more uniform cross-linking in EVM-g-furan results in a higher tensile strength and elongation at break. PMID:29213149

Designing, Describing and Disseminating New Materials by using the Network Topology Approach.

PubMed

Öhrström, Lars

2016-09-19

This Concept article describes how network topology analysis is applied to different fields of solid-state chemistry. Its usefulness is demonstrated by examples from metal-organic frameworks, group 14 allotropes and related compounds, ice polymorphs, zeolites, supramolecular (organic) solid-state chemistry, Zintl phases, and cathode materials for Li-ion batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nature's polyoxometalate chemistry: X-ray structure of the Mo storage protein loaded with discrete polynuclear Mo-O clusters.

PubMed

Kowalewski, Björn; Poppe, Juliane; Demmer, Ulrike; Warkentin, Eberhard; Dierks, Thomas; Ermler, Ulrich; Schneider, Klaus

2012-06-13

Some N(2)-fixing bacteria prolong the functionality of nitrogenase in molybdenum starvation by a special Mo storage protein (MoSto) that can store more than 100 Mo atoms. The presented 1.6 Å X-ray structure of MoSto from Azotobacter vinelandii reveals various discrete polyoxomolybdate clusters, three covalently and three noncovalently bound Mo(8), three Mo(5-7), and one Mo(3) clusters, and several low occupied, so far undefinable clusters, which are embedded in specific pockets inside a locked cage-shaped (αβ)(3) protein complex. The structurally identical Mo(8) clusters (three layers of two, four, and two MoO(n) octahedra) are distinguishable from the [Mo(8)O(26)](4-) cluster formed in acidic solutions by two displaced MoO(n) octahedra implicating three kinetically labile terminal ligands. Stabilization in the covalent Mo(8) cluster is achieved by Mo bonding to Hisα156-N(ε2) and Gluα129-O(ε1). The absence of covalent protein interactions in the noncovalent Mo(8) cluster is compensated by a more extended hydrogen-bond network involving three pronounced histidines. One displaced MoO(n) octahedron might serve as nucleation site for an inhomogeneous Mo(5-7) cluster largely surrounded by bulk solvent. In the Mo(3) cluster located on the 3-fold axis, the three accurately positioned His140-N(ε2) atoms of the α subunits coordinate to the Mo atoms. The formed polyoxomolybdate clusters of MoSto, not detectable in bulk solvent, are the result of an interplay between self- and protein-driven assembly processes that unite inorganic supramolecular and protein chemistry in a host-guest system. Template, nucleation/protection, and catalyst functions of the polypeptide as well as perspectives for designing new clusters are discussed.

Anatomy of a cluster IDP. Part 2: Noble gas abundances, trace element geochemistry, isotopic abundances, and trace organic chemistry of several fragments from L2008#5

NASA Technical Reports Server (NTRS)

Thomas, K. L.; Clemett, S. J.; Flynn, G. J.; Keller, L. P.; Mckay, David S.; Messenger, S.; Nier, A. O.; Schlutter, D. J.; Sutton, S. R.; Walker, R. M.

1994-01-01

The topics discussed include the following: noble gas content and release temperatures; trace element abundances; heating summary of cluster fragments; isotopic measurements; and trace organic chemistry.

From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry.

PubMed

Müller, Achim; Gouzerh, Pierre

2012-11-21

Following Nature's lessons, today chemists can cross the boundary of the small molecule world to construct multifunctional and highly complex molecular nano-objects up to protein size and even cell-like nanosystems showing responsive sensing. Impressive examples emerge from studies of the solutions of some oxoanions of the early transition metals especially under reducing conditions which enable the controlled linking of metal-oxide building blocks. The latter are available from constitutional dynamic libraries, thus providing the option to generate multifunctional unique nanoscale molecular systems with exquisite architectures, which even opens the way towards adaptive and evolutive (Darwinian) chemistry. The present review presents the first comprehensive report of current knowledge (including synthesis aspects not discussed before) regarding the related giant metal-oxide clusters mainly of the type {Mo(57)M'(6)} (M' = Fe(III), V(IV)) (torus structure), {M(72)M'(30)} (M = Mo, M' = V(IV), Cr(III), Fe(III), Mo(V)), {M(72)Mo(60)} (M = Mo, W) (Keplerates), {Mo(154)}, {Mo(176)}, {Mo(248)} ("big wheels"), and {Mo(368)} ("blue lemon") - all having the important transferable pentagonal {(M)M(5)} groups in common. These discoveries expanded the frontiers of inorganic chemistry to the mesoscopic world, while there is probably no collection of discrete inorganic compounds which offers such a versatile chemistry and the option to study new phenomena of interdisciplinary interest. The variety of different properties of the sphere- and wheel-type metal-oxide-based clusters can directly be related to their unique architectures: The spherical Keplerate-type capsules having 20 crown-ether-type pores and tunable internal functionalities allow the investigation of confined matter as well as that of sphere-surface-supramolecular and encapsulation chemistry - including related new aspects of the biologically important hydrophobic effects - but also of nanoscale ion transport and

Artificial neural networks for efficient clustering of conformational ensembles and their potential for medicinal chemistry.

PubMed

Pandini, Alessandro; Fraccalvieri, Domenico; Bonati, Laura

2013-01-01

The biological function of proteins is strictly related to their molecular flexibility and dynamics: enzymatic activity, protein-protein interactions, ligand binding and allosteric regulation are important mechanisms involving protein motions. Computational approaches, such as Molecular Dynamics (MD) simulations, are now routinely used to study the intrinsic dynamics of target proteins as well as to complement molecular docking approaches. These methods have also successfully supported the process of rational design and discovery of new drugs. Identification of functionally relevant conformations is a key step in these studies. This is generally done by cluster analysis of the ensemble of structures in the MD trajectory. Recently Artificial Neural Network (ANN) approaches, in particular methods based on Self-Organising Maps (SOMs), have been reported performing more accurately and providing more consistent results than traditional clustering algorithms in various data-mining problems. In the specific case of conformational analysis, SOMs have been successfully used to compare multiple ensembles of protein conformations demonstrating a potential in efficiently detecting the dynamic signatures central to biological function. Moreover, examples of the use of SOMs to address problems relevant to other stages of the drug-design process, including clustering of docking poses, have been reported. In this contribution we review recent applications of ANN algorithms in analysing conformational and structural ensembles and we discuss their potential in computer-based approaches for medicinal chemistry.

Geographic clustering of elderly people with above-norm anthropometric measurements and blood chemistry.

PubMed

Mena, Carlos; Fuentes, Eduardo; Ormazábal, Yony; Palomo, Iván

2017-05-11

The global percentage of people over 60 is strongly increasing and estimated to exceed 20% by 20,150, which means that there will be an increase in many pathological conditions related to aging. Mapping of the location of aging people and identification of their needs can be extremely valuable from a social-economic point of view. Participants in this study were 148 randomly selected adults from Talca City, Chile aged 60-74 at baseline. Geographic information systems (GIS) analyses were performed using ArcGIS software through its module Spatial Autocorrelation. In this study, we demonstrated that elderly people show geographic clustering according to above-norm results of anthropometric measurements and blood chemistry. The spatial identifications found would facilitate exploring the impact of treatment programmes in communities where many aging people live, thereby improving their quality of life as well as reducing overall costs.

Structural and thermoelectric properties of zintl-phase CaLiPn (Pn=As, Sb, Bi)

NASA Astrophysics Data System (ADS)

Chandran, Anoop K.; Gudelli, Vijay Kumar; Sreeparvathy, P. C.; Kanchana, V.

2016-11-01

First-principles calculations were carried out to study the structural, mechanical, dynamical and transport properties of zintl phase materials CaLiPn (Pn=As, Sb and Bi). We have used two different approaches to solve the system based on density functional theory. The plane wave pseudopotential approach has been used to study the structural and dynamical properties whereas, full potential linear augment plane wave method is used to examine the electronic structure, mechanical and thermoelectric properties. The calculated ground-state properties agree quite well with experimental values. The computed electronic structure shows the investigated compounds to be direct band gap semiconductors. Further, we have calculated the thermoelectric properties of all the investigated compounds for both the carriers at various temperatures. We found a high thermopower for both the carriers, especially n-type doping to be more favourable, which enabled us to predict that CaLiPn might have promising applications as a good thermoelectric material. Further, the phonon dispersion curves of the investigated compounds showed flat phonon modes and we also find lower optical and acoustic modes to cut each other at the lower frequency range, which further indicate the investigated compounds to possess reasonably low thermal conductivity. We have also analysed the low value of the thermal conductivity through the empirical relations and discussions are presented here.

Quantifying the pattern of microbial cell dispersion, density and clustering on surfaces of differing chemistries and topographies using multifractal analysis.

PubMed

Wickens, David; Lynch, Stephen; West, Glen; Kelly, Peter; Verran, Joanna; Whitehead, Kathryn A

2014-09-01

The effects of surface topography on bacterial distribution across a surface are of extreme importance when designing novel, hygienic or antimicrobial surface coatings. The majority of methods that are deployed to describe the pattern of cell dispersion, density and clustering across surfaces are currently qualitative. This paper presents a novel application of multifractal analysis to quantitatively measure these factors using medically relevant microorganisms (Staphylococcus aureus or Staphylococcus epidermidis). Surfaces (medical grade 316 stainless steel) and coatings (Ti-ZrN, Ti-ZrN/6.0%Ag, Ti-ZrN/15.6%Ag, TiZrN/24.7%Ag) were used in microbiological retention assays. Results demonstrated that S. aureus displayed a more heterogeneous cell dispersion (∆αAS<1) whilst the dispersion of S. epidermidis was more symmetric and homogeneous (∆αAS≥1). Further, although the surface topography and chemistry had an effect on cell dispersion, density and clustering, the type of bonding that occurred at the surface interface was also important. Both types of cells were influenced by both surface topographical and chemical effects; however, S. aureus was influenced marginally more by surface chemistry whilst S. epidermidis cells was influenced marginally more by surface topography. Thus, this effect was bacterially species specific. The results demonstrate that multifractal analysis is a method that can be used to quantitatively analyse the cell dispersion, density and clustering of retained microorganisms on surfaces. Using quantitative descriptors has the potential to aid the understanding the effect of surface properties on the production of hygienic and antimicrobial coatings. Copyright © 2014 Elsevier B.V. All rights reserved.

Emerging themes in radical SAM chemistry

PubMed Central

Shisler, Krista A; Broderick, Joan B

2014-01-01

Enzymes in the radical SAM (RS) superfamily catalyze a wide variety of reactions through unique radical chemistry. The characteristic markers of the superfamily include a [4Fe–4S] cluster coordinated to the protein via a cysteine triad motif, typically CX3CX2C, with the fourth iron coordinated by S-adenosylmethionine (SAM). The SAM serves as a precursor for a 5′-deoxyadenosyl radical, the central intermediate in nearly all RS enzymes studied to date. The SAM-bound [4Fe–4S] cluster is located within a partial or full triosephosphate isomerase (TIM) barrel where the radical chemistry occurs protected from the surroundings. In addition to the TIM barrel and a RS [4Fe–4S] cluster, many members of the superfamily contain additional domains and/or additional Fe–S clusters. Recently characterized superfamily members are providing new examples of the remarkable range of reactions that can be catalyzed, as well as new structural and mechanistic insights into these fascinating reactions. PMID:23141873

Different Topological Quantum States in Ternary Zintl compounds: BaCaX (X = Si, Ge, Sn and Pb)

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

Wang, Lin-Lin; Kaminski, Adam; Canfield, Paul C.

Topological quantum states require stringent combination of crystal symmetry and spin–orbit coupling (SOC) strength. Here in this paper, we report that the ternary Zintl compound series BaCaX (X = Si, Ge, Sn and Pb, Group IV) in the same crystal structure having eight valence electrons per formula unit can host two different topological quantum phases, controlled by atomic size and SOC strength. BaCaSi is a nodal-line semimetal (NLSM) with band inversion protected by mirror symmetry and hosts a strong topological insulator (TI) state when SOC is turned on, thus, a NLSM-TI phase. Moving to larger atomic sizes and heavier atoms,more » BaCaGe and BaCaSn are normal insulators (NIs); then, with the strongest SOC in BaCaPb, a different band inversion is induced, giving a strong TI phase without the need of NLSM. Thus, we also predict two types of topological transitions in a phase diagram for BaCaX: (1) NLSM-TI to NI, then to TI by tuning atomic size and SOC strength via alloying, and (2) NI or TI to NLSM-TI via pressure.« less

Different Topological Quantum States in Ternary Zintl compounds: BaCaX (X = Si, Ge, Sn and Pb)

DOE PAGES

Wang, Lin-Lin; Kaminski, Adam; Canfield, Paul C.; ...

2017-12-14

Topological quantum states require stringent combination of crystal symmetry and spin–orbit coupling (SOC) strength. Here in this paper, we report that the ternary Zintl compound series BaCaX (X = Si, Ge, Sn and Pb, Group IV) in the same crystal structure having eight valence electrons per formula unit can host two different topological quantum phases, controlled by atomic size and SOC strength. BaCaSi is a nodal-line semimetal (NLSM) with band inversion protected by mirror symmetry and hosts a strong topological insulator (TI) state when SOC is turned on, thus, a NLSM-TI phase. Moving to larger atomic sizes and heavier atoms,more » BaCaGe and BaCaSn are normal insulators (NIs); then, with the strongest SOC in BaCaPb, a different band inversion is induced, giving a strong TI phase without the need of NLSM. Thus, we also predict two types of topological transitions in a phase diagram for BaCaX: (1) NLSM-TI to NI, then to TI by tuning atomic size and SOC strength via alloying, and (2) NI or TI to NLSM-TI via pressure.« less

Eu9Cd4-xCM2+x-y□ySb9: Ca9Mn4Bi9-type structure stuffed with coinage metals (Cu, Ag, and Au) and the challenges with classical valence theory in describing these possible zintl phases.

PubMed

Kazem, Nasrin; Hurtado, Antonio; Klobes, Benedikt; Hermann, Raphaël P; Kauzlarich, Susan M

2015-02-02

The synthesis, crystal structure, magnetic properties, and europium Mössbauer spectroscopy of the new members of the 9-4-9 Zintl family of Eu(9)Cd(4-x)CM(2+x-y)□(y)Sb(9) (CM = coinage metal: Au, Ag, and Cu) are reported. These compounds crystallize in the Ca(9)Mn(4)Bi(9) structure type (9-4-9) with the 4g interstitial site almost half-occupied by coinage metals; these are the first members in the 9-4-9 family where the interstitial positions are occupied by a monovalent metal. All previously known compounds with this structure type include divalent interstitials where these interstitials are typically the same as the transition metals in the anionic framework. Single-crystal magnetic susceptibility data indicate paramagnetic behavior for all three compounds with antiferromagnetic ordering below 10 K (at 100 Oe) that shifts to lower temperature (<7 K) by applying a 3 T magnetic field. (151)Eu Mössbauer spectra were collected on polycrystalline powder samples of Eu(9)Cd(4-x)CM(2+x-y)□(y)Sb(9) at 50 and 6.5 K in order to evaluate the valence of Eu cations. Although the Zintl formalism states that the five crystallographically distinct Eu sites in Eu(9)Cd(4-x)CM(2+x-y)□(y)Sb9 should bear Eu(2+), the Mössbauer spectral isomer shifts are clearly indicative of both 2+ and 3+ valence of the Eu cations with the Cu- and Au-containing compounds showing higher amounts of Eu(3+). This electronic configuration leads to an excess of negative charge in these compounds that contradicts the expected valence-precise requirement of Zintl phases. The spectra obtained at 6.5 K reveal magnetic ordering for both Eu(2+) and Eu(3+). The field dependence of Eu(2+) indicates two distinct magnetic sublattices, with higher and lower fields, and of a small field for Eu(3+). The site symmetry of the five Eu sites is not distinguishable from the Mössbauer data.

Synthesis and Characterization of Novel Compound Clusters

DTIC Science & Technology

1997-08-26

also be intrinsically stable, they cannot be formed by this plasma chemistry presumably because the metals are less reactive. Plasma chemistry reactions...samples without the presence of hydrogen. Vaporization of these composite samples produces the metal carbide clusters in many cases where plasma chemistry does...antimony or bismuth cannot be produced by the hydrocarbon plasma chemistry method, but they are produced readily from composite sample (metal film on

Roles of cations, electronegativity difference, and anionic interlayer interactions in the metallic versus nonmetallic character of Zintl phases related to arsenic.

PubMed

Alemany, Pere; Llunell, Miquel; Canadell, Enric

2008-10-01

A first-principles Density Functional Theory study of several layered solids structurally related to rhombohedral arsenic has been carried out. The electronic structures of rhombohedral arsenic, CaSi(2), CaAl(2)Si(2), KSnSb, and SrSn(2)As(2) are discussed in detail, emphasizing on the origins of their metallic or nonmetallic behaviours. It is found that all of these systems are metallic except KSnSb. Electronegativity differences between the elements in the anionic sublattice and/or direct interlayer interactions play the main role in controlling the conductivity behavior. CaSi(2) exhibits a peculiar feature since the cation directly influences the conductivity but is not essential for its appearance. Cation-anion interactions are shown to have an important covalent contribution, but despite this fact and the metallic character found for most of these phases, the Zintl approach still provides a valid approximation to their electronic structure. (c) 2008 Wiley Periodicals, Inc.

Antibonding Holes Induce Good Thermoelectric Properties of p-type Ca5Ga2As6

NASA Astrophysics Data System (ADS)

Yu, Qingxiu; Wang, Yuan Xu; Shao, Hehong

2017-07-01

The arrangement of anionic tetrahedra in Zintl compounds plays a key role in determining their thermoelectric properties. We manifest this idea by investigating the crystal structure, electronic structure, and thermoelectric properties of the Zintl compounds Ca3GaAs3 and Ca5Ga2As6. By comparing various properties of Ca3GaAs3 and Ca5Ga2As6, we found that with decreasing calcium content from Ca3GaAs3 to Ca5Ga2As6, the two adjacent covalent chains formed by GaAs4 tetrahedra are connected by As-As bonds. In Ca5Ga2As6, the appearance of such As-As bonds not only supports the charge balance but also provides two nearly degenerate bands at the top of its valence bands. These two bands determine the thermoelectric behavior of p-type Ca5Ga2As6. The calculated band-decomposed charge density shows that the two bands have a π* antibonding feature of the As pz orbital. Our calculations also reveal that the formation or non-formation of As-As bonds plays an important role in the difference in the thermoelectric properties between Ca3GaAs3 and Ca5Ga2As6. The optimal carrier concentration for achieving the highest thermoelectric performance was explored by calculating the trends in their thermoelectric properties with the carrier concentration. Our work may stimulate further experimental and theoretical work to increase understanding of Zintl chemistry and improve the thermoelectric performance of Zintl compounds.

Methanethiol chemistry on TiO 2-supported Ni clusters

NASA Astrophysics Data System (ADS)

Ozturk, O.; Park, J. B.; Black, T. J.; Rodriguez, J. A.; Hrbek, J.; Chen, D. A.

2008-10-01

The thermal decomposition of methanethiol on Ni clusters grown on TiO 2(1 1 0) was studied by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). On all of the Ni surfaces investigated, methane and hydrogen were observed as gaseous products in the TPD experiments, and the only sulfur-containing species that desorbed from the surface was methanethiol itself at low temperatures. The two pathways for methanethiol reaction were hydrodesulfurization to produce methane and nonselective decomposition, which leaves atomic carbon and sulfur on the surface. From high resolution XPS studies, methyl thiolate was identified as the surface intermediate for reaction on TiO 2 and on all of the Ni surfaces investigated, similar to what is observed on single-crystal Ni surfaces. However, the binding sites for methyl thiolate on the 1 ML (monolayer) Ni clusters were different from those on the Ni clusters at coverages of 2.5 ML and higher, based on the S(2p) binding energies for methyl thiolate. No distinct changes in activity or selectivity were observed for the smaller Ni clusters grown at low coverage compared to the more film-like Ni surfaces other than what could be accounted for by changes in total surface area. Interactions between the Ni clusters and the TiO 2 support had two main effects on chemical activity. First, carbon was oxidized by oxygen from the TiO 2 lattice to produce CO at temperatures above 800 K. Second, annealing induced encapsulation of the Ni clusters by reduced TiO x and chemisorbed oxygen. At 800 K, the Ni clusters were totally encapsulated, resulting in a complete loss of methanethiol activity; partial encapsulation at 700 K caused a smaller decrease in activity accompanied by increased oxidation of carbon by lattice oxygen.

Electron attachment to molecules in a cluster environment: suppression and enhancement effects

NASA Astrophysics Data System (ADS)

Fabrikant, Ilya I.

2018-05-01

Cluster environments can strongly influence dissociative electron attachment (DEA) processes. These effects are important in many applications, particularly for surface chemistry, radiation damage, and atmospheric physics. We review several mechanisms for DEA suppression and enhancement due to cluster environments, particularly due to microhydration. Long-range electron-molecule and electron-cluster interactions play often a significant role in these effects and can be analysed by using theoretical models. Nevertheless many observations remain unexplained due to complexity of the physics and chemistry of interaction of DEA fragments with the cluster environment.

STM-electroluminescence from clustered C3N4 nanodomains synthesized via green chemistry process.

PubMed

Andrade, E P; Costa, B B A; Chaves, C R; de Paula, A M; Cury, L A; Malachias, A; Safar, G A M

2018-01-01

A Scanning Tunneling Microscopy/Spectroscopy (STM/STS) and synchrotron X-ray diffraction study on clustered C 3 N 4 nanoparticles (nanoflakes) is conducted on green-chemistry synthesized samples obtained from chitosan through high power sonication. Morphological aspects and the electronic characteristics are investigated. The observed bandgap of the nanoflakes reveals the presence of different phases in the material. Combining STM morphology, STS spectra and X-ray diffraction (XRD) results one finds that the most abundant phase is graphitic C 3 N 4 . A high density of defects is inferred from the XRD measurements. Additionally, STM-electroluminescence (STMEL) is detected in C 3 N 4 nanoflakes deposited on a gold substrate. The tunneling current creates photons that are three times more energetic than the tunneling electrons of the STM sample. We ponder about the two most probable models to explain the observed photon emission energy: either a nonlinear optical phenomenon or a localized state emission. Copyright © 2017 Elsevier B.V. All rights reserved.

New developments in theoretical thermochemistry and electronic structure applications in supramolecular chemistry and cluster science

NASA Astrophysics Data System (ADS)

Ramabhadran, Raghunath Ozhapakkam

In a concise display of the power and diversity of electronic structure theory (EST), the work presented herein involves the development of new computational methods to advance the practical utility of quantum chemistry, as well as solving different types of challenging chemical problems by applying existing EST tools. The research presented is highly interdisciplinary in nature and features synergistic collaborations to solve real-life problems such as regulating toxic chemicals and generating alternative sources of energy. In the first chapter of this dissertation, the solution to a long-standing problem in theoretical thermochemistry is accomplished by the development of the automated, chemically intuitive and generalized thermochemical hierarchy, Connectivity-Based Hierarchy (CBH) to accurately predict the thermochemical properties of organic molecules. The extension of the hierarchy to predict the enthalpies of formations of biomonomers such as amino acids is also presented. The development of a computationally efficient protocol to accurately extrapolate to high CCSD(T) energies based on MP2 and DFT energies using CBH is presented in the second chapter, thus merging theoretical thermochemistry with fragment-based methods in quantum chemistry. This merger drastically reduces the computational cost involved in a CCSD(T) calculation, while retaining the impeccable accuracy it offers. The practical utility of the CH hydrogen bond, commonly thought as being too weak to be used in supramolecular applications has been demonstrated by DFT calculations (along with experimental results from the Flood group) in the third chapter. This is accomplished by systematically studying the binding of monoatomic chloride, diatomic and toxic cyanide and the polyatomic bi-fluoride anions for the first time using only CH hydrogen bonds within a triazolophane macrocycle. The fourth chapter contains the introduction of the concept of fluxionality in the chemical reactions of

Site-Specific Biomolecule Labeling with Gold Clusters

PubMed Central

Ackerson, Christopher J.; Powell, Richard D.; Hainfeld, James F.

2013-01-01

Site-specific labeling of biomolecules in vitro with gold clusters can enhance the information content of electron cryomicroscopy experiments. This chapter provides a practical overview of well-established techniques for forming biomolecule/gold cluster conjugates. Three bioconjugation chemistries are covered: Linker-mediated bioconjugation, direct gold–biomolecule bonding, and coordination-mediated bonding of nickel(II) nitrilotriacetic acid (NTA)-derivatized gold clusters to polyhistidine (His)-tagged proteins. PMID:20887859

A New Approach to the General Chemistry Laboratory

NASA Astrophysics Data System (ADS)

Bieron, Joseph F.; McCarthy, Paul J.; Kermis, Thomas W.

1996-11-01

Background Canisius College is a medium-sized liberal arts college with a longstanding tradition of maintaining an excellent chemistry program. We realized a few years ago, however, that this tradition was not being sustained by our General Chemistry laboratory course, which had not changed significantly in years. With the help of a grant from the National Science Foundation, our department has been able to design a new laboratory course built around several guiding principles. The design called for experiments to be grouped in units or clusters. Each cluster has a unifying theme or common thread, which gives some coherence to the experiments. The clusters and experiments are listed in the appendix and briefly explained below. Course Design Cluster A's topic is organic and polymer chemistry, and its main objective is to show that chemistry can be enjoyable and relevant to common experiences. Data collection is minimal and hands-on manipulation with observable products is emphasized. Cluster B is a case study of the chemistry of maintaining a swimming pool. The common theme is solution chemistry, and the experiments are designed to promote critical thinking. Cluster C encompasses both oxidation - reduction reactions and electrochemistry, and attempts to show the commonality of these important topics. Cluster D is a series of experiments on methods and techniques of analytical chemistry; in this group the analysis of unknown materials is undertaken. Cluster E is covered last in the second semester, and it stresses important concepts in chemistry at a slightly more advanced level. The emphasis is on the relationship of experiment to theory, and the cluster involves experiments in kinetics, equilibrium, and synthesis. Other guidelines that we considered important in our design were the use of computers (when appropriate), the introduction of microscale chemistry, and the use of instrumentation whenever possible. A separate cluster, labeled Mac, was developed to provide

Hybrid quantum and molecular mechanics embedded cluster models for chemistry on silicon and silicon carbide surfaces

NASA Astrophysics Data System (ADS)

Shoemaker, James Richard

Fabrication of silicon carbide (SiC) semiconductor devices are of interest for aerospace applications because of their high-temperature tolerance. Growth of an insulating SiO2 layer on SiC by oxidation is a poorly understood process, and sometimes produces interface defects that degrade device performance. Accurate theoretical models of surface chemistry, using quantum mechanics (QM), do not exist because of the huge computational cost of solving Schrodinger's equation for a molecular cluster large enough to represent a surface. Molecular mechanics (MM), which describes a molecule as a collection of atoms interacting through classical potentials, is a fast computational method, good at predicting molecular structure, but cannot accurately model chemical reactions. A new hybrid QM/MM computational method for surface chemistry was developed and applied to silicon and SiC surfaces. The addition of MM steric constraints was shown to have a large effect on the energetics of O atom adsorption on SiC. Adsorption of O atoms on Si-terminated SiC(111) favors above surface sites, in contrast to Si(111), but favors subsurface adsorption sites on C- terminated SiC(111). This difference, and the energetics of C atom etching via CO2 desorption, can explain the observed poor performance of SiC devices in which insulating layers were grown on C-terminated surfaces.

Heterogeneous atmospheric chemistry

NASA Technical Reports Server (NTRS)

Schryer, D. R.

1982-01-01

The present conference on heterogeneous atmospheric chemistry considers such topics concerning clusters, particles and microparticles as common problems in nucleation and growth, chemical kinetics, and catalysis, chemical reactions with aerosols, electron beam studies of natural and anthropogenic microparticles, and structural studies employing molecular beam techniques, as well as such gas-solid interaction topics as photoassisted reactions, catalyzed photolysis, and heterogeneous catalysis. Also discussed are sulfur dioxide absorption, oxidation, and oxidation inhibition in falling drops, sulfur dioxide/water equilibria, the evidence for heterogeneous catalysis in the atmosphere, the importance of heterogeneous processes to tropospheric chemistry, soot-catalyzed atmospheric reactions, and the concentrations and mechanisms of formation of sulfate in the atmospheric boundary layer.

Keeping the ball rolling: fullerene-like molecular clusters.

PubMed

Kong, Xiang-Jian; Long, La-Sheng; Zheng, Zhiping; Huang, Rong-Bin; Zheng, Lan-Sun

2010-02-16

The discovery of fullerenes in 1985 opened a new chapter in the chemistry of highly symmetric molecules. Fullerene-like metal clusters, characterized by (multi)shell-like structures, are one rapidly developing class of molecules that share this shape. In addition to creating aesthetically pleasing molecular structures, the ordered arrangement of metal atoms within such frameworks provides the opportunity to develop materials with properties not readily achieved in corresponding mononuclear or lower-nuclearity complexes. In this Account, we survey the great variety of fullerene-like metal-containing clusters with an emphasis on their synthetic and structural chemistry, a first step in the discussion of this fascinating field of cluster chemistry. We group the compounds of interest into three categories based on the atomic composition of the cluster core: those with formal metal-metal bonding, those characterized by ligand participation, and those supported by polyoxometalate building blocks. The number of clusters in the first group, containing metal-metal bonds, is relatively small. However, because of the unique and complex bonding scenarios observed for some of these species, these metalloid clusters present a number of research questions with significant ramifications. Because these cores contain molecular clusters of precious metals at the nanoscale, they offer an opportunity to study chemical properties at size ranges from the molecular to nanoscale and to gain insights into the electronic structures and properties of nanomaterials of similar chemical compositions. Clusters of the second type, whose core structures are facilitated by ligand participation, could aid in the development of functional materials. Of particular interest are the magnetic clusters containing both transition and lanthanide elements. A series of such heterometallic clusters that we prepared demonstrates diverse magnetic properties including antiferromagnetism, ferrimagnetism, and

New ligand platforms featuring boron-rich clusters as organomimetic substituents*,**

PubMed Central

Spokoyny, Alexander M.

2013-01-01

200 years of research with carbon-rich molecules have shaped the development of modern chemistry. Research pertaining to the chemistry of boron-rich species has historically trailed behind its more distinguished neighbor (carbon) in the periodic table. Notably, a potentially rich and, in many cases, unmatched field of coordination chemistry using boronrich clusters remains fundamentally underdeveloped. Our work has been devoted to examining several basic concepts related to the functionalization of icosahedral boron-rich clusters and their use as ligands, aimed at designing fundamentally new hybrid molecular motifs and materials. Particularly interesting are icosahedral carboranes, which can be regarded as 3D analogs of benzene. These species comprise a class of boron-rich clusters that were discovered in the 1950s during the “space race” while researchers were developing energetic materials for rocket fuels. Ultimately, the unique chemical and physical properties of carborane species, such as rigidity, indefinite stability to air and moisture, and 3D aromaticity, may allow one to access a set of properties not normally available in carbon-based chemistry. While technically these species are considered as inorganic clusters, the chemical properties they possess make these boron-rich species suitable for replacing and/or altering structural and functional features of the organic and organometallic molecules—a phenomenon best described as “organomimetic”. Aside from purely fundamental features associated with the organomimetic chemistry of icosahedral carboranes, their use can also provide new avenues in the development of systems relevant to solving current problems associated with energy production, storage, and conversion. PMID:24311823

Investigation of glutathione-derived electrostatic and hydrogen-bonding interactions and their role in defining Grx5 [2Fe-2S] cluster optical spectra and transfer chemistry.

PubMed

Sen, Sambuddha; Bonfio, Claudia; Mansy, Sheref S; Cowan, J A

2018-03-01

Human glutaredoxin 5 (Grx5) is one of the core components of the Isc (iron-sulfur cluster) assembly and trafficking machinery, and serves as an intermediary cluster carrier, putatively delivering cluster from the Isu scaffold protein to target proteins. The tripeptide glutathione is intimately involved in this role, providing cysteinyl coordination to the iron center of the Grx5-bound [2Fe-2S] cluster. Grx5 has a well-defined glutathione-binding pocket with protein amino acid residues providing many ionic and hydrogen binding contacts to the bound glutathione. In this report, we investigated the importance of these interactions in cluster chirality and exchange reactivity by systematically perturbing the crucial contacts by use of natural and non-natural amino acid substitutions to disrupt the binding contacts from both the protein and glutathione. Native Grx5 could be reconstituted with all of the glutathione analogs used, as well as other thiol ligands, such as DTT or L-cysteine, by in vitro chemical reconstitution, and the holo proteins were found to transfer [2Fe-2S] cluster to apo ferredoxin 1 at comparable rates. However, the circular dichroism spectra of these derivatives displayed prominent differences that reflect perturbations in local cluster chirality. These studies provided a detailed molecular understanding of glutathione-protein interactions in holo Grx5 that define both cluster spectroscopy and exchange chemistry.

Site-specific biomolecule labeling with gold clusters.

PubMed

Ackerson, Christopher J; Powell, Richard D; Hainfeld, James F

2010-01-01

Site-specific labeling of biomolecules in vitro with gold clusters can enhance the information content of electron cryomicroscopy experiments. This chapter provides a practical overview of well-established techniques for forming biomolecule/gold cluster conjugates. Three bioconjugation chemistries are covered: linker-mediated bioconjugation, direct gold-biomolecule bonding, and coordination-mediated bonding of nickel(II) nitrilotriacetic acid (NTA)-derivatized gold clusters to polyhistidine (His)-tagged proteins. Copyright © 2010 Elsevier Inc. All rights reserved.

Structural, elastic, electronic, optical and thermoelectric properties of the Zintl-phase Ae3AlAs3 (Ae = Sr, Ba)

NASA Astrophysics Data System (ADS)

Benahmed, A.; Bouhemadou, A.; Alqarni, B.; Guechi, N.; Al-Douri, Y.; Khenata, R.; Bin-Omran, S.

2018-05-01

First-principles calculations were performed to investigate the structural, elastic, electronic, optical and thermoelectric properties of the Zintl-phase Ae3AlAs3 (Ae = Sr, Ba) using two complementary approaches based on density functional theory. The pseudopotential plane-wave method was used to explore the structural and elastic properties whereas the full-potential linearised augmented plane wave approach was used to study the structural, electronic, optical and thermoelectric properties. The calculated structural parameters are in good consistency with the corresponding measured ones. The single-crystal and polycrystalline elastic constants and related properties were examined in details. The electronic properties, including energy band dispersions, density of states and charge-carrier effective masses, were computed using Tran-Blaha modified Becke-Johnson functional for the exchange-correlation potential. It is found that both studied compounds are direct band gap semiconductors. Frequency-dependence of the linear optical functions were predicted for a wide photon energy range up to 15 eV. Charge carrier concentration and temperature dependences of the basic parameters of the thermoelectric properties were explored using the semi-classical Boltzmann transport model. Our calculations unveil that the studied compounds are characterised by a high thermopower for both carriers, especially the p-type conduction is more favourable.

Quantum chemistry of the minimal CdSe clusters

NASA Astrophysics Data System (ADS)

Yang, Ping; Tretiak, Sergei; Masunov, Artëm E.; Ivanov, Sergei

2008-08-01

Colloidal quantum dots are semiconductor nanocrystals (NCs) which have stimulated a great deal of research and have attracted technical interest in recent years due to their chemical stability and the tunability of photophysical properties. While internal structure of large quantum dots is similar to bulk, their surface structure and passivating role of capping ligands (surfactants) are not fully understood to date. We apply ab initio wavefunction methods, density functional theory, and semiempirical approaches to study the passivation effects of substituted phosphine and amine ligands on the minimal cluster Cd2Se2, which is also used to benchmark different computational methods versus high level ab initio techniques. Full geometry optimization of Cd2Se2 at different theory levels and ligand coverage is used to understand the affinities of various ligands and the impact of ligands on cluster structure. Most possible bonding patterns between ligands and surface Cd/Se atoms are considered, including a ligand coordinated to Se atoms. The degree of passivation of Cd and Se atoms (one or two ligands attached to one atom) is also studied. The results suggest that B3LYP/LANL2DZ level of theory is appropriate for the system modeling, whereas frequently used semiempirical methods (such as AM1 and PM3) produce unphysical results. The use of hydrogen atom for modeling of the cluster passivating ligands is found to yield unphysical results as well. Hence, the surface termination of II-VI semiconductor NCs with hydrogen atoms often used in computational models should probably be avoided. Basis set superposition error, zero-point energy, and thermal corrections, as well as solvent effects simulated with polarized continuum model are found to produce minor variations on the ligand binding energies. The effects of Cd-Se complex structure on both the electronic band gap (highest occupied molecular orbital-lowest unoccupied molecular orbital energy difference) and ligand binding

Surveys of research in the Chemistry Division, Argonne National Laboratory

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

Grazis, B.M.

1992-01-01

Research reports are presented on reactive intermediates in condensed phase (radiation chemistry, photochemistry), electron transfer and energy conversion, photosynthesis and solar energy conversion, metal cluster chemistry, chemical dynamics in gas phase, photoionization-photoelectrons, characterization and reactivity of coal and coal macerals, premium coal sample program, chemical separations, heavy elements coordination chemistry, heavy elements photophysics/photochemistry, f-electron interactions, radiation chemistry of high-level wastes (gas generation in waste tanks), ultrafast molecular electronic devices, and nuclear medicine. Separate abstracts have been prepared. Accelerator activites and computer system/network services are also reported.

Surveys of research in the Chemistry Division, Argonne National Laboratory

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

Grazis, B.M.

1992-11-01

Research reports are presented on reactive intermediates in condensed phase (radiation chemistry, photochemistry), electron transfer and energy conversion, photosynthesis and solar energy conversion, metal cluster chemistry, chemical dynamics in gas phase, photoionization-photoelectrons, characterization and reactivity of coal and coal macerals, premium coal sample program, chemical separations, heavy elements coordination chemistry, heavy elements photophysics/photochemistry, f-electron interactions, radiation chemistry of high-level wastes (gas generation in waste tanks), ultrafast molecular electronic devices, and nuclear medicine. Separate abstracts have been prepared. Accelerator activites and computer system/network services are also reported.

The relationship between the electronic structure and thermoelectric properties of Zintl compounds M2Zn5As4 (M = K, Rb).

PubMed

Yang, Gui; Yang, Jueming; Yan, Yuli; Wang, Yuanxu

2014-03-28

The electronic structure and the thermoelectric properties of M2Zn5As4 (M = K, Rb) are studied by the first principles and the semiclassical BoltzTraP theory. It is determined that they are semiconductors with an indirect band gap of about 1 eV, which is much larger than that of Ca5Al2Sb6 (0.50 eV). The calculated electronic localization function indicates that they are typical Zintl bonding compounds. The combination of heavy and light bands near the valence band maximum may improve their thermoelectric performance. Rb2Zn5As4 exhibits relatively large Seebeck coefficients, high electrical conductivities, and the large "maximum" thermoelectric figures of merit (ZeT). Compared with Ca5Al2Sb6, the highest ZeT of Rb2Zn5As4 appears at relatively low carrier concentration. For Rb2Zn4As5, the p-type doping may achieve a higher thermoelectric performance than n-type doping. The thermoelectric properties of Rb2Zn5As4 are possibly superior to those of Ca5Al2Sb6.

Computational Design of Clusters for Catalysis

NASA Astrophysics Data System (ADS)

Jimenez-Izal, Elisa; Alexandrova, Anastassia N.

2018-04-01

When small clusters are studied in chemical physics or physical chemistry, one perhaps thinks of the fundamental aspects of cluster electronic structure, or precision spectroscopy in ultracold molecular beams. However, small clusters are also of interest in catalysis, where the cold ground state or an isolated cluster may not even be the right starting point. Instead, the big question is: What happens to cluster-based catalysts under real conditions of catalysis, such as high temperature and coverage with reagents? Myriads of metastable cluster states become accessible, the entire system is dynamic, and catalysis may be driven by rare sites present only under those conditions. Activity, selectivity, and stability are highly dependent on size, composition, shape, support, and environment. To probe and master cluster catalysis, sophisticated tools are being developed for precision synthesis, operando measurements, and multiscale modeling. This review intends to tell the messy story of clusters in catalysis.

Molecular growth from a Mo176 to a Mo248 cluster

NASA Astrophysics Data System (ADS)

Müller, A.; Shah, Syed Q. N.; Bögge, H.; Schmidtmann, M.

1999-01-01

In polyoxometalate chemistry a large variety of compounds, clusters and solid-state structures can be formed by the linking together of well-defined metal-oxygen building blocks, . These species exhibit unusual topological and electronic properties, andfind applications ranging from medicine to industrial processes. The recently reported ring-shaped mixed-valence polyoxomolybdates of the type {Mo154} (refs 5, 6) and {Mo176} (refs 7, 8) represent a new class of giant clusters with nanometre-sized cavities and interesting properties for host-guest chemistry. Here we describe the formation of related clusters of the type {Mo248} formed by addition of further units to the inner surface of the {Mo176 } `wheel'. The additional units arrange themselves into two {Mo36} `hub-caps' on the initial wheel-clusters that are not stable in isolation. These findings reveal a new pathway to the development of complex coordination clusters.

Occupational Listings Arranged by Cluster and Subject Matter Areas.

ERIC Educational Resources Information Center

Schwarz, Otto

Approximately 850 occupations are listed under 27 occupational clusters. The Dictionary of Occupational Title (DOT) number is specified for occupations in the clusters of business training and distributive education, chemistry, general shop and industrial arts, home economics, foreign language, music, social studies, art, agriculture, physics, and…

Chemistry and Processing of Nanostructured Materials

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

Fox, G A; Baumann, T F; Hope-Weeks, L J

2002-01-18

Nanostructured materials can be formed through the sol-gel polymerization of inorganic or organic monomer systems. For example, a two step polymerization of tetramethoxysilane (TMOS) was developed such that silica aerogels with densities as low as 3 kg/m{sup 3} ({approx} two times the density of air) could be achieved. Organic aerogels based upon resorcinol-formaldehyde and melamine-formaldehyde can also be prepared using the sol-gel process. Materials of this type have received significant attention at LLNL due to their ultrafine cell sizes, continuous porosity, high surface area and low mass density. For both types of aerogels, sol-gel polymerization depends upon the transformation ofmore » these monomers into nanometer-sized clusters followed by cross-linking into a 3-dimensional gel network. While sol-gel chemistry provides the opportunity to synthesize new material compositions, it suffers from the inability to separate the process of cluster formation from gelation. This limitation results in structural deficiencies in the gel that impact the physical properties of the aerogel, xerogel or nanocomposite. In order to control the properties of the resultant gel, one should be able to regulate the formation of the clusters and their subsequent cross-linking. Towards this goal, we are utilizing dendrimer chemistry to separate the cluster formation from the gelation so that new nanostructured materials can be produced. Dendrimers are three-dimensional, highly branched macromolecules that are prepared in such a way that their size, shape and surface functionality are readily controlled. The dendrimers will be used as pre-formed clusters of known size that can be cross-linked to form an ordered gel network.« less

THREE DISCRETE GROUPS WITH HOMOGENEOUS CHEMISTRY ALONG THE RED GIANT BRANCH IN THE GLOBULAR CLUSTER NGC 2808

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

Carretta, E., E-mail: eugenio.carretta@oabo.inaf.it

2014-11-10

We present the homogeneous reanalysis of Mg and Al abundances from high resolution UVES/FLAMES spectra for 31 red giants in the globular cluster NGC 2808. We found a well defined Mg-Al anticorrelation reaching a regime of subsolar Mg abundance ratios, with a spread of about 1.4 dex in [Al/Fe]. The main result from the improved statistics of our sample is that the distribution of stars is not continuous along the anticorrelation because they are neatly clustered into three distinct clumps, each with different chemical compositions. One group (P) shows a primordial composition of field stars of similar metallicity, and the other twomore » (I and E) have increasing abundances of Al and decreasing abundances of Mg. The fraction of stars we found in the three components (P: 68%, I: 19%, E: 13%) is in excellent agreement with the ratios computed for the three distinct main sequences in NGC 2808: for the first time there is a clear correspondence between discrete photometric sequences of dwarfs and distinct groups of giants with homogeneous chemistry. The composition of the I group cannot be reproduced by mixing of matter with extreme processing in hot H-burning and gas with pristine, unprocessed composition, as also found in the recent analysis of three discrete groups in NGC 6752. This finding suggests that different classes of polluters were probably at work in NGC 2808 as well.« less

Alumina Paste Sublimation Suppression Barrier for Thermoelectric Device

NASA Technical Reports Server (NTRS)

Caillat, Thierry (Inventor); Paik, Jong-Ah (Inventor)

2014-01-01

Alumina as a sublimation suppression barrier for a Zintl thermoelectric material in a thermoelectric power generation device operating at high temperature, e.g. at or above 1000K, is disclosed. The Zintl thermoelectric material may comprise Yb.sub.14MnSb.sub.11. The alumina may be applied as an adhesive paste dried and cured on a substantially oxide free surface of the Zintl thermoelectric material and polished to a final thickness. The sublimation suppression barrier may be finalized by baking out the alumina layer on the Zintl thermoelectric material until it becomes substantially clogged with ytterbia.

Chemistry and cosmology.

PubMed

Black, John H

2006-01-01

The simplest elements, hydrogen and helium, offer a remarkably rich chemistry, which has controlled crucial features of the early evolution of the universe. Theoretical models of the origin of structure (stars, galaxies, clusters of galaxies, etc.) now incorporate this chemistry in some detail. In addition to the origin of structure, cosmologists are concerned with observational tests of competing world models. Primordial chemistry may give rise to some of the earliest departures from thermodynamic equilibrium in the universe. These effects may be observable as broad-band spectroscopic distortions of the cosmic background radiation, which otherwise exhibits a nearly perfect blackbody spectrum. The chemical history of the expanding universe is followed through a detailed calculation of the evolution of the abundances of H, H+, H-, H2, H2+, H3+, and other minor species. It is shown that continuous absorption by the small concentration of H- can produce a distortion in the cosmic background spectrum with a maximum at a frequency near nu/c = 9 cm-1 (wavelength 1.1 mm). The predicted effect lies only a factor of 5 below current limits. Its detection would provide an important test of our understanding of the recombination epoch of the universe.

Human frataxin activates Fe-S cluster biosynthesis by facilitating sulfur transfer chemistry.

PubMed

Bridwell-Rabb, Jennifer; Fox, Nicholas G; Tsai, Chi-Lin; Winn, Andrew M; Barondeau, David P

2014-08-05

Iron-sulfur clusters are ubiquitous protein cofactors with critical cellular functions. The mitochondrial Fe-S assembly complex, which consists of the cysteine desulfurase NFS1 and its accessory protein (ISD11), the Fe-S assembly protein (ISCU2), and frataxin (FXN), converts substrates l-cysteine, ferrous iron, and electrons into Fe-S clusters. The physiological function of FXN has received a tremendous amount of attention since the discovery that its loss is directly linked to the neurodegenerative disease Friedreich's ataxia. Previous in vitro results revealed a role for human FXN in activating the cysteine desulfurase and Fe-S cluster biosynthesis activities of the Fe-S assembly complex. Here we present radiolabeling experiments that indicate FXN accelerates the accumulation of sulfur on ISCU2 and that the resulting persulfide species is viable in the subsequent synthesis of Fe-S clusters. Additional mutagenesis, enzyme kinetic, UV-visible, and circular dichroism spectroscopic studies suggest conserved ISCU2 residue C104 is critical for FXN activation, whereas C35, C61, and C104 are all essential for Fe-S cluster formation on the assembly complex. These results cannot be fully explained by the hypothesis that FXN functions as an iron donor for Fe-S cluster biosynthesis, and further support an allosteric regulator role for FXN. Together, these results lead to an activation model in which FXN accelerates persulfide formation on NFS1 and favors a helix-to-coil interconversion on ISCU2 that facilitates the transfer of sulfur from NFS1 to ISCU2 as an initial step in Fe-S cluster biosynthesis.

Human Frataxin Activates Fe–S Cluster Biosynthesis by Facilitating Sulfur Transfer Chemistry

PubMed Central

2015-01-01

Iron–sulfur clusters are ubiquitous protein cofactors with critical cellular functions. The mitochondrial Fe–S assembly complex, which consists of the cysteine desulfurase NFS1 and its accessory protein (ISD11), the Fe–S assembly protein (ISCU2), and frataxin (FXN), converts substrates l-cysteine, ferrous iron, and electrons into Fe–S clusters. The physiological function of FXN has received a tremendous amount of attention since the discovery that its loss is directly linked to the neurodegenerative disease Friedreich’s ataxia. Previous in vitro results revealed a role for human FXN in activating the cysteine desulfurase and Fe–S cluster biosynthesis activities of the Fe–S assembly complex. Here we present radiolabeling experiments that indicate FXN accelerates the accumulation of sulfur on ISCU2 and that the resulting persulfide species is viable in the subsequent synthesis of Fe–S clusters. Additional mutagenesis, enzyme kinetic, UV–visible, and circular dichroism spectroscopic studies suggest conserved ISCU2 residue C104 is critical for FXN activation, whereas C35, C61, and C104 are all essential for Fe–S cluster formation on the assembly complex. These results cannot be fully explained by the hypothesis that FXN functions as an iron donor for Fe–S cluster biosynthesis, and further support an allosteric regulator role for FXN. Together, these results lead to an activation model in which FXN accelerates persulfide formation on NFS1 and favors a helix-to-coil interconversion on ISCU2 that facilitates the transfer of sulfur from NFS1 to ISCU2 as an initial step in Fe–S cluster biosynthesis. PMID:24971490

Extraordinary cluster formation and intramolecular ligand-ligand interactions in cyanoacetylene [corrected] mediated by Mg+*: implications for the atmospheric chemistry of titan and for circumstellar chemistry.

PubMed

Milburn, Rebecca K; Hopkinson, Alan C; Bohme, Diethard K

2005-09-21

Experimental results are reported that track the kinetics of gas-phase reactions initiated by Mg+*, (c-C5H5)Mg+ and (c-C5H5)2Mg+* in hydrogen cyanide and cyanoacetylene. The experiments were performed with a selected-ion flow tube (SIFT) tandem mass spectrometer at a helium buffer-gas pressure of 0.35 +/- 0.01 Torr and at 294 +/- 3 K. The observed chemistries of Mg+* and (c-C5H5)Mg+ are dominated by sequential ligation, while that of (c-C5H5)2Mg+* is by ligand switching. The rate-coefficient measurements for sequential addition of cyanoacetylene to Mg+* indicate an extraordinary pattern in alternating chemical reactivity while multiple-collision induced dissociation experiments revealed an extraordinary stability for the Mg(HC3N)4+* cluster ion. Molecular orbital calculations with density functional theory (DFT) at the B3LYP level, Hartree-Fock (HF) and second-order Mphiller-Plesset (MP2) levels, all performed with a 6-31+G(d) basis set, have been used to calculate structures and energies for the observed Mg(HC3N)1-4(+)* cations. These calculations indicate that the path of formation of Mg(HC3N)4+* involves ligand-ligand interactions leading to two cyclic (HC3N)2 ligands which then interact to form 2,4,6,8-tetracyanosemibullvalene-Mg+ or 1,2,5,6-tetracyano-1,3,5,7-cyclooctatetraene-Mg+ cations. A case is made for the formation of similar complex organomagnesium ions in the upper atmosphere of Titan where subsequent electron-ion recombination may produce cyano derivatives of large unsaturated hydrocarbons. In contrast, circumstellar environments with their much higher relative content of free electrons are less likely to give rise to such chemistry.

Glutathione-complexed [2Fe-2S] clusters function in Fe-S cluster storage and trafficking.

PubMed

Fidai, Insiya; Wachnowsky, Christine; Cowan, J A

2016-10-01

Glutathione-coordinated [2Fe-2S] complex is a non-protein-bound [2Fe-2S] cluster that is capable of reconstituting the human iron-sulfur cluster scaffold protein IscU. This complex demonstrates physiologically relevant solution chemistry and is a viable substrate for iron-sulfur cluster transport by Atm1p exporter protein. Herein, we report on some of the possible functional and physiological roles for this novel [2Fe-2S](GS4) complex in iron-sulfur cluster biosynthesis and quantitatively characterize its role in the broader network of Fe-S cluster transfer reactions. UV-vis and circular dichroism spectroscopy have been used in kinetic studies to determine second-order rate constants for [2Fe-2S] cluster transfer from [2Fe-2S](GS4) complex to acceptor proteins, such as human IscU, Schizosaccharomyces pombe Isa1, human and yeast glutaredoxins (human Grx2 and Saccharomyces cerevisiae Grx3), and human ferredoxins. Second-order rate constants for cluster extraction from these holo proteins were also determined by varying the concentration of glutathione, and a likely common mechanism for cluster uptake was determined by kinetic analysis. The results indicate that the [2Fe-2S](GS4) complex is stable under physiological conditions, and demonstrates reversible cluster exchange with a wide range of Fe-S cluster proteins, thereby supporting a possible physiological role for such centers.

Nitrogenase Cofactor: Inspiration for Model Chemistry.

PubMed

Djurdjevic, Ivana; Einsle, Oliver; Decamps, Laure

2017-07-04

The cofactor of nitrogenase is the largest and most intricate metal cluster known in nature. Its reactivity, mode of action and even the precise binding site of substrate remain a matter of debate. For decades, synthetic chemists have taken inspiration from the exceptional structural, electronic and catalytic features of the cofactor and have tried to either mimic the unique topology of the entire site, or to extract its functional principles and build them into novel catalysts that achieve the same-or very similar-astounding transformations. We review some of the available model chemistry as it represents the various approaches that have been taken from studying the cofactor, to eventually summarize the current state of knowledge on catalysis by nitrogenase and highlight the mutually beneficial role of model chemistry and enzymology in bioinorganic chemistry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigating Faculty Familiarity with Assessment Terminology by Applying Cluster Analysis to Interpret Survey Data

ERIC Educational Resources Information Center

Raker, Jeffrey R.; Holme, Thomas A.

2014-01-01

A cluster analysis was conducted with a set of survey data on chemistry faculty familiarity with 13 assessment terms. Cluster groupings suggest a high, middle, and low overall familiarity with the terminology and an independent high and low familiarity with terms related to fundamental statistics. The six resultant clusters were found to be…

A meteor ablation-cluster ion atmospheric sodium theory

NASA Technical Reports Server (NTRS)

Richter, E. S.; Sechrist, C. F., Jr.

1979-01-01

Neutral and ionic forms of sodium form narrow, well-defined layers which peak in the 90-95 km altitude region at midlatitudes. A new theory for the sodium layer is presented, which is found to be in good agreement with existing atmospheric observations as well as available laboratory measurements of rate constants. The layer is believed to result naturally from a meteor ablation source over a chemical sink with vertical transport of Na(+) playing an important role in the layer shape and variation. While the neutral chemistry is believed to consist of chemical equilibrium between Na and NaO, the ion chemistry departs from earlier studies and considers a cluster ion scheme. It is possible that higher-order cluster ions of sodium play a role in the formation of aerosols, through attachment or ion-induced nucleation processes.

Cluster-based analysis of multi-model climate ensembles

NASA Astrophysics Data System (ADS)

Hyde, Richard; Hossaini, Ryan; Leeson, Amber A.

2018-06-01

Clustering - the automated grouping of similar data - can provide powerful and unique insight into large and complex data sets, in a fast and computationally efficient manner. While clustering has been used in a variety of fields (from medical image processing to economics), its application within atmospheric science has been fairly limited to date, and the potential benefits of the application of advanced clustering techniques to climate data (both model output and observations) has yet to be fully realised. In this paper, we explore the specific application of clustering to a multi-model climate ensemble. We hypothesise that clustering techniques can provide (a) a flexible, data-driven method of testing model-observation agreement and (b) a mechanism with which to identify model development priorities. We focus our analysis on chemistry-climate model (CCM) output of tropospheric ozone - an important greenhouse gas - from the recent Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP). Tropospheric column ozone from the ACCMIP ensemble was clustered using the Data Density based Clustering (DDC) algorithm. We find that a multi-model mean (MMM) calculated using members of the most-populous cluster identified at each location offers a reduction of up to ˜ 20 % in the global absolute mean bias between the MMM and an observed satellite-based tropospheric ozone climatology, with respect to a simple, all-model MMM. On a spatial basis, the bias is reduced at ˜ 62 % of all locations, with the largest bias reductions occurring in the Northern Hemisphere - where ozone concentrations are relatively large. However, the bias is unchanged at 9 % of all locations and increases at 29 %, particularly in the Southern Hemisphere. The latter demonstrates that although cluster-based subsampling acts to remove outlier model data, such data may in fact be closer to observed values in some locations. We further demonstrate that clustering can provide a viable and

Supersonic Beam Observations of Semiconductor Clusters.

DTIC Science & Technology

1987-08-31

laser vaporization C 6 0 molecule, soccerball structure contains cenLrai cavity 20, ASIT"RACT’ (Contms an .evse &I if rvcwumV sodIdwnttY by block...Brucat, S. Yang, C.L. Pettiette, M.J. Craycraft, and R.E. Smalley, Proc. of the International Symposium on the Physics and Chemistry of Small Clusters

Understanding Boron through Size-Selected Clusters: Structure, Chemical Bonding, and Fluxionality

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

Sergeeva, Alina P.; Popov, Ivan A.; Piazza, Zachary A.

Conspectus Boron is an interesting element with unusual polymorphism. While three-dimensional (3D) structural motifs are prevalent in bulk boron, atomic boron clusters are found to have planar or quasi-planar structures, stabilized by localized two-center–two-electron (2c–2e) σ bonds on the periphery and delocalized multicenter–two-electron (nc–2e) bonds in both σ and π frameworks. Electron delocalization is a result of boron’s electron deficiency and leads to fluxional behavior, which has been observed in B13+ and B19–. A unique capability of the in-plane rotation of the inner atoms against the periphery of the cluster in a chosen direction by employing circularly polarized infrared radiationmore » has been suggested. Such fluxional behaviors in boron clusters are interesting and have been proposed as molecular Wankel motors. The concepts of aromaticity and antiaromaticity have been extended beyond organic chemistry to planar boron clusters. The validity of these concepts in understanding the electronic structures of boron clusters is evident in the striking similarities of the π-systems of planar boron clusters to those of polycyclic aromatic hydrocarbons, such as benzene, naphthalene, coronene, anthracene, or phenanthrene. Chemical bonding models developed for boron clusters not only allowed the rationalization of the stability of boron clusters but also lead to the design of novel metal-centered boron wheels with a record-setting planar coordination number of 10. The unprecedented highly coordinated borometallic molecular wheels provide insights into the interactions between transition metals and boron and expand the frontier of boron chemistry. Another interesting feature discovered through cluster studies is boron transmutation. Even though it is well-known that B–, formed by adding one electron to boron, is isoelectronic to carbon, cluster studies have considerably expanded the possibilities of new structures and new materials using the

Understanding boron through size-selected clusters: structure, chemical bonding, and fluxionality.

PubMed

Sergeeva, Alina P; Popov, Ivan A; Piazza, Zachary A; Li, Wei-Li; Romanescu, Constantin; Wang, Lai-Sheng; Boldyrev, Alexander I

2014-04-15

Boron is an interesting element with unusual polymorphism. While three-dimensional (3D) structural motifs are prevalent in bulk boron, atomic boron clusters are found to have planar or quasi-planar structures, stabilized by localized two-center-two-electron (2c-2e) σ bonds on the periphery and delocalized multicenter-two-electron (nc-2e) bonds in both σ and π frameworks. Electron delocalization is a result of boron's electron deficiency and leads to fluxional behavior, which has been observed in B13(+) and B19(-). A unique capability of the in-plane rotation of the inner atoms against the periphery of the cluster in a chosen direction by employing circularly polarized infrared radiation has been suggested. Such fluxional behaviors in boron clusters are interesting and have been proposed as molecular Wankel motors. The concepts of aromaticity and antiaromaticity have been extended beyond organic chemistry to planar boron clusters. The validity of these concepts in understanding the electronic structures of boron clusters is evident in the striking similarities of the π-systems of planar boron clusters to those of polycyclic aromatic hydrocarbons, such as benzene, naphthalene, coronene, anthracene, or phenanthrene. Chemical bonding models developed for boron clusters not only allowed the rationalization of the stability of boron clusters but also lead to the design of novel metal-centered boron wheels with a record-setting planar coordination number of 10. The unprecedented highly coordinated borometallic molecular wheels provide insights into the interactions between transition metals and boron and expand the frontier of boron chemistry. Another interesting feature discovered through cluster studies is boron transmutation. Even though it is well-known that B(-), formed by adding one electron to boron, is isoelectronic to carbon, cluster studies have considerably expanded the possibilities of new structures and new materials using the B(-)/C analogy. It is

UV-light-driven prebiotic synthesis of iron-sulfur clusters

NASA Astrophysics Data System (ADS)

Bonfio, Claudia; Valer, Luca; Scintilla, Simone; Shah, Sachin; Evans, David J.; Jin, Lin; Szostak, Jack W.; Sasselov, Dimitar D.; Sutherland, John D.; Mansy, Sheref S.

2017-12-01

Iron-sulfur clusters are ancient cofactors that play a fundamental role in metabolism and may have impacted the prebiotic chemistry that led to life. However, it is unclear whether iron-sulfur clusters could have been synthesized on prebiotic Earth. Dissolved iron on early Earth was predominantly in the reduced ferrous state, but ferrous ions alone cannot form polynuclear iron-sulfur clusters. Similarly, free sulfide may not have been readily available. Here we show that UV light drives the synthesis of [2Fe-2S] and [4Fe-4S] clusters through the photooxidation of ferrous ions and the photolysis of organic thiols. Iron-sulfur clusters coordinate to and are stabilized by a wide range of cysteine-containing peptides and the assembly of iron-sulfur cluster-peptide complexes can take place within model protocells in a process that parallels extant pathways. Our experiments suggest that iron-sulfur clusters may have formed easily on early Earth, facilitating the emergence of an iron-sulfur-cluster-dependent metabolism.

Chemistry That Applies. What Works Clearinghouse Intervention Report

ERIC Educational Resources Information Center

What Works Clearinghouse, 2012

2012-01-01

"Chemistry That Applies" is an instructional unit designed to help students in grades 8-10 understand the law of conservation of matter. It consists of 24 lessons organized in four clusters. Working in groups, students explore four chemical reactions: burning, rusting, the decomposition of water, and the reaction of baking soda and…

Molecular Dynamics Studies of Thermal Induced Chemistry in Tatb

NASA Astrophysics Data System (ADS)

Quenneville, J.; Germann, T. C.; Thompson, A. P.; Kober, E. M.

2007-12-01

A reactive force field (ReaxFF) is used with molecular dynamics to probe the chemistry induced by intense heating (`accelerated cook-off') of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). Large-system simulations are desired for TATB because of the high degree of carbon clustering expected in this material. Using small, 32-molecule simulations, we calculate the reaction rate as a function of temperature and compare the Arrhenius-predicted activation energy with experiment. Decomposition product evolution (mainly N2, H2O, CO2 and graphitic carbon clusters) is followed using a 576-molecule larger simulation, which also illustrates the effect of system size on both carbon clustering and reaction rate.

Metal cluster chemistry: Structure and stereochemistry in the polynuclear rhodium hydrides HnRhn[P(OR)3]2n

PubMed Central

Brown, R. K.; Williams, J. M.; Fredrich, M. F.; Day, V. W.; Sivak, A. J.; Muetterties, E. L.

1979-01-01

Crystallographic analyses of x-ray and neutron diffraction data have provided a definitive structural representation of {HRh[P(O-i-C3H7)3]2}2 and {HRh[P(OCH3)3]2}3. These polynuclear hydrides are generated from square planar H2Rh[P(OR)3]2 units by edge (hydrogen atom) sharing and by vertex (hydrogen atom) sharing to form the dimeric and trimeric structures, respectively. The square-planar units are held together through four-center and three-center two-electron Rh—H—Rh bonds in the dimer and trimer, respectively. The dimer and trimer molecules each add one molecule of hydrogen to form H[(i-C3H7O)3P]2RhH3Rh [P(O-i-C3H7)3]2 and H5Rh3[P(OCH3)3]6, respectively. NMR spectral information has served to define the stereochemical features of these polyhydrides. The significance of this chemistry in the metal cluster-metal surface analogy is described. PMID:16592645

Theoretical research program to study transition metal trimers and embedded clusters

NASA Technical Reports Server (NTRS)

Walch, Stephen P.

1987-01-01

The results of ab-initio calculations are reported for (1) small transition metal clusters and (2) potential energy surfaces for chemical reactions important in hydrogen combustion and high temperature air chemistry.

Hydration of a Large Anionic Charge Distribution - Naphthalene-Water Cluster Anions

NASA Astrophysics Data System (ADS)

Weber, J. Mathias; Adams, Christopher L.

2010-06-01

We report the infrared spectra of anionic clusters of naphthalene with up to three water molecules. Comparison of the experimental infrared spectra with theoretically predicted spectra from quantum chemistry calculations allow conclusions regarding the structures of the clusters under study. The first water molecule forms two hydrogen bonds with the π electron system of the naphthalene moiety. Subsequent water ligands interact with both the naphthalene and the other water ligands to form hydrogen bonded networks, similar to other hydrated anion clusters. Naphthalene-water anion clusters illustrate how water interacts with negative charge delocalized over a large π electron system. The clusters are interesting model systems that are discussed in the context of wetting of graphene surfaces and polyaromatic hydrocarbons.

Collaborative Physical Chemistry Projects Involving Computational Chemistry

NASA Astrophysics Data System (ADS)

Whisnant, David M.; Howe, Jerry J.; Lever, Lisa S.

2000-02-01

The physical chemistry classes from three colleges have collaborated on two computational chemistry projects using Quantum CAChe 3.0 and Gaussian 94W running on Pentium II PCs. Online communication by email and the World Wide Web was an important part of the collaboration. In the first project, students used molecular modeling to predict benzene derivatives that might be possible hair dyes. They used PM3 and ZINDO calculations to predict the electronic spectra of the molecules and tested the predicted spectra by comparing some with experimental measurements. They also did literature searches for real hair dyes and possible health effects. In the final phase of the project they proposed a synthetic pathway for one compound. In the second project the students were asked to predict which isomer of a small carbon cluster (C3, C4, or C5) was responsible for a series of IR lines observed in the spectrum of a carbon star. After preliminary PM3 calculations, they used ab initio calculations at the HF/6-31G(d) and MP2/6-31G(d) level to model the molecules and predict their vibrational frequencies and rotational constants. A comparison of the predictions with the experimental spectra suggested that the linear isomer of the C5 molecule was responsible for the lines.

Using Cluster Analysis to Characterize Meaningful Learning in a First-Year University Chemistry Laboratory Course

ERIC Educational Resources Information Center

Galloway, Kelli R.; Bretz, Stacey Lowery

2015-01-01

The Meaningful Learning in the Laboratory Instrument (MLLI) was designed to measure students' cognitive and affective learning in the university chemistry laboratory. The MLLI was administered at the beginning and the end of the first semester to first-year university chemistry students to measure their expectations and experiences for learning in…

Thermoelectric properties of AMg 2X 2, AZn 2Sb 2 (A = Ca, Sr, Ba; X = Sb, Bi), and Ba 2ZnX 2 (X = Sb, Bi) Zintl compounds

DOE PAGES

Sun, Jifeng; Singh, David J.

2017-04-03

In this paper, we report a theoretical investigation of the electronic structure and transport properties of eleven Zintl compounds including nine 122 phases (AMg 2X 2, AZn 2Sb 2 (A = Ca, Sr, Ba; X = Sb, Bi)) and two 212 phases (Ba 2ZnX 2 (X = Sb, Bi)). The electronic structures and electrical transport properties are studied using ab initio calculations and semi-classical Boltzmann theory within the constant relaxation time approximation. All the compounds are semiconducting. We find that the n-type 122 phases with the CaAl 2Si 2 structure type show better performance than p-type materials due to themore » multi-valley degeneracy with anisotropic carrier pockets at and near the conduction band minimum. The pocket anisotropy is beneficial in achieving high conductivity and Seebeck coefficient simultaneously. This mechanism yields substantial improvement in the power factor. Finally, the general performance of 212 phases is inferior to that of the 122 phases, with the Ba 2ZnSb 2 compound showing better performance.« less

Structural diversity in Ni II cluster chemistry: Ni 5, Ni 6, and {NiNa 2} n complexes bearing the Schiff-base ligand N-naphthalidene-2-amino-5-chlorobenzoic acid

DOE PAGES

Perlepe, Panagiota S.; Cunha-Silva, Luis; Bekiari, Vlasoula; ...

2016-05-23

The employment of the fluorescent bridging and chelating ligand N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH 2) in Ni II cluster chemistry has led to a series of pentanuclear and hexanuclear compounds with different structural motifs, magnetic and optical properties, as well as an interesting 1-D coordination polymer. Synthetic parameters such as the inorganic anion present in the NiX 2 starting materials (X = ClO 4 - or Cl -), the reaction solvent and the nature of the organic base employed for the deprotonation of nacbH 2 were also proved to be structure-directing components. Undoubtedly, the reported results demonstrate the rich coordination chemistry ofmore » nacbH 2 in the presence of Ni II metal ions and the ability of this chelate to adopt a variety of different modes, thus fostering the formation of high-nuclearity molecules with many physical properties.« less

Fission and fusion scenarios for magnetic microswimmer clusters

PubMed Central

Guzmán-Lastra, Francisca; Kaiser, Andreas; Löwen, Hartmut

2016-01-01

Fission and fusion processes of particle clusters occur in many areas of physics and chemistry from subnuclear to astronomic length scales. Here we study fission and fusion of magnetic microswimmer clusters as governed by their hydrodynamic and dipolar interactions. Rich scenarios are found that depend crucially on whether the swimmer is a pusher or a puller. In particular a linear magnetic chain of pullers is stable while a pusher chain shows a cascade of fission (or disassembly) processes as the self-propulsion velocity is increased. Contrarily, magnetic ring clusters show fission for any type of swimmer. Moreover, we find a plethora of possible fusion (or assembly) scenarios if a single swimmer collides with a ringlike cluster and two rings spontaneously collide. Our predictions are obtained by computer simulations and verifiable in experiments on active colloidal Janus particles and magnetotactic bacteria. PMID:27874006

Theoretical Studies of the Extraterrestrial Chemistry of Biogenic Elements and Compounds

NASA Technical Reports Server (NTRS)

Woon, D. E.

1998-01-01

The report discusses modeling gas-grain chemistry with ab initio quantum chemical cluster calculations which include heterogeneous hydrogenation of CO and H2CO on icy grain mantles, and ammonia-catalyzed, water-enhanced polymerization of formaldehyde in laboratory studies of astrophysical ices.

Trinuclear rhenium(III) halide clusters with carboxylate ligands

NASA Astrophysics Data System (ADS)

Dougan, Jeffrey Steven

Four mono(carboxylato)trirhenium complexes and three bis(carboxylato)trirhenium complexes have been synthesized and characterized, principally by mass spectrometry, with supporting evidence from X-ray diffraction. These compounds represent the first trinuclear rhenium carboxylate complexes. The reactions generally proceed readily under comparatively mild conditions. Mass spectrometry has again proved its usefulness as a technique in the field of metal cluster chemistry, having provided the initial identification of the products of the reactions studied. These compounds provide a further base to which future mass spectra of metal cluster compounds can be compared. Re-examination of a reaction reported by Taha and Wilkinson has also cast considerable doubt onto the validity of a conversion widely reported in the literature that transforms (Re3Cl9) x into [Re2(O2CCH3)4Cl 2]. We believe that the literature result is a consequence of the purity of the metal precursor, and suggest that the starting material in the earlier work may have contained ReCl4 or ReCl5. The importance of mass spectrometry in the characterization of the new compounds synthesized in this project has led to a thorough study of calculated isotopic distributions. The information gathered suggests that for isotopically simple molecules, the choice of algorithm for computing an isotopic distribution is unimportant. However, it is important to compute the mass spectrum of an isotopically complex molecule using an algorithm that can, if desired, show the underlying isotopic fine structure of a peak of interest. In the last chapter of this thesis, the results of a project in chemistry education research are presented. Predicting the success of students in general chemistry has long been of interest to the chemistry education community, and several factors have been identified as contributing factors. An off-hand comment by a student inspired an examination of whether continuity with the same instructor for

Polyhydrido Copper Clusters: Synthetic Advances, Structural Diversity, and Nanocluster-to-Nanoparticle Conversion.

PubMed

Dhayal, Rajendra S; van Zyl, Werner E; Liu, C W

2016-01-19

Metal hydride clusters have historically been studied to unravel their aesthetically pleasing molecular structures and interesting properties, especially toward hydrogen related applications. Central to this work is the hydride ligand, H¯, the smallest closed-shell spherical anion known. Two new developments in polyhydrido nanocluster chemistry include the determination of heretofore unknown hydride coordination modes and novel structural constructs, and conversion from the molecular entities to rhombus-shaped copper nanoparticles (CuNPs). These advances, together with hydrogen evolution and catalysis, have provided both experimentalists and theorists with a rich scientific directive to further explore. The isolation of hexameric [{(Ph3P)CuH}6] (Stryker reagent) could be regarded as the springboard for the recent emergence of polyhydrido copper cluster chemistry due to its utilization in a variety of organic chemical transformations. The stability of clusters of various nuclearity was improved through phosphine, pyridine, and carbene type ligands. Our focus lies with the isolation of novel copper (poly)hydride clusters using mostly the phosphor-1,1-dithiolato type ligands. We found such chalcogen-stabilized clusters to be exceptionally air and moisture stable over a wide range of nuclearities (Cu7 to Cu32). In this Account, we (i) report on state-of-the-art copper hydride cluster chemistry, especially with regards to the diverse and novel structural types generally, and newly discovered hydride coordination modes in particular, (ii) demonstrate the indispensable power of neutron diffraction for the unambiguous assignment and location of hydride ligand(s) within a cluster, and (iii) prove unique transformations that can occur not only between well characterized high nuclearity clusters, but also how such clusters can transform to uniquely shaped nanoparticles of several nanometers in diameter through copper hydride reduction. The increase in the number of low- to

Fission and fusion scenarios for magnetic microswimmer clusters

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

Guzmán-Lastra, Francisca; Kaiser, Andreas; Löwen, Hartmut

Fission and fusion processes of particle clusters occur in many areas of physics and chemistry from subnuclear to astronomic length scales. Here we study fission and fusion of magnetic microswimmer clusters as governed by their hydrodynamic and dipolar interactions. Rich scenarios are found that depend crucially on whether the swimmer is a pusher or a puller. In particular a linear magnetic chain of pullers is stable while a pusher chain shows a cascade of fission (or disassembly) processes as the self-propulsion velocity is increased. Contrarily, magnetic ring clusters show fission for any type of swimmer. Moreover, we find a plethoramore » of possible fusion (or assembly) scenarios if a single swimmer collides with a ringlike cluster and two rings spontaneously collide. Lastly, our predictions are obtained by computer simulations and verifiable in experiments on active colloidal Janus particles and magnetotactic bacteria.« less

Fission and fusion scenarios for magnetic microswimmer clusters

DOE PAGES

Guzmán-Lastra, Francisca; Kaiser, Andreas; Löwen, Hartmut

2016-11-22

Fission and fusion processes of particle clusters occur in many areas of physics and chemistry from subnuclear to astronomic length scales. Here we study fission and fusion of magnetic microswimmer clusters as governed by their hydrodynamic and dipolar interactions. Rich scenarios are found that depend crucially on whether the swimmer is a pusher or a puller. In particular a linear magnetic chain of pullers is stable while a pusher chain shows a cascade of fission (or disassembly) processes as the self-propulsion velocity is increased. Contrarily, magnetic ring clusters show fission for any type of swimmer. Moreover, we find a plethoramore » of possible fusion (or assembly) scenarios if a single swimmer collides with a ringlike cluster and two rings spontaneously collide. Lastly, our predictions are obtained by computer simulations and verifiable in experiments on active colloidal Janus particles and magnetotactic bacteria.« less

Low temperature surface chemistry and nanostructures

NASA Astrophysics Data System (ADS)

Sergeev, G. B.; Shabatina, T. I.

2002-03-01

The new scientific field of low temperature surface chemistry, which combines the low temperature chemistry (cryochemistry) and surface chemistry approaches, is reviewed in this paper. One of the most exciting achievements in this field of science is the development of methods to create highly ordered hybrid nanosized structures on different organic and inorganic surfaces and to encapsulate nanosized metal particles in organic and polymer matrices. We consider physical and chemical behaviour for the systems obtained by co-condensation of the components vapours on the surfaces cooled down to 4-10 and 70-100 K. In particular the size effect of both types, the number of atoms in the reactive species structure and the thickness of growing co-condensate film, on the chemical activity of the system is analysed in detail. The effect of the internal mechanical stresses on the growing interfacial co-condensate film formation and on the generation of fast (explosive) spontaneous reactions at low temperatures is discussed. The examples of unusual chemical interactions of metal atoms, clusters and nanosized particles, obtained in co-condensate films on the cooled surfaces under different conditions, are presented. The examples of highly ordered surface and volume hybrid nanostructures formation are analysed.

A grand unified model for liganded gold clusters

NASA Astrophysics Data System (ADS)

Xu, Wen Wu; Zhu, Beien; Zeng, Xiao Cheng; Gao, Yi

2016-12-01

A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three `flavours' (namely, bottom, middle and top) to represent three possible valence states. The `composite particles' in GUM are categorized into two groups: variants of triangular elementary block Au3(2e) and tetrahedral elementary block Au4(2e), all satisfying the duet rule (2e) of the valence shell, akin to the octet rule in general chemistry. The elementary blocks, when packed together, form the cores of liganded gold clusters. With the GUM, structures of 71 liganded gold clusters and their growth mechanism can be deciphered altogether. Although GUM is a predictive heuristic and may not be necessarily reflective of the actual electronic structure, several highly stable liganded gold clusters are predicted, thereby offering GUM-guided synthesis of liganded gold clusters by design.

A grand unified model for liganded gold clusters

PubMed Central

Xu, Wen Wu; Zhu, Beien; Zeng, Xiao Cheng; Gao, Yi

2016-01-01

A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three ‘flavours' (namely, bottom, middle and top) to represent three possible valence states. The ‘composite particles' in GUM are categorized into two groups: variants of triangular elementary block Au3(2e) and tetrahedral elementary block Au4(2e), all satisfying the duet rule (2e) of the valence shell, akin to the octet rule in general chemistry. The elementary blocks, when packed together, form the cores of liganded gold clusters. With the GUM, structures of 71 liganded gold clusters and their growth mechanism can be deciphered altogether. Although GUM is a predictive heuristic and may not be necessarily reflective of the actual electronic structure, several highly stable liganded gold clusters are predicted, thereby offering GUM-guided synthesis of liganded gold clusters by design. PMID:27910848

Molecular Dynamics Studies of Thermal Induced Chemistry in TATB

NASA Astrophysics Data System (ADS)

Quenneville, Jason; Germann, Timothy

2007-06-01

A reactive force field (ReaxFF^2) is used with molecular dynamics to probe the chemistry induced by intense heating (accelerated `cook-off') of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). Large-system simulations are desired for TATB because of the high degree of carbon clustering expected in this material. Using small, 800-atom, simulations, we will show the reaction rate as a function of temperature and density as well as the time evolution of reaction products. A larger simulation (with 14,000 atoms) will illustrate the effect of system size on both carbon clustering and reaction rate. Insight into the mechanisms of product formation will be given, as well as the chemical structure (graphitic or diamond-like) of the carbon clusters obtained. ^2 A. C. T. Van Duin, et al, J. Phys. Chem. A, 1005, 9396 (2001).

Clustering of water molecules in ultramicroporous carbon: In-situ small-angle neutron scattering

DOE PAGES

Bahadur, Jitendra; Contescu, Cristian I.; Rai, Durgesh K.; ...

2016-10-19

The adsorption of water is central to most of the applications of microporous carbon as adsorbent material. We report early kinetics of water adsorption in the microporous carbon using in-situ small-angle neutron scattering. It is observed that adsorption of water occurs via cluster formation of molecules. Interestingly, the cluster size remains constant throughout the adsorption process whereas number density of clusters increases with time. The role of surface chemistry of microporous carbon on the early kinetics of adsorption process was also investigated. Lastly, the present study provides direct experimental evidence for cluster assisted adsorption of water molecules in microporous carbonmore » (Do-Do model).« less

Atomically precise organomimetic cluster nanomolecules assembled via perfluoroaryl-thiol SNAr chemistry

NASA Astrophysics Data System (ADS)

Qian, Elaine A.; Wixtrom, Alex I.; Axtell, Jonathan C.; Saebi, Azin; Jung, Dahee; Rehak, Pavel; Han, Yanxiao; Moully, Elamar Hakim; Mosallaei, Daniel; Chow, Sylvia; Messina, Marco S.; Wang, Jing Yang; Royappa, A. Timothy; Rheingold, Arnold L.; Maynard, Heather D.; Král, Petr; Spokoyny, Alexander M.

2017-04-01

The majority of biomolecules are intrinsically atomically precise, an important characteristic that enables rational engineering of their recognition and binding properties. However, imparting a similar precision to hybrid nanoparticles has been challenging because of the inherent limitations of existing chemical methods and building blocks. Here we report a new approach to form atomically precise and highly tunable hybrid nanomolecules with well-defined three-dimensionality. Perfunctionalization of atomically precise clusters with pentafluoroaryl-terminated linkers produces size-tunable rigid cluster nanomolecules. These species are amenable to facile modification with a variety of thiol-containing molecules and macromolecules. Assembly proceeds at room temperature within hours under mild conditions, and the resulting nanomolecules exhibit high stabilities because of their full covalency. We further demonstrate how these nanomolecules grafted with saccharides can exhibit dramatically improved binding affinity towards a protein. Ultimately, the developed strategy allows the rapid generation of precise molecular assemblies to investigate multivalent interactions.

Simultaneous assessment of phase chemistry, phase abundance and bulk chemistry with statistical electron probe micro-analyses: Application to cement clinkers

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

Wilson, William; Krakowiak, Konrad J.; Ulm, Franz-Josef, E-mail: ulm@mit.edu

2014-01-15

According to recent developments in cement clinker engineering, the optimization of chemical substitutions in the main clinker phases offers a promising approach to improve both reactivity and grindability of clinkers. Thus, monitoring the chemistry of the phases may become part of the quality control at the cement plants, along with the usual measurements of the abundance of the mineralogical phases (quantitative X-ray diffraction) and the bulk chemistry (X-ray fluorescence). This paper presents a new method to assess these three complementary quantities with a single experiment. The method is based on electron microprobe spot analyses, performed over a grid located onmore » a representative surface of the sample and interpreted with advanced statistical tools. This paper describes the method and the experimental program performed on industrial clinkers to establish the accuracy in comparison to conventional methods. -- Highlights: •A new method of clinker characterization •Combination of electron probe technique with cluster analysis •Simultaneous assessment of phase abundance, composition and bulk chemistry •Experimental validation performed on industrial clinkers.« less

Protactinium and the intersection of actinide and transition metal chemistry

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

Wilson, Richard E.; De Sio, Stephanie; Vallet, Valérie

The role of the 5f and 6d orbitals in the chemistry of the actinide elements has been of considerable interest since their discovery and synthesis. Relativistic effects cause the energetics of the 5f and 6d orbitals to change as the actinide series is traversed left to right imparting a rich and complex chemistry. The 5f and 6d atomic states cross in energy at protactinium (Pa), making it a potential intersection between transition metal and actinide chemistries. Herein, we report the synthesis of a Pa-peroxo cluster, A(6)(Pa4O(O-2)(6)F-12) [A = Rb, Cs, (CH3)(4)N], formed in pursuit of an actinide polyoxometalate. Quantum chemicalmore » calculations at the density functional theory level demonstrate equal 5f and 6d orbital participation in the chemistry of Pa and increasing 5f orbital participation for the heavier actinides. Periodic changes in orbital character to the bonding in the early actinides highlights the influence of the 5f orbitals in their reactivity and chemical structure.« less

Iron-sulfur clusters as biological sensors: the chemistry of reactions with molecular oxygen and nitric oxide.

PubMed

Crack, Jason C; Green, Jeffrey; Thomson, Andrew J; Le Brun, Nick E

2014-10-21

Iron-sulfur cluster proteins exhibit a range of physicochemical properties that underpin their functional diversity in biology, which includes roles in electron transfer, catalysis, and gene regulation. Transcriptional regulators that utilize iron-sulfur clusters are a growing group that exploit the redox and coordination properties of the clusters to act as sensors of environmental conditions including O2, oxidative and nitrosative stress, and metabolic nutritional status. To understand the mechanism by which a cluster detects such analytes and then generates modulation of DNA-binding affinity, we have undertaken a combined strategy of in vivo and in vitro studies of a range of regulators. In vitro studies of iron-sulfur cluster proteins are particularly challenging because of the inherent reactivity and fragility of the cluster, often necessitating strict anaerobic conditions for all manipulations. Nevertheless, and as discussed in this Account, significant progress has been made over the past decade in studies of O2-sensing by the fumarate and nitrate reduction (FNR) regulator and, more recently, nitric oxide (NO)-sensing by WhiB-like (Wbl) and FNR proteins. Escherichia coli FNR binds a [4Fe-4S] cluster under anaerobic conditions leading to a DNA-binding dimeric form. Exposure to O2 converts the cluster to a [2Fe-2S] form, leading to protein monomerization and hence loss of DNA binding ability. Spectroscopic and kinetic studies have shown that the conversion proceeds via at least two steps and involves a [3Fe-4S](1+) intermediate. The second step involves the release of two bridging sulfide ions from the cluster that, unusually, are not released into solution but rather undergo oxidation to sulfane (S(0)) subsequently forming cysteine persulfides that then coordinate the [2Fe-2S] cluster. Studies of other [4Fe-4S] cluster proteins that undergo oxidative cluster conversion indicate that persulfide formation and coordination may be more common than previously

Polyoxometalates: from inorganic chemistry to materials science.

PubMed

Casañ-Pastor, Nieves; Gómez-Romero, Pedro

2004-05-01

Polyoxometalates have been traditionally the subject of study of molecular inorganic chemistry. Yet, these polynuclear molecules, reminiscent of oxide clusters, present a wide range of structures and with them ideal frameworks for the deployment of a plethora of useful magnetic, electroionic, catalytic, bioactive and photochemical properties. With this in mind, a new trend towards the application of these remarkable species in materials science is beginning to develop. In this review we analyze this trend and discuss two main lines of thought for the application of polyoxometalates as materials. On the one hand, there is their use as clusters with inherently useful properties on themselves, a line which has produced fundamental studies of their magnetic, electronic or photoelectrochemical properties and has shown these clusters as models for quantum-sized oxides. On the other hand, the encapsulation or integration of polyoxometalates into organic, polymeric or inorganic matrices or substrates opens a whole new field within the area of hybrid materials for harnessing the multifunctional properties of these versatile species in a wide variety of applications, ranging from catalysis to energy storage to biomedicine.

Mixed-metal cluster chemistry. 28. Core enlargement of tungsten-iridium clusters with alkynyl, ethyndiyl, and butadiyndiyl reagents.

PubMed

Dalton, Gulliver T; Viau, Lydie; Waterman, Susan M; Humphrey, Mark G; Bruce, Michael I; Low, Paul J; Roberts, Rachel L; Willis, Anthony C; Koutsantonis, George A; Skelton, Brian W; White, Allan H

2005-05-02

Reaction of [WIr3(mu-CO)3(CO)8(eta-C5Me5)] (1c) with [W(C[triple bond]CPh)(CO)3(eta-C5H5)] afforded the edge-bridged tetrahedral cluster [W2Ir3(mu4-eta2-C2Ph)(mu-CO)(CO)9(eta-C5H5)(eta-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W3Ir3(mu4-eta2-C2Ph)(mu-eta2-C=CHPh)(Cl)(CO)8(eta-C5Me5)(eta-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C[triple bond]CPh)(CO)3(eta-C5H5)] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a mu4-eta2 alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a mu4-eta2 fashion, as well as a vinylidene ligand bridging a W-W bond. Reaction of [WIr3(CO)11(eta-C5H5)] (1a) or 1c with [(eta-C5H5)(CO)2 Ru(C[triple bond]C)Ru(CO)2(eta-C5H5)] afforded [Ru2WIr3(mu5-eta2-C2)(mu-CO)3(CO)7(eta-C5H5)2(eta-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a WIr3 butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone Ru-C scission, with insertion of the C2 unit into a W-Ir bond of the cluster precursor. Reaction of [W2Ir2(CO)10(eta-C5H5)2] with the diruthenium ethyndiyl reagent gave [RuW2Ir2{mu4-eta2-(C2C[triple bond]C)Ru(CO)2(eta-C5H5)}(mu-CO)2(CO)6(eta-C5H5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2Ir2 unit capped by a Ru(eta-C5H5) group resulting from Ru-C scission; the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W-Ir bond. Reaction between 1a, [WIr3(CO)11(eta-C5H4Me)] (1b), or 1c and [(eta-C5H5)(CO)3W(C[triple bond]CC[triple bond]C)W(CO)3(eta-C5H5)] afforded [W2Ir3{mu4-eta2-(C2C[triple bond]C)W(CO)3(eta-C5H5)}(mu-CO)2(CO)2(eta-C5H5)(eta-C5R5)] [R = H (7a), Me (7c); R5 = H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3.

Preparation and Luminescence Thermochromism of Tetranuclear Copper(I)-Pyridine-Iodide Clusters

ERIC Educational Resources Information Center

Parmeggiani, Fabio; Sacchetti, Alessandro

2012-01-01

A simple and straightforward synthesis of a tetranuclear copper(I)-pyridine-iodide cluster is described as a laboratory experiment for advanced inorganic chemistry undergraduate students. The product is used to demonstrate the fascinating and visually impressive phenomenon of luminescence thermochromism: exposed to long-wave UV light, the…

Cyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn 16 and Mn 18 clusters

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

Alexandropoulos, Dimitris I.; Moushi, Eleni E.; Papatriantafyllopoulou, Constantina

Here, the employment of cyanato (OCN -) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn 16O 8(OR) 4(OCN) 4(O 2CMe) 12(hmp) 6(ROH) 2] (R = Me (1), Et (2)) and [Mn 18O 14(O 2CR) 18(hmp) 4(hmpH) 2(H 2O) 2] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O 2CMe) 2·4H 2O, hmpH, NaOCN and NEt 3 in solvent MeOH or EtOH afford the isostructural complexes [Mn 16O 8(OR) 4(OCN) 4(O 2CMe) 12(hmp) 6(ROH)more » 2] (R = Me (1), Et (2)). The [Mn 16(μ 4-O) 4(μ 3-O) 4(μ-OMe) 4(μ 3-OR) 6(μ-OR) 6] 10+ core of representative complex 1 comprises a Mn II 4Mn III 4 double-cubane subunit attached on either side to two symmetry-related Mn IIMn III 3 defective dicubanes. A similar reaction of Mn(O 2CR) 2·4H 2O, hmpH, NaOCN and NEt 3, but in solvent MeCN, led instead to the formation of [Mn 18O 14(O 2CR) 18(hmp) 4(hmpH) 2(H 2O) 2] (R = Me (3), Et (4)). Compounds 3 and 4 are very similar to each other and can be described as a central [Mn III 4(μ-O) 6] rodlike subunit attached on either side to two symmetry-related [Mn 7O 9] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possible S = 2 or 1 (for 1 and 2) and S = 0 (for 3 and 4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear Mn II/III complexes with structures different than these obtained from the use of the related azides.« less

Cyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn 16 and Mn 18 clusters

DOE PAGES

Alexandropoulos, Dimitris I.; Moushi, Eleni E.; Papatriantafyllopoulou, Constantina; ...

2015-12-02

Here, the employment of cyanato (OCN -) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn 16O 8(OR) 4(OCN) 4(O 2CMe) 12(hmp) 6(ROH) 2] (R = Me (1), Et (2)) and [Mn 18O 14(O 2CR) 18(hmp) 4(hmpH) 2(H 2O) 2] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O 2CMe) 2·4H 2O, hmpH, NaOCN and NEt 3 in solvent MeOH or EtOH afford the isostructural complexes [Mn 16O 8(OR) 4(OCN) 4(O 2CMe) 12(hmp) 6(ROH)more » 2] (R = Me (1), Et (2)). The [Mn 16(μ 4-O) 4(μ 3-O) 4(μ-OMe) 4(μ 3-OR) 6(μ-OR) 6] 10+ core of representative complex 1 comprises a Mn II 4Mn III 4 double-cubane subunit attached on either side to two symmetry-related Mn IIMn III 3 defective dicubanes. A similar reaction of Mn(O 2CR) 2·4H 2O, hmpH, NaOCN and NEt 3, but in solvent MeCN, led instead to the formation of [Mn 18O 14(O 2CR) 18(hmp) 4(hmpH) 2(H 2O) 2] (R = Me (3), Et (4)). Compounds 3 and 4 are very similar to each other and can be described as a central [Mn III 4(μ-O) 6] rodlike subunit attached on either side to two symmetry-related [Mn 7O 9] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possible S = 2 or 1 (for 1 and 2) and S = 0 (for 3 and 4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear Mn II/III complexes with structures different than these obtained from the use of the related azides.« less

From supramolecular chemistry towards constitutional dynamic chemistry and adaptive chemistry.

PubMed

Lehn, Jean-Marie

2007-02-01

Supramolecular chemistry has developed over the last forty years as chemistry beyond the molecule. Starting with the investigation of the basis of molecular recognition, it has explored the implementation of molecular information in the programming of chemical systems towards self-organisation processes, that may occur either on the basis of design or with selection of their components. Supramolecular entities are by nature constitutionally dynamic by virtue of the lability of non-covalent interactions. Importing such features into molecular chemistry, through the introduction of reversible bonds into molecules, leads to the emergence of a constitutional dynamic chemistry, covering both the molecular and supramolecular levels. It considers chemical objects and systems capable of responding to external solicitations by modification of their constitution through component exchange or reorganisation. It thus opens the way towards an adaptive and evolutive chemistry, a further step towards the chemistry of complex matter.

Characterization of Glutaredoxin Fe-S Cluster-Binding Interactions Using Circular Dichroism Spectroscopy.

PubMed

Albetel, Angela-Nadia; Outten, Caryn E

2018-01-01

Monothiol glutaredoxins (Grxs) with a conserved Cys-Gly-Phe-Ser (CGFS) active site are iron-sulfur (Fe-S) cluster-binding proteins that interact with a variety of partner proteins and perform crucial roles in iron metabolism including Fe-S cluster transfer, Fe-S cluster repair, and iron signaling. Various analytical and spectroscopic methods are currently being used to monitor and characterize glutaredoxin Fe-S cluster-dependent interactions at the molecular level. The electronic, magnetic, and vibrational properties of the protein-bound Fe-S cluster provide a convenient handle to probe the structure, function, and coordination chemistry of Grx complexes. However, some limitations arise from sample preparation requirements, complexity of individual techniques, or the necessity for combining multiple methods in order to achieve a complete investigation. In this chapter, we focus on the use of UV-visible circular dichroism spectroscopy as a fast and simple initial approach for investigating glutaredoxin Fe-S cluster-dependent interactions. © 2018 Elsevier Inc. All rights reserved.

Constitutional dynamic chemistry: bridge from supramolecular chemistry to adaptive chemistry.

PubMed

Lehn, Jean-Marie

2012-01-01

Supramolecular chemistry aims at implementing highly complex chemical systems from molecular components held together by non-covalent intermolecular forces and effecting molecular recognition, catalysis and transport processes. A further step consists in the investigation of chemical systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, thus behaving as programmed chemical systems. Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and the resulting ability of supramolecular species to exchange their constituents. The same holds for molecular chemistry when the molecular entity contains covalent bonds that may form and break reversibility, so as to allow a continuous change in constitution by reorganization and exchange of building blocks. These features define a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels.CDC introduces a paradigm shift with respect to constitutionally static chemistry. The latter relies on design for the generation of a target entity, whereas CDC takes advantage of dynamic diversity to allow variation and selection. The implementation of selection in chemistry introduces a fundamental change in outlook. Whereas self-organization by design strives to achieve full control over the output molecular or supramolecular entity by explicit programming, self-organization with selection operates on dynamic constitutional diversity in response to either internal or external factors to achieve adaptation.The merging of the features: -information and programmability, -dynamics and reversibility, -constitution and structural diversity, points to the emergence of adaptive and evolutive chemistry, towards a chemistry of complex matter.

Studies on the reactivity of [Ge9]4- towards [Fe(cot)(CO)3]: synthesis and characterization of [Ge8Fe(CO)3]3- and of the anionic organometallic species [Fe(cot)(CO)3]-.

PubMed

Zhou, Binbin; Goicoechea, Jose M

2010-09-24

Reaction of cyclooctatetraene (COT) iron(II) tricarbonyl, [Fe(cot)(CO)(3)], with one equivalent of K(4)Ge(9) in ethylenediamine (en) yielded the cluster anion [Ge(8)Fe(CO)(3)](3-) which was crystallographically-characterized as a [K(2,2,2-crypt)](+) salt in [K(2,2,2-crypt)](3)[Ge(8)Fe(CO)(3)]. The chemically-reduced organometallic species [Fe(η(3)-C(8)H(8))(CO)(3)](-) was also isolated as a side-product from this reaction as [K(2,2,2-crypt)][Fe(η(3)-C(8)H(8))(CO)(3)]. Both species were further characterized by EPR and IR spectroscopy and electrospray mass spectrometry. The [Ge(8)Fe(CO)(3)](3-) cluster anion represents an unprecedented functionalized germanium Zintl anion in which the nine-atom precursor cluster has lost a vertex, which has been replaced by a transition-metal moiety.

Semiconducting Ba 3Sn 3Sb 4 and Metallic Ba 7–xSn 11Sb 15–y ( x = 0.4, y = 0.6) Zintl Phases

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

Chen, Haijie; Narayan, Awadhesh; Stoumpos, Constantinos C.

In this paper, we report the discovery of two ternary Zintl phases Ba 3Sn 3Sb 4 and Ba 7-xSn 11Sb 15-y, (x = 0.4, y = 0.6). Ba 3Sn 3Sb 4 adopts the monoclinic space group P2 1/c with a = 14.669(3) Å, b = 6.9649(14) Å, c = 13.629(3) Å, and β = 104.98(3)°. It features a unique corrugated two-dimensional (2D) structure consisting of [Sn 3Sb 4] 6- layers extending along the ab plane with Ba 2+ atoms sandwiched between them. The non-stoichiometric Ba 6.6Sn 11Sb 14.4 has a complex one-dimensional (1D) structure adopting the orthorhombic space group Pnma,more » with unit cell parameters a = 37.964(8) Å, b = 4.4090(9) Å and c = 24.682(5) Å. It consists of large double Sn-Sb ribbons separated by Ba 2+ atoms. Ba3Sn3Sb4 is an n-type semiconductor which has a narrow energy gap of ~0.18 eV and a room temperature carrier concentration of ~4.2 × 10 18 cm -3. Lastly, Ba 6.6Sn 11Sb 14.4 is determined to be a metal with electrons being the dominant carriers.« less

Semiconducting Ba 3Sn 3Sb 4 and Metallic Ba 7–xSn 11Sb 15–y ( x = 0.4, y = 0.6) Zintl Phases

DOE PAGES

Chen, Haijie; Narayan, Awadhesh; Stoumpos, Constantinos C.; ...

2017-11-08

In this paper, we report the discovery of two ternary Zintl phases Ba 3Sn 3Sb 4 and Ba 7-xSn 11Sb 15-y, (x = 0.4, y = 0.6). Ba 3Sn 3Sb 4 adopts the monoclinic space group P2 1/c with a = 14.669(3) Å, b = 6.9649(14) Å, c = 13.629(3) Å, and β = 104.98(3)°. It features a unique corrugated two-dimensional (2D) structure consisting of [Sn 3Sb 4] 6- layers extending along the ab plane with Ba 2+ atoms sandwiched between them. The non-stoichiometric Ba 6.6Sn 11Sb 14.4 has a complex one-dimensional (1D) structure adopting the orthorhombic space group Pnma,more » with unit cell parameters a = 37.964(8) Å, b = 4.4090(9) Å and c = 24.682(5) Å. It consists of large double Sn-Sb ribbons separated by Ba 2+ atoms. Ba3Sn3Sb4 is an n-type semiconductor which has a narrow energy gap of ~0.18 eV and a room temperature carrier concentration of ~4.2 × 10 18 cm -3. Lastly, Ba 6.6Sn 11Sb 14.4 is determined to be a metal with electrons being the dominant carriers.« less

Cluster-cluster clustering

NASA Technical Reports Server (NTRS)

Barnes, J.; Dekel, A.; Efstathiou, G.; Frenk, C. S.

1985-01-01

The cluster correlation function xi sub c(r) is compared with the particle correlation function, xi(r) in cosmological N-body simulations with a wide range of initial conditions. The experiments include scale-free initial conditions, pancake models with a coherence length in the initial density field, and hybrid models. Three N-body techniques and two cluster-finding algorithms are used. In scale-free models with white noise initial conditions, xi sub c and xi are essentially identical. In scale-free models with more power on large scales, it is found that the amplitude of xi sub c increases with cluster richness; in this case the clusters give a biased estimate of the particle correlations. In the pancake and hybrid models (with n = 0 or 1), xi sub c is steeper than xi, but the cluster correlation length exceeds that of the points by less than a factor of 2, independent of cluster richness. Thus the high amplitude of xi sub c found in studies of rich clusters of galaxies is inconsistent with white noise and pancake models and may indicate a primordial fluctuation spectrum with substantial power on large scales.

Microstructure and surface chemistry of amorphous alloys important to their friction and wear behavior

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1983-01-01

An investigation was conducted to examine the microstructure and surface chemistry of amorphous alloys, and their effects on tribological behavior. The results indicate that the surface oxide layers present on amorphous alloys are effective in providing low friction and a protective film against wear in air. Clustering and crystallization in amorphous alloys can be enhanced as a result of plastic flow during the sliding process at a low sliding velocity, at room temperature. Clusters or crystallines with sizes to 150 nm and a diffused honeycomb-shaped structure are produced on the wear surface. Temperature effects lead to drastic changes in surface chemistry and friction behavior of the alloys at temperatures to 750 C. Contaminants can come from the bulk of the alloys to the surface upon heating and impart to the surface oxides at 350 C and boron nitride above 500 C. The oxides increase friction while the boron nitride reduces friction drastically in vacuum.

Isomers and energy landscapes of micro-hydrated sulfite and chlorate clusters

NASA Astrophysics Data System (ADS)

Hey, John C.; Doyle, Emily J.; Chen, Yuting; Johnston, Roy L.

2018-03-01

We present putative global minima for the micro-hydrated sulfite SO32-(H2O)N and chlorate ClO32(H2O)N systems in the range 3≤N≤15 found using basin-hopping global structure optimization with an empirical potential. We present a structural analysis of the hydration of a large number of minimized structures for hydrated sulfite and chlorate clusters in the range 3≤N≤50. We show that sulfite is a significantly stronger net acceptor of hydrogen bonding within water clusters than chlorate, completely suppressing the appearance of hydroxyl groups pointing out from the cluster surface (dangling OH bonds), in low-energy clusters. We also present a qualitative analysis of a highly explored energy landscape in the region of the global minimum of the eight water hydrated sulfite and chlorate systems. This article is part of the theme issue `Modern theoretical chemistry'.

Ion collision-induced chemistry in pure and mixed loosely bound clusters of coronene and C60 molecules.

PubMed

Domaracka, Alicja; Delaunay, Rudy; Mika, Arkadiusz; Gatchell, Michael; Zettergren, Henning; Cederquist, Henrik; Rousseau, Patrick; Huber, Bernd A

2018-05-23

Ionization, fragmentation and molecular growth have been studied in collisions of 22.5 keV He2+- or 3 keV Ar+-projectiles with pure loosely bound clusters of coronene (C24H12) molecules or with loosely bound mixed C60-C24H12 clusters by using mass spectrometry. The heavier and slower Ar+ projectiles induce prompt knockout-fragmentation - C- and/or H-losses - from individual molecules and highly efficient secondary molecular growth reactions before the clusters disintegrate on picosecond timescales. The lighter and faster He2+ projectiles have a higher charge and the main reactions are then ionization by ions that are not penetrating the clusters. This leads mostly to cluster fragmentation without molecular growth. However, here penetrating collisions may also lead to molecular growth but to a much smaller extent than with 3 keV Ar+. Here we present fragmentation and molecular growth mass distributions with 1 mass unit resolution, which reveals that the same numbers of C- and H-atoms often participate in the formation and breaking of covalent bonds inside the clusters. We find that masses close to those with integer numbers of intact coronene molecules, or with integer numbers of both intact coronene and C60 molecules, are formed where often one or several H-atoms are missing or have been added on. We also find that super-hydrogenated coronene is formed inside the clusters.

Isomers and energy landscapes of micro-hydrated sulfite and chlorate clusters.

PubMed

Hey, John C; Doyle, Emily J; Chen, Yuting; Johnston, Roy L

2018-03-13

We present putative global minima for the micro-hydrated sulfite SO 3 2- (H 2 O) N and chlorate ClO 3 - (H 2 O) N systems in the range 3≤ N ≤15 found using basin-hopping global structure optimization with an empirical potential. We present a structural analysis of the hydration of a large number of minimized structures for hydrated sulfite and chlorate clusters in the range 3≤ N ≤50. We show that sulfite is a significantly stronger net acceptor of hydrogen bonding within water clusters than chlorate, completely suppressing the appearance of hydroxyl groups pointing out from the cluster surface (dangling OH bonds), in low-energy clusters. We also present a qualitative analysis of a highly explored energy landscape in the region of the global minimum of the eight water hydrated sulfite and chlorate systems.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Authors.

Real-time visualization of clustering and intracellular transport of gold nanoparticles by correlative imaging

NASA Astrophysics Data System (ADS)

Liu, Mengmeng; Li, Qian; Liang, Le; Li, Jiang; Wang, Kun; Li, Jiajun; Lv, Min; Chen, Nan; Song, Haiyun; Lee, Joon; Shi, Jiye; Wang, Lihua; Lal, Ratnesh; Fan, Chunhai

2017-05-01

Mechanistic understanding of the endocytosis and intracellular trafficking of nanoparticles is essential for designing smart theranostic carriers. Physico-chemical properties, including size, clustering and surface chemistry of nanoparticles regulate their cellular uptake and transport. Significantly, even single nanoparticles could cluster intracellularly, yet their clustering state and subsequent trafficking are not well understood. Here, we used DNA-decorated gold (fPlas-gold) nanoparticles as a dually emissive fluorescent and plasmonic probe to examine their clustering states and intracellular transport. Evidence from correlative fluorescence and plasmonic imaging shows that endocytosis of fPlas-gold follows multiple pathways. In the early stages of endocytosis, fPlas-gold nanoparticles appear mostly as single particles and they cluster during the vesicular transport and maturation. The speed of encapsulated fPlas-gold transport was critically dependent on the size of clusters but not on the types of organelle such as endosomes and lysosomes. Our results provide key strategies for engineering theranostic nanocarriers for efficient health management.

Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

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

Arslan, Ilke; Dixon, David A.; Gates, Bruce C.

2015-09-30

To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-themore » art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to

At the Intersection of Chemistry, Biology, and Medicine.

PubMed

Walsh, Christopher T

2017-06-20

After an undergraduate degree in biology at Harvard, I started graduate school at The Rockefeller Institute for Medical Research in New York City in July 1965. I was attracted to the chemical side of biochemistry and joined Fritz Lipmann's large, hierarchical laboratory to study enzyme mechanisms. That work led to postdoctoral research with Robert Abeles at Brandeis, then a center of what, 30 years later, would be called chemical biology. I spent 15 years on the Massachusetts Institute of Technology faculty, in both the Chemistry and Biology Departments, and then 26 years on the Harvard Medical School Faculty. My research interests have been at the intersection of chemistry, biology, and medicine. One unanticipated major focus has been investigating the chemical logic and enzymatic machinery of natural product biosynthesis, including antibiotics and antitumor agents. In this postgenomic era it is now recognized that there may be from 10 5 to 10 6 biosynthetic gene clusters as yet uncharacterized for potential new therapeutic agents.

Carbon nitride supported Fe2 cluster catalysts with superior performance for alkene epoxidation.

PubMed

Tian, Shubo; Fu, Qiang; Chen, Wenxing; Feng, Quanchen; Chen, Zheng; Zhang, Jian; Cheong, Weng-Chon; Yu, Rong; Gu, Lin; Dong, Juncai; Luo, Jun; Chen, Chen; Peng, Qing; Draxl, Claudia; Wang, Dingsheng; Li, Yadong

2018-06-15

Sub-nano metal clusters often exhibit unique and unexpected properties, which make them particularly attractive as catalysts. Herein, we report a "precursor-preselected" wet-chemistry strategy to synthesize highly dispersed Fe 2 clusters that are supported on mesoporous carbon nitride (mpg-C 3 N 4 ). The obtained Fe 2 /mpg-C 3 N 4 sample exhibits superior catalytic performance for the epoxidation of trans-stilbene to trans-stilbene oxide, showing outstanding selectivity of 93% at high conversion of 91%. Molecular oxygen is the only oxidant and no aldehyde is used as co-reagent. Under the same condition, by contrast, iron porphyrin, single-atom Fe, and small Fe nanoparticles (ca. 3 nm) are nearly reactively inert. First-principles calculations reveal that the unique reactivity of the Fe 2 clusters originates from the formation of active oxygen species. The general applicability of the synthesis approach is further demonstrated by producing other diatomic clusters like Pd 2 and Ir 2 , which lays the foundation for discovering diatomic cluster catalysts.

A new family of Ln₇ clusters with an ideal D(3h) metal-centered trigonal prismatic geometry, and SMM and photoluminescence behaviors.

PubMed

Mazarakioti, Eleni C; Poole, Katye M; Cunha-Silva, Luis; Christou, George; Stamatatos, Theocharis C

2014-08-14

The first use of the flexible Schiff base ligand N-salicylidene-2-aminocyclohexanol in metal cluster chemistry has afforded a new family of Ln7 clusters with ideal D(3h) point group symmetry and metal-centered trigonal prismatic topology; solid-state and solution studies revealed SMM and photoluminescence behaviors.

Probing the Adsorption of Carbon Monoxide on Transition Metal Clusters Using IR Action Spectroscopy

NASA Astrophysics Data System (ADS)

Lapoutre, Vivike J. F.; Oomens, Jos; Bakker, Joost M.

2012-06-01

The discovery of enhanced catalytic activity of small gold clusters has led to a great interest in size-dependent catalytic properties of metal clusters. To obtain a better understanding of the catalytic mechanisms it is essential to know the structures of these clusters and the nature of their interaction with reactant molecules. We have studied the structure of gas-phase niobium clusters with a carbon monoxide adsorbed using IR action spectroscopy. We present size-selective IR spectra obtained via IR multiple photon spectroscopy monitoring either photodetachment or photodissociation depending on the charge state. The combination of these spectra with DFT calculations allows for the structural determination of the adsorption product. M. Haruta et al., Journal of Catalysis 115 301-309 (1989). M. Haertelt et al., The Journal of Physical Chemistry Letters 2 1720-1724 (2011)

Structure, stability and magnetism of cobalt doped (ZnO)n clusters.

PubMed

Yang, Jack; Zhang, Y B; Li, Sean

2011-03-01

Clusters of magnetic impurities are believed to play an important role in retaining ferromagnetism in diluted magnetic semiconductors (DMS), the origin of which has been a long debated issue. Controlling the dopant homogeneity in magnetic semiconductors is therefore a critical issue for the fabrication of high performance DMS. The current paper presents a first principle study on the stability and magnetic properties of Co doped (ZnO)n (n = 12 and 15) clusters using density functional theory. The results show that cobalt ions in these clusters tend to increase their stabilities by maximizing their co-ordination numbers to oxygen. This will likely to be the case for (ZnO)n clusters with n other than 12 and 15 in order for Co to reside in a stable local crystal field. Expansive (shrinkage) stress is introduced when cobalt resides in exohedral substitutional (endohedral interstitial) sites; such strain can be offset by the cluster deformation. Bidoped cluster is found to be unstable due to the increase of system strain energy. All the doped clusters were found to preserve 3 microg of magnetic moments from Co in the overall clusters, but with part of the local moments on cobalt re-distributed onto neighboring oxygen atoms. Current findings may provide a better understanding on the structural chemistry of magnetic dopants in nanocrystallined DMS materials.

Chemistry Rocks: Redox Chemistry as a Geologic Tool.

ERIC Educational Resources Information Center

Burns, Mary Sue

2001-01-01

Applies chemistry to earth science, uses rocks in chemistry laboratories, and teaches about transition metal chemistry, oxidation states, and oxidation-reduction reactions from firsthand experiences. (YDS)

REFLECTIONS ON PHYSICAL CHEMISTRY: Science and Scientists

NASA Astrophysics Data System (ADS)

Jortner, Joshua

2006-05-01

This is the story of a young person who grew up in Tel-Aviv during the period of the establishment of the State of Israel and was inspired to become a physical chemist by the cultural environment, by the excellent high-school education, and by having been trained by some outstanding scientists at the Hebrew University of Jerusalem and, subsequently, by the intellectual environment and high-quality scientific endeavor at the University of Chicago. Since serving as the first chairman of the Chemistry Department of the newly formed Tel-Aviv University he has been immersed in research, in the training of young scientists, and in intensive and extensive international scientific collaboration. Together with the members of his "scientific family" he has explored the phenomena of energy acquisition, storage and disposal and structure-dynamics-function relations in large molecules, condensed phase, clusters and biomolecules, and is looking forward to many future adventures in physical chemistry. "What to leave out and what to put in? That's the problem." Hugh Lofting, Doctor Dolittle's Zoo, 1925

Significant steps in the evolution of analytical chemistry--is the today's analytical chemistry only chemistry?

PubMed

Karayannis, Miltiades I; Efstathiou, Constantinos E

2012-12-15

In this review the history of chemistry and specifically the history and the significant steps of the evolution of analytical chemistry are presented. In chronological time spans, covering the ancient world, the middle ages, the period of the 19th century, and the three evolutional periods, from the verge of the 19th century to contemporary times, it is given information for the progress of chemistry and analytical chemistry. During this period, analytical chemistry moved gradually from its pure empirical nature to more rational scientific activities, transforming itself to an autonomous branch of chemistry and a separate discipline. It is also shown that analytical chemistry moved gradually from the status of exclusive serving the chemical science, towards serving, the environment, health, law, almost all areas of science and technology, and the overall society. Some recommendations are also directed to analytical chemistry educators concerning the indispensable nature of knowledge of classical analytical chemistry and the associated laboratory exercises and to analysts, in general, why it is important to use the chemical knowledge to make measurements on problems of everyday life. Copyright © 2012 Elsevier B.V. All rights reserved.

Accurate prediction of secondary metabolite gene clusters in filamentous fungi.

PubMed

Andersen, Mikael R; Nielsen, Jakob B; Klitgaard, Andreas; Petersen, Lene M; Zachariasen, Mia; Hansen, Tilde J; Blicher, Lene H; Gotfredsen, Charlotte H; Larsen, Thomas O; Nielsen, Kristian F; Mortensen, Uffe H

2013-01-02

Biosynthetic pathways of secondary metabolites from fungi are currently subject to an intense effort to elucidate the genetic basis for these compounds due to their large potential within pharmaceutics and synthetic biochemistry. The preferred method is methodical gene deletions to identify supporting enzymes for key synthases one cluster at a time. In this study, we design and apply a DNA expression array for Aspergillus nidulans in combination with legacy data to form a comprehensive gene expression compendium. We apply a guilt-by-association-based analysis to predict the extent of the biosynthetic clusters for the 58 synthases active in our set of experimental conditions. A comparison with legacy data shows the method to be accurate in 13 of 16 known clusters and nearly accurate for the remaining 3 clusters. Furthermore, we apply a data clustering approach, which identifies cross-chemistry between physically separate gene clusters (superclusters), and validate this both with legacy data and experimentally by prediction and verification of a supercluster consisting of the synthase AN1242 and the prenyltransferase AN11080, as well as identification of the product compound nidulanin A. We have used A. nidulans for our method development and validation due to the wealth of available biochemical data, but the method can be applied to any fungus with a sequenced and assembled genome, thus supporting further secondary metabolite pathway elucidation in the fungal kingdom.

Presence of Li Clusters in Molten LiCl-Li

PubMed Central

Merwin, Augustus; Phillips, William C.; Williamson, Mark A.; Willit, James L.; Motsegood, Perry N.; Chidambaram, Dev

2016-01-01

Molten mixtures of lithium chloride and metallic lithium are of significant interest in various metal oxide reduction processes. These solutions have been reported to exhibit seemingly anomalous physical characteristics that lack a comprehensive explanation. In the current work, the physical chemistry of molten solutions of lithium chloride and metallic lithium, with and without lithium oxide, was investigated using in situ Raman spectroscopy. The Raman spectra obtained from these solutions were in agreement with the previously reported spectrum of the lithium cluster, Li8. This observation is indicative of a nanofluid type colloidal suspension of Li8 in a molten salt matrix. It is suggested that the formation and suspension of lithium clusters in lithium chloride is the cause of various phenomena exhibited by these solutions that were previously unexplainable. PMID:27145895

Presence of Li clusters in molten LiCl-Li

DOE PAGES

Merwin, Augustus; Phillips, William C.; Williamson, Mark A.; ...

2016-05-05

Molten mixtures of lithium chloride and metallic lithium are of significant interest in various metal oxide reduction processes. These solutions have been reported to exhibit seemingly anomalous physical characteristics that lack a comprehensive explanation. ln the current work, the physical chemistry of molten solutions of lithium chloride and metallic lithium, with and without lithium oxide, was investigated using in situ Raman spectroscopy. The Raman spectra obtained from these solutions were in agreement with the previously reported spectrum of the lithium cluster, Li 8. Furthermore, this observation is indicative of a nanofluid type colloidal suspension of Li 8, in a moltenmore » salt matrix. It is suggested that the formation and suspension of lithium clusters in lithium chloride is the cause of various phenomena exhibited by these solutions that were previously unexplainable.« less

Intra-cluster Globular Clusters in a Simulated Galaxy Cluster

NASA Astrophysics Data System (ADS)

Ramos-Almendares, Felipe; Abadi, Mario; Muriel, Hernán; Coenda, Valeria

2018-01-01

Using a cosmological dark matter simulation of a galaxy-cluster halo, we follow the temporal evolution of its globular cluster population. To mimic the red and blue globular cluster populations, we select at high redshift (z∼ 1) two sets of particles from individual galactic halos constrained by the fact that, at redshift z = 0, they have density profiles similar to observed ones. At redshift z = 0, approximately 60% of our selected globular clusters were removed from their original halos building up the intra-cluster globular cluster population, while the remaining 40% are still gravitationally bound to their original galactic halos. As the blue population is more extended than the red one, the intra-cluster globular cluster population is dominated by blue globular clusters, with a relative fraction that grows from 60% at redshift z = 0 up to 83% for redshift z∼ 2. In agreement with observational results for the Virgo galaxy cluster, the blue intra-cluster globular cluster population is more spatially extended than the red one, pointing to a tidally disrupted origin.

Clustering in the stellar abundance space

NASA Astrophysics Data System (ADS)

Boesso, R.; Rocha-Pinto, H. J.

2018-03-01

We have studied the chemical enrichment history of the interstellar medium through an analysis of the n-dimensional stellar abundance space. This work is a non-parametric analysis of the stellar chemical abundance space. The main goal is to study the stars from their organization within this abundance space. Within this space, we seek to find clusters (in a statistical sense), that is, stars likely to share similar chemo-evolutionary history, using two methods: the hierarchical clustering and the principal component analysis. We analysed some selected abundance surveys available in the literature. For each sample, we labelled the group of stars according to its average abundance curve. In all samples, we identify the existence of a main enrichment pattern of the stars, which we call chemical enrichment flow. This flow is set by the structured and well-defined mean rate at which the abundances of the interstellar medium increase, resulting from the mixture of the material ejected from the stars and stellar mass-loss and interstellar medium gas. One of the main results of our analysis is the identification of subgroups of stars with peculiar chemistry. These stars are situated in regions outside of the enrichment flow in the abundance space. These peculiar stars show a mismatch in the enrichment rate of a few elements, such as Mg, Si, Sc and V, when compared to the mean enrichment rate of the other elements of the same stars. We believe that the existence of these groups of stars with peculiar chemistry may be related to the accretion of planetary material on to stellar surfaces or may be due to production of the same chemical element by different nucleosynthetic sites.

Water oxidation chemistry of photosystem II.

PubMed Central

Vrettos, John S; Brudvig, Gary W

2002-01-01

The O(2)-evolving complex of photosystem II catalyses the light-driven four-electron oxidation of water to dioxygen in photosynthesis. In this article, the steps leading to photosynthetic O(2) evolution are discussed. Emphasis is given to the proton-coupled electron-transfer steps involved in oxidation of the manganese cluster by oxidized tyrosine Z (Y(*)(Z)), the function of Ca(2+) and the mechanism by which water is activated for formation of an O-O bond. Based on a consideration of the biophysical studies of photosystem II and inorganic manganese model chemistry, a mechanism for photosynthetic O(2) evolution is presented in which the O-O bond-forming step occurs via nucleophilic attack on an electron-deficient Mn(V)=O species by a calcium-bound water molecule. The proposed mechanism includes specific roles for the tetranuclear manganese cluster, calcium, chloride, Y(Z) and His190 of the D1 polypeptide. Recent studies of the ion selectivity of the calcium site in the O(2)-evolving complex and of a functional inorganic manganese model system that test key aspects of this mechanism are also discussed. PMID:12437878

Forensic Chemistry

NASA Astrophysics Data System (ADS)

Bell, Suzanne

2009-07-01

Forensic chemistry is unique among chemical sciences in that its research, practice, and presentation must meet the needs of both the scientific and the legal communities. As such, forensic chemistry research is applied and derivative by nature and design, and it emphasizes metrology (the science of measurement) and validation. Forensic chemistry has moved away from its analytical roots and is incorporating a broader spectrum of chemical sciences. Existing forensic practices are being revisited as the purview of forensic chemistry extends outward from drug analysis and toxicology into such diverse areas as combustion chemistry, materials science, and pattern evidence.

The anatomy of a cluster IDP. Part 1: Carbon abundance, bulk chemistry, and mineralogy of fragments from L2008#5

NASA Technical Reports Server (NTRS)

Thomas, K. L.; Keller, L. P.; Klock, W.; Warren, J.; Blanford, G. E.; Mckay, David S.

1994-01-01

The objective of this study was to determine whether or not cluster particles are sufficiently homogeneous to enable observations from one fragment of the cluster to be extrapolated to the entire cluster. We report on the results of a consortium study of the fragments of a large cluster particle. Multiple fragments from one large cluster were distributed to several research groups and were subjected to a variety of mineralogical and chemical analyses including: SEM, TEM, ion probe, SXRF, noble gas measurements, and microprobe laser mass spectrometry of individual fragments.

Mechanical gate control for atom-by-atom cluster assembly with scanning probe microscopy.

PubMed

Sugimoto, Yoshiaki; Yurtsever, Ayhan; Hirayama, Naoki; Abe, Masayuki; Morita, Seizo

2014-07-11

Nanoclusters supported on substrates are of great importance in physics and chemistry as well as in technical applications, such as single-electron transistors and nanocatalysts. The properties of nanoclusters differ significantly from those of either the constituent atoms or the bulk solid, and are highly sensitive to size and chemical composition. Here we propose a novel atom gating technique to assemble various atom clusters composed of a defined number of atoms at room temperature. The present gating operation is based on the transfer of single diffusing atoms among nanospaces governed by gates, which can be opened in response to the chemical interaction force with a scanning probe microscope tip. This method provides an alternative way to create pre-designed atom clusters with different chemical compositions and to evaluate their chemical stabilities, thus enabling investigation into the influence that a single dopant atom incorporated into the host clusters has on a given cluster stability.

Is coccolithophore distribution in the Mediterranean Sea related to seawater carbonate chemistry?

NASA Astrophysics Data System (ADS)

Oviedo, A.; Ziveri, P.; Álvarez, M.; Tanhua, T.

2015-01-01

The Mediterranean Sea is considered a "hot spot" for climate change, being characterized by oligotrophic to ultra-oligotrophic waters and rapidly increasing seasurface temperature and changing carbonate chemistry. Coccolithophores are considered a dominant phytoplankton group in these waters. As marine calcifying organisms they are expected to respond to the ongoing changes in seawater carbonate chemistry. We provide here a description of the springtime coccolithophore distribution in the Mediterranean Sea and relate this to a broad set of in situ-measured environmental variables. Samples were taken during the R/V Meteor (M84/3) oceanographic cruise in April 2011, between 0 and 100 m water depth from 28 stations. Total diatom and silicoflagellate cell concentrations are also presented. Our results highlight the importance of seawater carbonate chemistry, especially [CO32-] but also [PO43-] in unraveling the distribution of heterococcolithophores, the most abundant coccolithophore life phase. Holo- and heterococcolithophores respond differently to environmental factors. For instance, changes in heterococcolithophore assemblages were best linked to the combination of [CO32-], pH, and salinity (ρ = 0.57), although salinity might be not functionally related to coccolithophore assemblage distribution. Holococcolithophores, on the other hand, showed higher abundances and species diversity in oligotrophic areas (best fit, ρ = 0.32 for nutrients), thriving in nutrient-depleted waters. Clustering of heterococcolithophores revealed three groups of species sharing more than 65% similarities. These clusters could be assigned to the eastern and western basins and deeper layers (below 50 m), respectively. In addition, the species Gephyrocapsa oceanica, G. muellerae, and Emiliania huxleyi morphotype B/C are spatially distributed together and trace the influx of Atlantic waters into the Mediterranean Sea. The results of the present work emphasize the importance

Development and Application of Single-Referenced Perturbation and Coupled-Cluster Theories for Excited Electronic States

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Langhoff, Stephen R. (Technical Monitor)

1997-01-01

Recent work on the development of single-reference perturbation theories for the study of excited electronic states will be discussed. The utility of these methods will be demonstrated by comparison to linear-response coupled-cluster excitation energies. Results for some halogen molecules of interest in stratospheric chemistry will be presented.

Synthesis, crystal structures, and physical properties of the new Zintl phases A{sub 21}Zn{sub 4}Pn{sub 18} (A=Ca, Eu; Pn=As, Sb)—Versatile arrangements of [ZnPn{sub 4}] tetrahedra

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

Suen, Nian-Tzu; Wang, Yi; Bobev, Svilen, E-mail: bobev@udel.edu

Four new Zintl phases, Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18} and Eu{sub 21}Zn{sub 4}Sb{sub 18} have been synthesized by metal flux reactions. Their structures have been established from single-crystal X-ray diffraction. Despite the similar chemical makeup and the identical formulae, the structures of the four compounds are not the same—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18} and Eu{sub 21}Zn{sub 4}As{sub 18} crystallize in the monoclinic space group C2/m (No. 12, Z=4) with the β-Ca{sub 21}Mn{sub 4}Sb{sub 18} structure type, while Eu{sub 21}Zn{sub 4}Sb{sub 18} adopts the Ba{sub 21}Cd{sub 4}Sb{sub 18} structure type withmore » the orthorhombic space group Cmce (No. 64, Z=8). Both structures are based on ZnAs{sub 4} or ZnSb{sub 4} tetrahedra, linked in slightly different ways, and Ca{sup 2+} and Eu{sup 2+} cations that fill the space between them. The structural relationships between the title compounds and other known ternary phases with intricate structures are discussed. Electrical resistivity measurement on single-crystalline Eu{sub 21}Zn{sub 4}Sb{sub 18} suggests an intrinsic semiconductor behavior with a band gap of ca. 0.2 eV. The temperature dependent DC magnetization measurement on the same material indicates Curie–Weiss paramagnetism in the high-temperature regime, and a spontaneous antiferromagnetic ordering below 8 K. The calculated effective moments of Eu confirm the divalent Eu{sup 2+} ground state, as expected from the Zintl–Klemm concept. - Graphical abstract: The four new Zintl phases—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb{sub 18}—crystallize in two structure types, showing the versatility in the arrangements of ZnAs{sub 4} and ZnSb{sub 4} tetrahedra. - Highlights: • Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb

Chemistry Notes.

ERIC Educational Resources Information Center

School Science Review, 1982

1982-01-01

Presents background information, laboratory procedures, classroom materials/activities, and experiments for chemistry. Topics include superheavy elements, polarizing power and chemistry of alkali metals, particulate carbon from combustion, tips for the chemistry laboratory, interesting/colorful experiments, behavior of bismuth (III) iodine, and…

Clinical chemistry through Clinical Chemistry: a journal timeline.

PubMed

Rej, Robert

2004-12-01

The establishment of the modern discipline of clinical chemistry was concurrent with the foundation of the journal Clinical Chemistry and that of the American Association for Clinical Chemistry in the late 1940s and early 1950s. To mark the 50th volume of this Journal, I chronicle and highlight scientific milestones, and those within the discipline, as documented in the pages of Clinical Chemistry. Amazing progress has been made in the field of laboratory diagnostics over these five decades, in many cases paralleling-as well as being bolstered by-the rapid pace in the development of computer technologies. Specific areas of laboratory medicine particularly well represented in Clinical Chemistry include lipids, endocrinology, protein markers, quality of laboratory measurements, molecular diagnostics, and general advances in methodology and instrumentation.

Functionalization of Mechanochemically Passivated Germanium Nanoparticles via "Click" Chemistry

NASA Astrophysics Data System (ADS)

Purkait, Tapas Kumar

. Copper(I) catalyzed "click" chemistry also can be explored with azido-terminated Ge NPs which were synthesized by azidation of chloro-terminated Ge NPs. Water soluble PEGylated Ge NPs were synthesized by "click" reaction for biological application. PEGylated Ge NP clusters were prepared using alpha, o-bis alkyno or bis-azido polyethylene glycol (PEG) derivatives by copper catalyzed "click" reaction via inter-particle linking. These nanoparticles were further functionalized by azido beta-cyclodextrin (beta-CD) and azido adamantane via alkyne-azide "click" reactions. Nanoparticle clusters were made from the functionalized Ge NPs by "host-guest" chemistry of beta-CD functionalized Ge NPs either with adamantane functionalized Ge NPs or fullerene, C60.

DanceChemistry: Helping Students Visualize Chemistry Concepts through Dance Videos

ERIC Educational Resources Information Center

Tay, Gidget C.; Edwards, Kimberly D.

2015-01-01

A visual aid teaching tool, the DanceChemistry video series, has been developed to teach fundamental chemistry concepts through dance. These educational videos portray chemical interactions at the molecular level using dancers to represent chemical species. Students reported that the DanceChemistry videos helped them visualize chemistry ideas in a…

Interaction of boron cluster ions with water: Single collision dynamics and sequential etching

NASA Astrophysics Data System (ADS)

Hintz, Paul A.; Ruatta, Stephen A.; Anderson, Scott L.

1990-01-01

Reactions of mass-selected, cooled, boron cluster ions (B+n, n=1-14) with water have been studied for collision energies from 0.1 to 6.0 eV. Most work was done with D2O, however isotope effects were examined for selected reactant cluster ions. For all size clusters there are exoergic product channels, which in most cases have no activation barriers. Cross sections are generally large, however there are fluctuations with cluster size in total reactivity, collision energy dependences, and in product distributions. For small cluster ions, there is a multitude of product channels. For clusters larger than B+6, the product distributions are dominated by a single channel: Bn-1D++DBO. Under multiple collision conditions, the primary products undergo a remarkable sequence of secondary ``etching'' reactions. As these occur, boron atoms are continuously replaced by hydrogen, and the intermediate products retain the composition: Bn-mH+m. This highly efficient chemistry appears to continue unchanged as the composition changes from pure boron to mostly hydrogen. Comparison of these results is made with boron cluster ion reactions with O2 and D2, as well as reactions with water of aluminum and silicon cluster ions. Some discussion is given of the thermochemistry for these reactions, and a possible problem with the thermochemical data in the BOD/DBO system is discussed.

Excess electrons in methanol clusters: Beyond the one-electron picture

NASA Astrophysics Data System (ADS)

Pohl, Gábor; Mones, Letif; Turi, László

2016-10-01

We performed a series of comparative quantum chemical calculations on various size negatively charged methanol clusters, ("separators=" CH 3 OH ) n - . The clusters are examined in their optimized geometries (n = 2-4), and in geometries taken from mixed quantum-classical molecular dynamics simulations at finite temperature (n = 2-128). These latter structures model potential electron binding sites in methanol clusters and in bulk methanol. In particular, we compute the vertical detachment energy (VDE) of an excess electron from increasing size methanol cluster anions using quantum chemical computations at various levels of theory including a one-electron pseudopotential model, several density functional theory (DFT) based methods, MP2 and coupled-cluster CCSD(T) calculations. The results suggest that at least four methanol molecules are needed to bind an excess electron on a hydrogen bonded methanol chain in a dipole bound state. Larger methanol clusters are able to form stronger interactions with an excess electron. The two simulated excess electron binding motifs in methanol clusters, interior and surface states, correlate well with distinct, experimentally found VDE tendencies with size. Interior states in a solvent cavity are stabilized significantly stronger than electron states on cluster surfaces. Although we find that all the examined quantum chemistry methods more or less overestimate the strength of the experimental excess electron stabilization, MP2, LC-BLYP, and BHandHLYP methods with diffuse basis sets provide a significantly better estimate of the VDE than traditional DFT methods (BLYP, B3LYP, X3LYP, PBE0). A comparison to the better performing many electron methods indicates that the examined one-electron pseudopotential can be reasonably used in simulations for systems of larger size.

Excess electrons in methanol clusters: Beyond the one-electron picture.

PubMed

Pohl, Gábor; Mones, Letif; Turi, László

2016-10-28

We performed a series of comparative quantum chemical calculations on various size negatively charged methanol clusters, CH 3 OH n - . The clusters are examined in their optimized geometries (n = 2-4), and in geometries taken from mixed quantum-classical molecular dynamics simulations at finite temperature (n = 2-128). These latter structures model potential electron binding sites in methanol clusters and in bulk methanol. In particular, we compute the vertical detachment energy (VDE) of an excess electron from increasing size methanol cluster anions using quantum chemical computations at various levels of theory including a one-electron pseudopotential model, several density functional theory (DFT) based methods, MP2 and coupled-cluster CCSD(T) calculations. The results suggest that at least four methanol molecules are needed to bind an excess electron on a hydrogen bonded methanol chain in a dipole bound state. Larger methanol clusters are able to form stronger interactions with an excess electron. The two simulated excess electron binding motifs in methanol clusters, interior and surface states, correlate well with distinct, experimentally found VDE tendencies with size. Interior states in a solvent cavity are stabilized significantly stronger than electron states on cluster surfaces. Although we find that all the examined quantum chemistry methods more or less overestimate the strength of the experimental excess electron stabilization, MP2, LC-BLYP, and BHandHLYP methods with diffuse basis sets provide a significantly better estimate of the VDE than traditional DFT methods (BLYP, B3LYP, X3LYP, PBE0). A comparison to the better performing many electron methods indicates that the examined one-electron pseudopotential can be reasonably used in simulations for systems of larger size.

Study of BenW (n = 1-12) clusters: An electron collision perspective

NASA Astrophysics Data System (ADS)

Modak, Paresh; Kaur, Jaspreet; Antony, Bobby

2017-08-01

This article explores electron scattering cross sections by Beryllium-Tungsten clusters (BenW). Beryllium and tungsten are important elements for plasma facing wall components, especially for the deuterium/tritium phase of ITER and in the recently installed JET. The present study focuses on different electron impact interactions in terms of elastic cross section (Qel), inelastic cross section (Qinel), ionization cross section (Qion), and momentum transfer cross section (Qmtcs) for the first twelve clusters belonging to the BenW family. It also predicts the evolution of the cross section with the size of the cluster. These cross sections are used as an input to model processes in plasma. The ionization cross section presented here is compared with the available reported data. This is the first comprehensive report on cross section data for all the above-mentioned scattering channels, to the best of our knowledge. Such broad analysis of cross section data gives vital insight into the study of local chemistry of electron interactions with BenW (n = 1-12) clusters in plasma.

Fe-S cluster biosynthesis controls uptake of aminoglycosides in a ROS-less death pathway.

PubMed

Ezraty, Benjamin; Vergnes, Alexandra; Banzhaf, Manuel; Duverger, Yohann; Huguenot, Allison; Brochado, Ana Rita; Su, Shu-Yi; Espinosa, Leon; Loiseau, Laurent; Py, Béatrice; Typas, Athanasios; Barras, Frédéric

2013-06-28

All bactericidal antibiotics were recently proposed to kill by inducing reactive oxygen species (ROS) production, causing destabilization of iron-sulfur (Fe-S) clusters and generating Fenton chemistry. We find that the ROS response is dispensable upon treatment with bactericidal antibiotics. Furthermore, we demonstrate that Fe-S clusters are required for killing only by aminoglycosides. In contrast to cells, using the major Fe-S cluster biosynthesis machinery, ISC, cells using the alternative machinery, SUF, cannot efficiently mature respiratory complexes I and II, resulting in impendence of the proton motive force (PMF), which is required for bactericidal aminoglycoside uptake. Similarly, during iron limitation, cells become intrinsically resistant to aminoglycosides by switching from ISC to SUF and down-regulating both respiratory complexes. We conclude that Fe-S proteins promote aminoglycoside killing by enabling their uptake.

Dynamic Reactive Ionization with Cluster Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Tian, Hua; Wucher, Andreas; Winograd, Nicholas

2016-02-01

Gas cluster ion beams (GCIB) have been tuned to enhance secondary ion yields by doping small gas molecules such as CH4, CO2, and O2 into an Ar cluster projectile, Arn + ( n = 1000-10,000) to form a mixed cluster. The `tailored beam' has the potential to expand the application of secondary ion mass spectrometry for two- and three-dimensional molecular specific imaging. Here, we examine the possibility of further enhancing the ionization by doping HCl into the Ar cluster. Water deposited on the target surface facilitates the dissociation of HCl. This concerted effect, occurring only at the impact site of the cluster, arises since the HCl is chemically induced to ionize to H+ and Cl- , allowing improved protonation of neutral molecular species. This hypothesis is confirmed by depth profiling through a trehalose thin film exposed to D2O vapor, resulting in ~20-fold increase in protonated molecules. The results show that it is possible to dynamically maintain optimum ionization conditions during depth profiling by proper adjustment of the water vapor pressure. H-D exchange in the trehalose molecule M was monitored upon deposition of D2O on the target surface, leading to the observation of [Mn* + H]+ or [Mn* + D]+ ions, where n = 1-8 hydrogen atoms in the trehalose molecule M have been replaced by deuterium. In general, we discuss the role of surface chemistry and dynamic reactive ionization of organic molecules in increasing the secondary ion yield.

Spectroscopic and computational studies of ionic clusters as models of solvation and atmospheric reactions

NASA Astrophysics Data System (ADS)

Kuwata, Keith T.

Ionic clusters are useful as model systems for the study of fundamental processes in solution and in the atmosphere. Their structure and reactivity can be studied in detail using vibrational predissociation spectroscopy, in conjunction with high level ab initio calculations. This thesis presents the applications of infrared spectroscopy and computation to a variety of gas-phase cluster systems. A crucial component of the process of stratospheric ozone depletion is the action of polar stratospheric clouds (PSCs) to convert the reservoir species HCl and chlorine nitrate (ClONO2) to photochemically labile compounds. Quantum chemistry was used to explore one possible mechanism by which this activation is effected: Cl- + ClONO2 /to Cl2 + NO3- eqno(1)Correlated ab initio calculations predicted that the direct reaction of chloride ion with ClONO2 is facile, which was confirmed in an experimental kinetics study. In the reaction a weakly bound intermediate Cl2-NO3- is formed, with ~70% of the charge localized on the nitrate moiety. This enables the Cl2-NO3- cluster to be well solvated even in bulk solution, allowing (1) to be facile on PSCs. Quantum chemistry was also applied to the hydration of nitrosonium ion (NO+), an important process in the ionosphere. The calculations, in conjunction with an infrared spectroscopy experiment, revealed the structure of the gas-phase clusters NO+(H2O)n. The large degree of covalent interaction between NO+ and the lone pairs of the H2O ligands is contrasted with the weak electrostatic bonding between iodide ion and H2O. Finally, the competition between ion solvation and solvent self-association is explored for the gas-phase clusters Cl/-(H2O)n and Cl-(NH3)n. For the case of water, vibrational predissociation spectroscopy reveals less hydrogen bonding among H2O ligands than predicted by ab initio calculations. Nevertheless, for n /ge 5, cluster structure is dominated by water-water interactions, with Cl- only partially solvated by the

Chemistry for whom? Gender awareness in teaching and learning chemistry

NASA Astrophysics Data System (ADS)

Andersson, Kristina

2017-06-01

Marie Ståhl and Anita Hussénius have defined what discourses dominate national tests in chemistry for Grade 9 in Sweden by using feminist, critical didactic perspectives. This response seeks to expand the results in Ståhl and Hussénius's article Chemistry inside an epistemological community box!— Discursive exclusions and inclusions in the Swedish national tests in chemistry, by using different facets of gender awareness. The first facet—Gender awareness in relations to the test designers' own conceptions—highlighted how the gender order where women are subordinated men becomes visible in the national tests as a consequence of the test designers internalized conceptions. The second facet—Gender awareness in relation to chemistry—discussed the hierarchy between discourses within chemistry. The third facet—Gender awareness in relation to students—problematized chemistry in relation to the students' identity formation. In summary, I suggest that the different discourses can open up new ways to interpret chemistry and perhaps dismantle the hegemonic chemistry discourse.

Weighted similarity-based clustering of chemical structures and bioactivity data in early drug discovery.

PubMed

Perualila-Tan, Nolen Joy; Shkedy, Ziv; Talloen, Willem; Göhlmann, Hinrich W H; Moerbeke, Marijke Van; Kasim, Adetayo

2016-08-01

The modern process of discovering candidate molecules in early drug discovery phase includes a wide range of approaches to extract vital information from the intersection of biology and chemistry. A typical strategy in compound selection involves compound clustering based on chemical similarity to obtain representative chemically diverse compounds (not incorporating potency information). In this paper, we propose an integrative clustering approach that makes use of both biological (compound efficacy) and chemical (structural features) data sources for the purpose of discovering a subset of compounds with aligned structural and biological properties. The datasets are integrated at the similarity level by assigning complementary weights to produce a weighted similarity matrix, serving as a generic input in any clustering algorithm. This new analysis work flow is semi-supervised method since, after the determination of clusters, a secondary analysis is performed wherein it finds differentially expressed genes associated to the derived integrated cluster(s) to further explain the compound-induced biological effects inside the cell. In this paper, datasets from two drug development oncology projects are used to illustrate the usefulness of the weighted similarity-based clustering approach to integrate multi-source high-dimensional information to aid drug discovery. Compounds that are structurally and biologically similar to the reference compounds are discovered using this proposed integrative approach.

ABCluster: the artificial bee colony algorithm for cluster global optimization.

PubMed

Zhang, Jun; Dolg, Michael

2015-10-07

Global optimization of cluster geometries is of fundamental importance in chemistry and an interesting problem in applied mathematics. In this work, we introduce a relatively new swarm intelligence algorithm, i.e. the artificial bee colony (ABC) algorithm proposed in 2005, to this field. It is inspired by the foraging behavior of a bee colony, and only three parameters are needed to control it. We applied it to several potential functions of quite different nature, i.e., the Coulomb-Born-Mayer, Lennard-Jones, Morse, Z and Gupta potentials. The benchmarks reveal that for long-ranged potentials the ABC algorithm is very efficient in locating the global minimum, while for short-ranged ones it is sometimes trapped into a local minimum funnel on a potential energy surface of large clusters. We have released an efficient, user-friendly, and free program "ABCluster" to realize the ABC algorithm. It is a black-box program for non-experts as well as experts and might become a useful tool for chemists to study clusters.

Understanding the Cu-Zn brass alloys using a short-range-order cluster model: significance of specific compositions of industrial alloys

PubMed Central

Hong, H. L.; Wang, Q.; Dong, C.; Liaw, Peter K.

2014-01-01

Metallic alloys show complex chemistries that are not yet understood so far. It has been widely accepted that behind the composition selection lies a short-range-order mechanism for solid solutions. The present paper addresses this fundamental question by examining the face-centered-cubic Cu-Zn α-brasses. A new structural approach, the cluster-plus-glue-atom model, is introduced, which suits specifically for the description of short-range-order structures in disordered systems. Two types of formulas are pointed out, [Zn-Cu12]Zn1~6 and [Zn-Cu12](Zn,Cu)6, which explain the α-brasses listed in the American Society for Testing and Materials (ASTM) specifications. In these formulas, the bracketed parts represent the 1st-neighbor cluster, and each cluster is matched with one to six 2nd-neighbor Zn atoms or with six mixed (Zn,Cu) atoms. Such a cluster-based formulism describes the 1st- and 2nd-neighbor local atomic units where the solute and solvent interactions are ideally satisfied. The Cu-Ni industrial alloys are also explained, thus proving the universality of the cluster-formula approach in understanding the alloy selections. The revelation of the composition formulas for the Cu-(Zn,Ni) industrial alloys points to the common existence of simple composition rules behind seemingly complex chemistries of industrial alloys, thus offering a fundamental and practical method towards composition interpretations of all kinds of alloys. PMID:25399835

Understanding the Cu-Zn brass alloys using a short-range-order cluster model: Significance of specific compositions of industrial alloys

DOE PAGES

Hong, H. L.; Wang, Q.; Dong, C.; ...

2014-11-17

Metallic alloys show complex chemistries that are not yet understood so far. It has been widely accepted that behind the composition selection lies a short-range-order mechanism for solid solutions. The present paper addresses this fundamental question by examining the face-centered-cubic Cu-Zn α-brasses. A new structural approach, the cluster-plus-glue-atom model, is introduced, which suits specifically for the description of short-range-order structures in disordered systems. Two types of formulas are pointed out, [Zn-Cu 12]Zn 1~6 and [Zn-Cu 12](Zn,Cu) 6, which explain the α-brasses listed in the American Society for Testing and Materials (ASTM) specifications. In these formulas, the bracketed parts represent themore » 1 st-neighbor cluster, and each cluster is matched with one to six 2 nd-neighbor Zn atoms or with six mixed (Zn,Cu) atoms. Such a cluster-based formulism describes the 1 st- and 2 nd-neighbor local atomic units where the solute and solvent interactions are ideally satisfied. The Cu-Ni industrial alloys are also explained, thus proving the universality of the cluster-formula approach in understanding the alloy selections. As a result, the revelation of the composition formulas for the Cu-(Zn,Ni) industrial alloys points to the common existence of simple composition rules behind seemingly complex chemistries of industrial alloys, thus offering a fundamental and practical method towards composition interpretations of all kinds of alloys.« less

Peer Mentoring in the General Chemistry and Organic Chemistry Laboratories: The Pinacol Rearrangement--An Exercise in NMR and IR Spectroscopy for General Chemistry and Organic Chemistry Laboratories

ERIC Educational Resources Information Center

Arrington, Caleb A.; Hill, Jameica B.; Radfar, Ramin; Whisnant, David M.; Bass, Charles G.

2008-01-01

This article describes a discovery experiment for general chemistry and organic chemistry labs. Although the pinacol rearrangement has been employed in undergraduate organic laboratories before, in this application organic chemistry students act as mentors to students of general chemistry. Students work together using distillation--a new technique…

Exploration of fluorine chemistry at the multidisciplinary interface of chemistry and biology.

PubMed

Ojima, Iwao

2013-07-05

Over the last three decades, my engagement in "fluorine chemistry" has evolved substantially because of the multidisciplinary nature of the research programs. I began my research career as a synthetic chemist in organometallic chemistry and homogeneous catalysis directed toward organic synthesis. Then, I was brought into a very unique world of "fluorine chemistry" in the end of 1970s. I started exploring the interface of fluorine chemistry and transition metal homogeneous catalysis first, which was followed by amino acids, peptides, and peptidomimetics for medicinal chemistry. Since then, I have been exploring the interfaces of fluorine chemistry and multidisciplinary fields of research involving medicinal chemistry, chemical biology, cancer biology, and molecular imaging. This perspective intends to cover my fruitful endeavor in the exploration of fluorine chemistry at the multidisciplinary interface of chemistry and biology in a chronological order to show the evolution of my research interest and strategy.

Copper chalcogenide clusters stabilized with ferrocene-based diphosphine ligands.

PubMed

Khadka, Chhatra B; Najafabadi, Bahareh Khalili; Hesari, Mahdi; Workentin, Mark S; Corrigan, John F

2013-06-17

The redox-active diphosphine ligand 1,1'-bis(diphenylphosphino)ferrocene (dppf) has been used to stabilize the copper(I) chalcogenide clusters [Cu12(μ4-S)6(μ-dppf)4] (1), [Cu8(μ4-Se)4(μ-dppf)3] (2), [Cu4(μ4-Te)(μ4-η(2)-Te2)(μ-dppf)2] (3), and [Cu12(μ5-Te)4(μ8-η(2)-Te2)2(μ-dppf)4] (4), prepared by the reaction of the copper(I) acetate coordination complex (dppf)CuOAc (5) with 0.5 equiv of E(SiMe3)2 (E = S, Se, Te). Single-crystal X-ray analyses of complexes 1-4 confirm the presence of {Cu(2x)E(x)} cores stabilized by dppf ligands on their surfaces, where the bidentate ligands adopt bridging coordination modes. The redox chemistry of cluster 1 was examined using cyclic voltammetry and compared to the electrochemistry of the free ligand dppf and the corresponding copper(I) acetate coordination complex 5. Cluster 1 shows the expected consecutive oxidations of the ferrocene moieties, Cu(I) centers, and phosphine of the dppf ligand.

Chemistry: Experiments, Demonstrations and Other Activities Suggested for Chemistry.

ERIC Educational Resources Information Center

New York State Education Dept., Albany. Bureau of Secondary Curriculum Development.

This publication is a handbook used in conjunction with the course of study in chemistry developed through the New York State Education Department and The University of the State of New York. It contains experiments, demonstrations, and other activities for a chemistry course. Areas covered include the science of chemistry, the atomic structure of…

Plant metabolic clusters - from genetics to genomics.

PubMed

Nützmann, Hans-Wilhelm; Huang, Ancheng; Osbourn, Anne

2016-08-01

Contents 771 I. 771 II. 772 III. 780 IV. 781 V. 786 786 References 786 SUMMARY: Plant natural products are of great value for agriculture, medicine and a wide range of other industrial applications. The discovery of new plant natural product pathways is currently being revolutionized by two key developments. First, breakthroughs in sequencing technology and reduced cost of sequencing are accelerating the ability to find enzymes and pathways for the biosynthesis of new natural products by identifying the underlying genes. Second, there are now multiple examples in which the genes encoding certain natural product pathways have been found to be grouped together in biosynthetic gene clusters within plant genomes. These advances are now making it possible to develop strategies for systematically mining multiple plant genomes for the discovery of new enzymes, pathways and chemistries. Increased knowledge of the features of plant metabolic gene clusters - architecture, regulation and assembly - will be instrumental in expediting natural product discovery. This review summarizes progress in this area. © 2016 The Authors. New Phytologist © 2016 New Phytologist Trust.

Workshop report on large-scale matrix diagonalization methods in chemistry theory institute

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

Bischof, C.H.; Shepard, R.L.; Huss-Lederman, S.

The Large-Scale Matrix Diagonalization Methods in Chemistry theory institute brought together 41 computational chemists and numerical analysts. The goal was to understand the needs of the computational chemistry community in problems that utilize matrix diagonalization techniques. This was accomplished by reviewing the current state of the art and looking toward future directions in matrix diagonalization techniques. This institute occurred about 20 years after a related meeting of similar size. During those 20 years the Davidson method continued to dominate the problem of finding a few extremal eigenvalues for many computational chemistry problems. Work on non-diagonally dominant and non-Hermitian problems asmore » well as parallel computing has also brought new methods to bear. The changes and similarities in problems and methods over the past two decades offered an interesting viewpoint for the success in this area. One important area covered by the talks was overviews of the source and nature of the chemistry problems. The numerical analysts were uniformly grateful for the efforts to convey a better understanding of the problems and issues faced in computational chemistry. An important outcome was an understanding of the wide range of eigenproblems encountered in computational chemistry. The workshop covered problems involving self- consistent-field (SCF), configuration interaction (CI), intramolecular vibrational relaxation (IVR), and scattering problems. In atomic structure calculations using the Hartree-Fock method (SCF), the symmetric matrices can range from order hundreds to thousands. These matrices often include large clusters of eigenvalues which can be as much as 25% of the spectrum. However, if Cl methods are also used, the matrix size can be between 10{sup 4} and 10{sup 9} where only one or a few extremal eigenvalues and eigenvectors are needed. Working with very large matrices has lead to the development of« less

Are clusters important in understanding the mechanisms in atmospheric pressure ionization? Part 1: Reagent ion generation and chemical control of ion populations.

PubMed

Klee, Sonja; Derpmann, Valerie; Wißdorf, Walter; Klopotowski, Sebastian; Kersten, Hendrik; Brockmann, Klaus J; Benter, Thorsten; Albrecht, Sascha; Bruins, Andries P; Dousty, Faezeh; Kauppila, Tiina J; Kostiainen, Risto; O'Brien, Rob; Robb, Damon B; Syage, Jack A

2014-08-01

It is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region.

The performance of low-cost commercial cloud computing as an alternative in computational chemistry.

PubMed

Thackston, Russell; Fortenberry, Ryan C

2015-05-05

The growth of commercial cloud computing (CCC) as a viable means of computational infrastructure is largely unexplored for the purposes of quantum chemistry. In this work, the PSI4 suite of computational chemistry programs is installed on five different types of Amazon World Services CCC platforms. The performance for a set of electronically excited state single-point energies is compared between these CCC platforms and typical, "in-house" physical machines. Further considerations are made for the number of cores or virtual CPUs (vCPUs, for the CCC platforms), but no considerations are made for full parallelization of the program (even though parallelization of the BLAS library is implemented), complete high-performance computing cluster utilization, or steal time. Even with this most pessimistic view of the computations, CCC resources are shown to be more cost effective for significant numbers of typical quantum chemistry computations. Large numbers of large computations are still best utilized by more traditional means, but smaller-scale research may be more effectively undertaken through CCC services. © 2015 Wiley Periodicals, Inc.

Multielectron donors based on TTF-phosphine and ferrocene-phosphine hybrid complexes of a hexarhenium(III) octahedral cluster core.

PubMed

Perruchas, Sandrine; Avarvari, Narcis; Rondeau, David; Levillain, Eric; Batail, Patrick

2005-05-16

Electroactive molecular materials precursors are obtained through coordination chemistry of the hexarhenium cluster core [Re(6)Se(8)](2+) on the six available apical positions with redox-active phosphines bearing tetrathiafulvalene- or ferrocene-based moieties. Single-crystal X-ray diffraction study and electrospray mass spectrometry ascertain the synthesis of these hexasubstituted electroactive clusters, containing up to 12 redox active sites. Cyclic voltammetry experiments demonstrate that these compounds can be reversibly oxidized at rather low potentials, thus allowing an easy access to the corresponding radical species which should provide new conducting and/or magnetic molecular materials.

National Chemistry Week 2000: JCE Resources in Food Chemistry

NASA Astrophysics Data System (ADS)

Jacobsen, Erica K.

2000-10-01

November brings another National Chemistry Week, and this year's theme is food chemistry. I was asked to collect and evaluate JCE resources for use with this theme, a project that took me deep into past issues of JCE and yielded many treasures. Here we present the results of searches for food chemistry information and activities. While the selected articles are mainly at the high school and college levels, there are some excellent ones for the elementary school level and some that can be adapted for younger students. The focus of all articles is on the chemistry of food itself. Activities that only use food to demonstrate a principle other than food chemistry are not included. Articles that cover household products such as cleansers and pharmaceuticals are also not included. Each article has been characterized as a demonstration, experiment, calculation, activity, or informational item; several fit more than one classification. Also included are keywords and an evaluation as to which levels the article may serve.

The N2O activation by Rh5 clusters. A quantum chemistry study.

PubMed

Olvera-Neria, Oscar; Avilés, Roberto; Francisco-Rodríguez, Héctor; Bertin, Virineya; García-Cruz, Raúl; González-Torres, Julio César; Poulain, Enrique

2015-04-01

Nitrous oxide (N2O) is a by-product of exhaust pipe gases treatment produced by motor vehicles. Therefore, the N2O reduction to N2 is necessary to meet the actual environmental legislation. The N2O adsorption and dissociation assisted by the square-based pyramidal Rh5 cluster was investigated using the density functional theory and the zero-order regular approximation (ZORA). The Rh5 sextet ground state is the most active in N2O dissociation, though the quartet and octet states are also active because they are degenerate. The Rh5 cluster spontaneously activates the N2─O cleavage, and the reaction is highly exothermic ca. -75 kcal mol(-1). The N2─O breaking is obtained for the geometrical arrangement that maximizes the overlap and electron transfers between the N2O and Rh5 frontier orbitals. The Rh5 high activity is due to the Rh 3d orbitals are located between the N2O HOMO and LUMO orbitals, which makes possible the interactions between them. In particular, the O 2p states strongly interact with Rh 3d orbitals, which finally weaken the N2─O bond. The electron transfer is from the Rh5 HOMO orbital to the N2O antibonding orbital.

Chemistry in the Comics: Part 2. Classic Chemistry.

ERIC Educational Resources Information Center

Carter, Henry A.

1989-01-01

Describes topics in chemistry as related in the Classics Illustrated publications. Provides a list from "The Pioneers of Science" series with issue date, number, and biograhical topic. Lists references to topics in chemistry. Presents many pages from these comics. (MVL)

The Significance of the Origin of Physical Chemistry for Physical Chemistry Education: The Case of Electrolyte Solution Chemistry

ERIC Educational Resources Information Center

de Berg, Kevin Charles

2014-01-01

Physical Chemistry's birth was fraught with controversy, a controversy about electrolyte solution chemistry which has much to say about how scientific knowledge originates, matures, and responds to challenges. This has direct implications for the way our students are educated in physical chemistry in particular and science in general. The…

Chemistry on Stamps.

ERIC Educational Resources Information Center

Schreck, James O.

1986-01-01

Suggests how postage stamps can be incorporated into chemistry teaching. Categories considered include emergence of chemistry as a science, metric system, atoms (and molecules and ions), stoichiometry, energy relationships in chemical systems, chemical bonding, nuclear chemistry, biochemistry, geochemistry, matter (gases, liquids, and solids),…

Is Chemistry Attractive for Pupils? Czech Pupils' Perception of Chemistry

ERIC Educational Resources Information Center

Kubiatko, Milan

2015-01-01

Chemistry is an important subject due to understanding the composition and structure of the things around us. The main aim of the study was to find out the perception of chemistry by lower secondary school pupils. The partial aims were to find out the influence of gender, year of study and favorite subject on the perception of chemistry. The…

Applying the Coupled-Cluster Ansatz to Solids and Surfaces in the Thermodynamic Limit

NASA Astrophysics Data System (ADS)

Gruber, Thomas; Liao, Ke; Tsatsoulis, Theodoros; Hummel, Felix; Grüneis, Andreas

2018-04-01

Modern electronic structure theories can predict and simulate a wealth of phenomena in surface science and solid-state physics. In order to allow for a direct comparison with experiment, such ab initio predictions have to be made in the thermodynamic limit, substantially increasing the computational cost of many-electron wave-function theories. Here, we present a method that achieves thermodynamic limit results for solids and surfaces using the "gold standard" coupled cluster ansatz of quantum chemistry with unprecedented efficiency. We study the energy difference between carbon diamond and graphite crystals, adsorption energies of water on h -BN, as well as the cohesive energy of the Ne solid, demonstrating the increased efficiency and accuracy of coupled cluster theory for solids and surfaces.

A Model for Protostellar Cluster Luminosities and the Impact on the CO–H2 Conversion Factor

NASA Astrophysics Data System (ADS)

Gaches, Brandt A. L.; Offner, Stella S. R.

2018-02-01

We construct a semianalytic model to study the effect of far-ultraviolet (FUV) radiation on gas chemistry from embedded protostars. We use the protostellar luminosity function (PLF) formalism of Offner & McKee to calculate the total, FUV, and ionizing cluster luminosity for various protostellar accretion histories and cluster sizes. We2 compare the model predictions with surveys of Gould Belt star-forming regions and find that the tapered turbulent core model matches best the mean luminosities and the spread in the data. We combine the cluster model with the photodissociation region astrochemistry code, 3D-PDR, to compute the impact of the FUV luminosity from embedded protostars on the CO-to-H2 conversion factor, X CO, as a function of cluster size, gas mass, and star formation efficiency. We find that X CO has a weak dependence on the FUV radiation from embedded sources for large clusters owing to high cloud optical depths. In smaller and more efficient clusters the embedded FUV increases X CO to levels consistent with the average Milky Way values. The internal physical and chemical structures of the cloud are significantly altered, and X CO depends strongly on the protostellar cluster mass for small efficient clouds.

Towards "Bildung"-Oriented Chemistry Education

ERIC Educational Resources Information Center

Sjöström, Jesper

2013-01-01

This paper concerns "Bildung"-oriented chemistry education, based on a reflective and critical discourse of chemistry. It is contrasted with the dominant type of chemistry education, based on the mainstream discourse of chemistry. "Bildung"-oriented chemistry education includes not only content knowledge in chemistry, but also…

Green Chemistry Metrics with Special Reference to Green Analytical Chemistry.

PubMed

Tobiszewski, Marek; Marć, Mariusz; Gałuszka, Agnieszka; Namieśnik, Jacek

2015-06-12

The concept of green chemistry is widely recognized in chemical laboratories. To properly measure an environmental impact of chemical processes, dedicated assessment tools are required. This paper summarizes the current state of knowledge in the field of development of green chemistry and green analytical chemistry metrics. The diverse methods used for evaluation of the greenness of organic synthesis, such as eco-footprint, E-Factor, EATOS, and Eco-Scale are described. Both the well-established and recently developed green analytical chemistry metrics, including NEMI labeling and analytical Eco-scale, are presented. Additionally, this paper focuses on the possibility of the use of multivariate statistics in evaluation of environmental impact of analytical procedures. All the above metrics are compared and discussed in terms of their advantages and disadvantages. The current needs and future perspectives in green chemistry metrics are also discussed.

Exploration of Fluorine Chemistry at the Multidisciplinary Interface of Chemistry and Biology

PubMed Central

Ojima, Iwao

2013-01-01

Over the last three decades, my engagement in “fluorine chemistry” has evolved substantially, because of the multidisciplinary nature of the research programs. I began my research career as a synthetic chemist in organometallic chemistry and homogeneous catalysis directed toward organic synthesis. Then, I was brought into a very unique world of “fluorine chemistry” in the end of 1970s. I started exploring the interface of fluorine chemistry and transition metal homogeneous catalysis first, which was followed by amino acids, peptides, and peptidomimetics for medicinal chemistry. Since then, I have been exploring the interfaces of fluorine chemistry and multidisciplinary fields of research involving medicinal chemistry, chemical biology, cancer biology and molecular imaging. This perspective intends to cover my fruitful endeavor in the exploration of fluorine chemistry at the multidisciplinary interface of chemistry and biology in a chronological order to show the evolution of my research interest and strategy. PMID:23614876

A New Chemistry Course for Non-Chemistry Majors.

ERIC Educational Resources Information Center

Ariel, Magda; And Others

1982-01-01

A two-semester basic chemistry course for nonchemistry engineering majors is described. First semester provides introductory chemistry for freshmen while second semester is "customer-oriented," based on a departmental choice of three out of six independent modules. For example, aeronautical engineering "customers" would select…

College Chemistry: how a textbook can reveal the values embedded in chemistry.

PubMed

Bensaude-Vincent, Bernadette

2007-12-01

This paper explores the norms, values and ethical attitudes that Linus Pauling wanted to convey to his students in his famous textbook College Chemistry. In this classic textbook, Pauling aimed to introduce beginners into the world of chemistry by presenting chemistry as a systematic science based on a collection of empirical data and a recent theoretical framework. In doing so, he expressed his epistemic and didactic choices clearly. College Chemistry therefore offers an ideal opportunity to examine some of the norms at the core of chemistry's 'moral economy'.

Tracking chemistry self-efficacy and achievement in a preparatory chemistry course

NASA Astrophysics Data System (ADS)

Garcia, Carmen Alicia

Self-efficacy is a person's own perception about performing a task with a certain level of proficiency (Bandura, 1986). An important affective aspect of learning chemistry is chemistry self-efficacy (CSE). Several researchers have found chemistry self-efficacy to be a fair predictor of achievement in chemistry. This study was done in a college preparatory chemistry class for science majors exploring chemistry self-efficacy and its change as it relates to achievement. A subscale of CAEQ, Chemistry Attitudes and Experiences Questionnaire (developed by Dalgety et al, 2003) as well as student interviews were used to determine student chemistry self-efficacy as it changed during the course. The questionnaire was given to the students five times during the semester: in the first class and the class before each the four tests taken through the semester. Twenty-six students, both men and women, of the four major races/ethnicities were interviewed three times during the semester and events that triggered changes in CSE were followed through the interviews. HLM (hierarchical linear modeling) was used to model the results of the CSE surveys. Among the findings, women who started at significantly lower CSE than men accomplished a significant gain by the end of the semester. Blacks' CSE trends through the semester were found to be significantly different from the rest of the ethnicities.

Green Chemistry Pedagogy

NASA Astrophysics Data System (ADS)

Kolopajlo, Larry

2017-02-01

This chapter attempts to show how the practice of chemistry teaching and learning is enriched by the incorporation of green chemistry (GC) into lectures and labs. To support this viewpoint, evidence from a wide range of published papers serve as a cogent argument that GC attracts and engages both science and nonscience students, enhances chemistry content knowledge, and improves the image of the field, while preparing the world for a sustainable future. Published pedagogy associated with green and sustainable chemistry is critically reviewed and discussed.

Transuranic Computational Chemistry.

PubMed

Kaltsoyannis, Nikolas

2018-02-26

Recent developments in the chemistry of the transuranic elements are surveyed, with particular emphasis on computational contributions. Examples are drawn from molecular coordination and organometallic chemistry, and from the study of extended solid systems. The role of the metal valence orbitals in covalent bonding is a particular focus, especially the consequences of the stabilization of the 5f orbitals as the actinide series is traversed. The fledgling chemistry of transuranic elements in the +II oxidation state is highlighted. Throughout, the symbiotic interplay of experimental and computational studies is emphasized; the extraordinary challenges of experimental transuranic chemistry afford computational chemistry a particularly valuable role at the frontier of the periodic table. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

OCCAM: a flexible, multi-purpose and extendable HPC cluster

NASA Astrophysics Data System (ADS)

Aldinucci, M.; Bagnasco, S.; Lusso, S.; Pasteris, P.; Rabellino, S.; Vallero, S.

2017-10-01

The Open Computing Cluster for Advanced data Manipulation (OCCAM) is a multipurpose flexible HPC cluster designed and operated by a collaboration between the University of Torino and the Sezione di Torino of the Istituto Nazionale di Fisica Nucleare. It is aimed at providing a flexible, reconfigurable and extendable infrastructure to cater to a wide range of different scientific computing use cases, including ones from solid-state chemistry, high-energy physics, computer science, big data analytics, computational biology, genomics and many others. Furthermore, it will serve as a platform for R&D activities on computational technologies themselves, with topics ranging from GPU acceleration to Cloud Computing technologies. A heterogeneous and reconfigurable system like this poses a number of challenges related to the frequency at which heterogeneous hardware resources might change their availability and shareability status, which in turn affect methods and means to allocate, manage, optimize, bill, monitor VMs, containers, virtual farms, jobs, interactive bare-metal sessions, etc. This work describes some of the use cases that prompted the design and construction of the HPC cluster, its architecture and resource provisioning model, along with a first characterization of its performance by some synthetic benchmark tools and a few realistic use-case tests.

Chemistry Notes

ERIC Educational Resources Information Center

School Science Review, 1976

1976-01-01

Described are eight chemistry experiments and demonstrations applicable to introductory chemistry courses. Activities include: measure of lattice enthalpy, Le Chatelier's principle, decarboxylation of soap, use of pocket calculators in pH measurement, and making nylon. (SL)

Chemistry and Art.

ERIC Educational Resources Information Center

Berry, Martyn

1999-01-01

Describes a Chemistry and Art project developed for secondary students and teachers sponsored by the National Gallery and The Royal Society of Chemistry in the United Kingdom. Discusses aspects of the techniques used in creating five paintings as well as the chemistry involved in their making, deterioration, conservation, and restoration.…

Teaching School Chemistry.

ERIC Educational Resources Information Center

Waddington, D. J., Ed.

This eight-chapter book is intended for use by chemistry teachers, curriculum developers, teacher educators, and other key personnel working in the field of chemical education. The chapters are: (1) "The Changing Face of Chemistry" (J. A. Campbell); (2) "Curriculum Innovation in School Chemistry" (R. B. Ingel and A. M.…

Bioinorganic modeling chemistry of carbon monoxide dehydrogenases: description of model complexes, current status and possible future scopes.

PubMed

Majumdar, Amit

2014-08-28

Carbon monoxide dehydrogenases (CODHs) use CO as their sole source of carbon and energy and are found in both aerobic and anaerobic carboxidotrophic bacteria. Reversible transformation of CO to CO2 is catalyzed by a bimetallic [Mo-(μ2-S)-Cu] system in aerobic and by a highly asymmetric [Ni-Fe-S] cluster in anaerobic CODH active sites. The CODH activity in the microorganisms effects the removal of almost 10(8) tons of CO annually from the lower atmosphere and earth and thus help to maintain a sub-toxic concentration of CO. Despite an appreciable amount of work, the mechanism of CODH activity is not clearly understood yet. Moreover, biomimetic chemistry directed towards the active sites of CODHs faces several synthetic challenges. The synthetic problems associated with the modeling chemistry and strategies adopted to overcome those problems are discussed along with their limitations. A critical analysis of the exciting results delineating the present status of CODH modeling chemistry and its future prospects are presented.

ENVIRONMENTAL CHEMISTRY

EPA Science Inventory

Environmental chemistry is applied to estimating the exposure of ecosystems and humans to various chemical environmental stressors. Among the stressors of concern are mercury, pesticides, and arsenic. Advanced analytical chemistry techniques are used to measure these stressors ...

Exploring the Sources of Turkish Pre-Service Chemistry Teachers' Chemistry Self-Efficacy Beliefs

ERIC Educational Resources Information Center

Uzuntiryaki, Esen

2008-01-01

This study aimed to examine the underlying sources in developing chemistry self-efficacy beliefs of Turkish pre-service chemistry teachers. For this purpose, the College Chemistry Selfefficacy Scale (CCSS) was administered to 20 pre-service chemistry teachers. Then, phenomenological approach was employed and semi-structured interviews were…

History of Chemistry.

ERIC Educational Resources Information Center

Servos, John W.

1985-01-01

Discusses the development of chemistry in the United States by considering: (1) chemistry as an evolving body of ideas/techniques, and as a set of conceptual resources affecting and affected by the development of other sciences; and (2) chemistry related to the history of American social and economic institutions and practices. (JN)

Chemistry Notes.

ERIC Educational Resources Information Center

School Science Review, 1983

1983-01-01

Presents background information, laboratory procedures, classroom materials/activities, and chemistry experiments. Topics include sublimation, electronegativity, electrolysis, experimental aspects of strontianite, halide test, evaluation of present and future computer programs in chemistry, formula building, care of glass/saturated calomel…

Chemistry Notes

ERIC Educational Resources Information Center

School Science Review, 1972

1972-01-01

Thirteen ideas are presented that may be of use to chemistry teachers. Topics covered include vitamin C, industrial chemistry, electrical conductivity, electrolysis, alkali metals, vibration modes infra-red, dynamic equilibrium, and some new demonstrations in gaseous combinations. (PS)

Chemistry Dashboard

EPA Pesticide Factsheets

The Chemistry Dashboard is part of a suite of dashboards developed by EPA to help evaluate the safety of chemicals. The Chemistry Dashboard provides access to a variety of information on over 700,000 chemicals currently in use.

Circumstellar chemistry

NASA Technical Reports Server (NTRS)

Glassgold, Alfred E.; Huggins, Patrick J.

1987-01-01

The study of the outer envelopes of cool evolved stars has become an active area of research. The physical properties of CS envelopes are presented. Observations of many wavelengths bands are relevant. A summary of observations and a discussion of theoretical considerations concerning the chemistry are summarized. Recent theoretical considerations show that the thermal equilibrium model is of limited use for understanding the chemistry of the outer CS envelopes. The theoretical modeling of the chemistry of CS envelopes provides a quantitive test of chemical concepts which have a broader interest than the envelopes themselves.

PREFACE: Nuclear Cluster Conference; Cluster'07

NASA Astrophysics Data System (ADS)

Freer, Martin

2008-05-01

The Cluster Conference is a long-running conference series dating back to the 1960's, the first being initiated by Wildermuth in Bochum, Germany, in 1969. The most recent meeting was held in Nara, Japan, in 2003, and in 2007 the 9th Cluster Conference was held in Stratford-upon-Avon, UK. As the name suggests the town of Stratford lies upon the River Avon, and shortly before the conference, due to unprecedented rainfall in the area (approximately 10 cm within half a day), lay in the River Avon! Stratford is the birthplace of the `Bard of Avon' William Shakespeare, and this formed an intriguing conference backdrop. The meeting was attended by some 90 delegates and the programme contained 65 70 oral presentations, and was opened by a historical perspective presented by Professor Brink (Oxford) and closed by Professor Horiuchi (RCNP) with an overview of the conference and future perspectives. In between, the conference covered aspects of clustering in exotic nuclei (both neutron and proton-rich), molecular structures in which valence neutrons are exchanged between cluster cores, condensates in nuclei, neutron-clusters, superheavy nuclei, clusters in nuclear astrophysical processes and exotic cluster decays such as 2p and ternary cluster decay. The field of nuclear clustering has become strongly influenced by the physics of radioactive beam facilities (reflected in the programme), and by the excitement that clustering may have an important impact on the structure of nuclei at the neutron drip-line. It was clear that since Nara the field had progressed substantially and that new themes had emerged and others had crystallized. Two particular topics resonated strongly condensates and nuclear molecules. These topics are thus likely to be central in the next cluster conference which will be held in 2011 in the Hungarian city of Debrechen. Martin Freer Participants and Cluster'07

Molecular Composition and Chemistry of Isolated Dense Cores

NASA Astrophysics Data System (ADS)

Cook, Amanda; Boogert, A.

2009-01-01

The composition of molecular clouds and the envelopes and disks surrounding low mass protostars within them is still poorly known. There is little doubt that a large fraction of the molecules is frozen on grains, but the abundance of several crucial species (e.g. ammonia, methanol, ions) in the ices is still uncertain. In addition, prominent spectral features discovered decades ago are still not securely identified (e.g. the 6.85-micron absorption band). Gas phase and grain surface chemistry play pivotal roles in molecule formation, but numerous other processes could have significant impacts as well: shocks, thermal heating, irradiation of ices by ultraviolet photons and cosmic rays. Complex species could be formed this way, profoundly influencing cloud, disk and planetary/cometary chemistry. We have obtained Spitzer/IRS spectra of an unprecedented sample of sight-lines tracing 25 dense isolated cores. These cores physically differ from the large, cluster-forming molecular clouds (e.g. Ophiuchus, Perseus) that are commonly studied: they are less turbulent, colder, less dense, and likely longer lived. These IRS spectra of isolated cores thus provide unique information on ice formation and destruction mechanisms. Toward the same cores, we observed 33 highly extincted background stars as well, tracing the quiescent cloud medium against which the ices around protostars can be contrasted.

Chemistry Notes.

ERIC Educational Resources Information Center

School Science Review, 1981

1981-01-01

Outlines laboratory procedures, demonstrations, teaching suggestions, and content information related to chemistry. Topics include polarizing power; calorimetry and momentum; microcomputers in school chemistry; a constant-volume dispenser for liquids, floating magnets, and crystal lattices; preparation of chromium; and solvent polarity and…

Will water act as a photocatalyst for cluster phase chemical reactions? Vibrational overtone-induced dehydration reaction of methanediol

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

Kramer, Zeb C.; Takahashi, Kaito; Skodje, Rex T.

2012-04-28

The possibility of water catalysis in the vibrational overtone-induced dehydration reaction of methanediol is investigated using ab initio dynamical simulations of small methanediol-water clusters. Quantum chemistry calculations employing clusters with one or two water molecules reveal that the barrier to dehydration is lowered by over 20 kcal/mol because of hydrogen-bonding at the transition state. Nevertheless, the simulations of the reaction dynamics following OH-stretch excitation show little catalytic effect of water and, in some cases, even show an anticatalytic effect. The quantum yield for the dehydration reaction exhibits a delayed threshold effect where reaction does not occur until the photon energymore » is far above the barrier energy. Unlike thermally induced reactions, it is argued that competition between reaction and the irreversible dissipation of photon energy may be expected to raise the dynamical threshold for the reaction above the transition state energy. It is concluded that quantum chemistry calculations showing barrier lowering are not sufficient to infer water catalysis in photochemical reactions, which instead require dynamical modeling.« less

Beyond Academic Tracking: Using Cluster Analysis and Self-Organizing Maps to Investigate Secondary Students' Chemistry Self-Concept

ERIC Educational Resources Information Center

Nielsen, Sara E.; Yezierski, Ellen J.

2016-01-01

Academic tracking, placing students in different classes based on past performance, is a common feature of the American secondary school system. A longitudinal study of secondary students' chemistry self-concept scores was conducted, and one feature of the study was the presence of academic tracking. Though academic tracking is one way to group…

Versatile Method for the Site-Specific Modification of DNA with Boron Clusters: Anti-Epidermal Growth Factor Receptor (EGFR) Antisense Oligonucleotide Case.

PubMed

Ebenryter-Olbińska, Katarzyna; Kaniowski, Damian; Sobczak, Milena; Wojtczak, Błażej A; Janczak, Sławomir; Wielgus, Ewelina; Nawrot, Barbara; Leśnikowski, Zbigniew J

2017-11-21

A general and convenient approach for the incorporation of different types of boron clusters into specific locations of the DNA-oligonucleotide chain based on the automated phosphoramidite method of oligonucleotide synthesis and post-synthetic "click chemistry" modification has been developed. Pronounced effects of boron-cluster modification on the physico- and biochemical properties of the antisense oligonucleotides were observed. The silencing activity of antisense oligonucleotides bearing a single boron cluster modification in the middle of the oligonucleotide chain was substantially higher than that of unmodified oligonucleotides. This finding may be of importance for the design of therapeutic nucleic acids with improved properties. The proposed synthetic methodology broadens the availability of nucleic acid-boron cluster conjugates and opens up new avenues for their potential practical use. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Art in Chemistry: Chemistry in Art. Second Edition

ERIC Educational Resources Information Center

Greenberg, Barbara R.; Patterson, Dianne

2008-01-01

This textbook integrates chemistry and art with hands-on activities and fascinating demonstrations that enable students to see and understand how the science of chemistry is involved in the creation of art. It investigates such topics as color integrated with electromagnetic radiation, atoms, and ions; paints integrated with classes of matter,…

Chemistry, Poetry, and Artistic Illustration: An Interdisciplinary Approach to Teaching and Promoting Chemistry

NASA Astrophysics Data System (ADS)

Furlan, Ping Y.; Kitson, Herbert; Andes, Cynthia

2007-10-01

This article describes a successful interdisciplinary collaboration among chemistry, humanities and English faculty members, who utilized poetry and artistic illustration to help students learn, appreciate, and enjoy chemistry. Students taking general chemistry classes were introduced to poetry writing and museum-type poster preparation during one class period. They were then encouraged to use their imagination and creativity to brainstorm and write chemistry poems or humors on the concepts and principles covered in the chemistry classes and artistically illustrate their original work on posters. The project, 2 3 months in length, was perceived by students as effective at helping them learn chemistry and express their understanding in a fun, personal, and creative way. The instructors found students listened to the directives because many posters were witty, clever, and eye-catching. They showed fresh use of language and revealed a good understanding of chemistry. The top posters were created by a mix of A-, B-, and C-level students. The fine art work, coupled with poetry, helped chemistry come alive on campus, providing an aesthetic presentation of materials that engaged the general viewer.

Document clustering methods, document cluster label disambiguation methods, document clustering apparatuses, and articles of manufacture

DOEpatents

Sanfilippo, Antonio [Richland, WA; Calapristi, Augustin J [West Richland, WA; Crow, Vernon L [Richland, WA; Hetzler, Elizabeth G [Kennewick, WA; Turner, Alan E [Kennewick, WA

2009-12-22

Document clustering methods, document cluster label disambiguation methods, document clustering apparatuses, and articles of manufacture are described. In one aspect, a document clustering method includes providing a document set comprising a plurality of documents, providing a cluster comprising a subset of the documents of the document set, using a plurality of terms of the documents, providing a cluster label indicative of subject matter content of the documents of the cluster, wherein the cluster label comprises a plurality of word senses, and selecting one of the word senses of the cluster label.

Biosynthetic inorganic chemistry.

PubMed

Lu, Yi

2006-08-25

Inorganic chemistry and biology can benefit greatly from each other. Although synthetic and physical inorganic chemistry have been greatly successful in clarifying the role of metal ions in biological systems, the time may now be right to utilize biological systems to advance coordination chemistry. One such example is the use of small, stable, easy-to-make, and well-characterized proteins as ligands to synthesize novel inorganic compounds. This biosynthetic inorganic chemistry is possible thanks to a number of developments in biology. This review summarizes the progress in the synthesis of close models of complex metalloproteins, followed by a description of recent advances in using the approach for making novel compounds that are unprecedented in either inorganic chemistry or biology. The focus is mainly on synthetic "tricks" learned from biology, as well as novel structures and insights obtained. The advantages and disadvantages of this biosynthetic approach are discussed.

Sodium dopants in helium clusters: Structure, equilibrium and submersion kinetics

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

Calvo, F.

Alkali impurities bind to helium nanodroplets very differently depending on their size and charge state, large neutral or charged dopants being wetted by the droplet whereas small neutral impurities prefer to reside aside. Using various computational modeling tools such as quantum Monte Carlo and path-integral molecular dynamics simulations, we have revisited some aspects of the physical chemistry of helium droplets interacting with sodium impurities, including the onset of snowball formation in presence of many-body polarization forces, the transition from non-wetted to wetted behavior in larger sodium clusters, and the kinetics of submersion of small dopants after sudden ionization.

Receptor signaling clusters in the immune synapse(in eng)

DOE PAGES

Dustin, Michael L.; Groves, Jay T.

2012-02-23

Signaling processes between various immune cells involve large-scale spatial reorganization of receptors and signaling molecules within the cell-cell junction. These structures, now collectively referred to as immune synapses, interleave physical and mechanical processes with the cascades of chemical reactions that constitute signal transduction systems. Molecular level clustering, spatial exclusion, and long-range directed transport are all emerging as key regulatory mechanisms. The study of these processes is drawing researchers from physical sciences to join the effort and represents a rapidly growing branch of biophysical chemistry. Furthermore, recent advances in physical and quantitative analyses of signaling within the immune synapses are reviewedmore » here.« less

Receptor signaling clusters in the immune synapse (in eng)

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

Dustin, Michael L.; Groves, Jay T.

2012-02-23

Signaling processes between various immune cells involve large-scale spatial reorganization of receptors and signaling molecules within the cell-cell junction. These structures, now collectively referred to as immune synapses, interleave physical and mechanical processes with the cascades of chemical reactions that constitute signal transduction systems. Molecular level clustering, spatial exclusion, and long-range directed transport are all emerging as key regulatory mechanisms. The study of these processes is drawing researchers from physical sciences to join the effort and represents a rapidly growing branch of biophysical chemistry. Furthermore, recent advances in physical and quantitative analyses of signaling within the immune synapses are reviewedmore » here.« less

Final Project Report for ER15351 “A Study of New Actinide Zintl Ion Materials”

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

Peter K. Dorhout

2007-11-12

The structural chemistry of actinide main-group metal materials provides the fundamental basis for the understanding of structural coordination chemistry and the formation of materials with desired or predicted structural features. The main-group metal building blocks, comprising sulfur-group, phosphorous-group, or silicon-group elements, have shown versatility in oxidation state, coordination, and bonding preferences. These building blocks have allowed us to elucidate a series of structures that are unique to the actinide elements, although we can find structural relationships to transition metal and 4f-element materials. In the past year, we investigated controlled metathesis and self-propagating reactions between actinide metal halides and alkali metalmore » salts of main-group metal chalcogenides such as K-P-S salts. Ternary plutonium thiophosphates have resulted from these reactions at low temperature in sealed ampules. we have also focused efforts to examine reactions of Th, U, and Pu halide salts with other alkali metal salts such as Na-Ge-S and Na-Si-Se and copper chloride to identify if self-propagating reactions may be used as a viable reaction to prepare new actinide materials and we prepared a series of U and Th copper chalcogenide materials. Magnetic measurements continued to be a focus of actinide materials prepared in our laboratory. We also contributed to the XANES work at Los Alamos by preparing materials for study and for comparison with environmental samples.« less

Infusing the Chemistry Curriculum with Green Chemistry Using Real-World Examples, Web Modules, and Atom Economy in Organic Chemistry Courses

ERIC Educational Resources Information Center

Cann, Michael C.; Dickneider, Trudy A.

2004-01-01

Green chemistry is the awareness of the damaging environmental effects due to chemical research and inventions. There is emphasis on a need to include green chemistry in synthesis with atom economy in organic chemistry curriculum to ensure an environmentally conscious future generation of chemists, policy makers, health professionals and business…

International year of Chemistry 2011. A guide to the history of clinical chemistry.

PubMed

Kricka, Larry J; Savory, John

2011-08-01

This review was written as part of the celebration of the International Year of Chemistry 2011. In this review we provide a chronicle of the history of clinical chemistry, with a focus on North America. We outline major methodological advances and trace the development of professional societies and journals dedicated to clinical chemistry. This review also serves as a guide to reference materials for those interested in the history of clinical chemistry. The various resources available, in sound recordings, videos, moving images, image and document archives, museums, and websites dedicated to diagnostic company timelines, are surveyed. These resources provide a map of how the medical subspecialty of clinical chemistry arrived at its present state. This information will undoubtedly help visionaries to determine in which direction clinical chemistry will move in the future.

Cluster model studies of anion and molecular specificities via electrospray ionization photoelectron spectroscopy

DOE PAGES

Wang, Xue -Bin

2017-01-06

Ion specificity, a widely observed macroscopic phenomenon in condensed phases and at interfaces, is essentially a fundamental chemical physical issue. We have been investigating such effects using cluster models in an “atom-by-atom” and “molecule-by-molecule” fashion not possible with condensed-phase methods. We use electrospray ionization (ESI) to generate molecular and ionic clusters to simulate key molecular entities involved in local binding regions, and characterize them employing negative ion photoelectron spectroscopy (NIPES). Inter- and intramolecular interactions and binding configurations are directly obtained as functions of cluster size and composition, providing insightful molecular-level description and characterization over the local active sites that playmore » crucial roles in determining solution chemistry and condensed phase phenomena. Finally, the topics covered in this article are relevant to a wide scope of research fields ranging from ion specific effects in electrolyte solutions, ion selectivity/recognition in normal functioning of life, to molecular specificity in aerosol particle formation, as well as in rational material design and synthesis.« less

Why Teach Environmental Chemistry?

ERIC Educational Resources Information Center

Gardner, Marjorie H.

1974-01-01

Discusses the importance of teaching environmental chemistry in secondary school science classes, and outlines five examples of environmental chemistry problems that focus on major concepts of chemistry and have critical implications for human survival and well-being. (JR)

Effect of the size-selective silver clusters on lithium peroxide morphology in lithium–oxygen batteries

DOE PAGES

Lu, Jun; Cheng, Lei; Lau, Kah Chun; ...

2014-09-12

Lithium–oxygen batteries have the potential needed for long-range electric vehicles, but the charge and discharge chemistries are complex and not well understood. The active sites on cathode surfaces and their role in electrochemical reactions in aprotic lithium–oxygen cells are difficult to ascertain because the exact nature of the sites is unknown. In this paper, we report the deposition of subnanometre silver clusters of exact size and number of atoms on passivated carbon to study the discharge process in lithium–oxygen cells. The results reveal dramatically different morphologies of the electrochemically grown lithium peroxide dependent on the size of the clusters. Thismore » dependence is found to be due to the influence of the cluster size on the formation mechanism, which also affects the charge process. Finally, the results of this study suggest that precise control of subnanometre surface structure on cathodes can be used as a means to improve the performance of lithium–oxygen cells.« less

Introducing Chemistry Students to the "Real World" of Chemistry

ERIC Educational Resources Information Center

Brown, Michael E.; Cosser, Ronald C.; Davies-Coleman, Michael T.; Kaye, Perry T.; Klein, Rosalyn; Lamprecht, Emmanuel; Lobb, Kevin; Nyokong, Tebello; Sewry, Joyce D.; Tshentu, Zenixole R.; van der Zeyde, Tino; Watkins, Gareth M.

2010-01-01

A majority of chemistry graduates seek employment in a rapidly changing chemical industry. Our attempts to provide the graduates with skills in entrepreneurship and the ability to understand and communicate with their chemical engineering colleagues, in addition to their fundamental knowledge of chemistry, are described. This is done at…

Logic, History, and the Chemistry Textbook: I. Does Chemistry Have a Logical Structure?

ERIC Educational Resources Information Center

Jensen, William B.

1998-01-01

Presents the first of three invited keynote lectures from the 1995 conference of the New England Association of Chemistry Teachers. Discusses the relevance of the history of chemistry to the teaching of chemistry. Contains 27 references. (DDR)

The Inorganic Illustrator: A 3-D Graphical Supplement for Inorganic and Bioinorganic Chemistry Courses Distributed on CD-ROM

NASA Astrophysics Data System (ADS)

Childs, Scott L.; Hagen, Karl S.

1996-10-01

The visualization of molecular and solid state chemical structures in three dimensions is a particularly difficult problem for students to overcome when the primary means of communication is the two-dimensional world of textbooks, blackboards, and overhead projector screens. Recent editions of popular textbooks in organic, inorganic, and biochemistry have included stereoviews of molecules to aid the student, and stereoviews of crystal structures have been used in inorganic chemistry publications for many years. These are powerful aids for visualizing complex molecules, but with the exception of the biochemistry text mentioned above, they are limited to single, static images generally in black and white. Molecular model kits are routinely used very effectively in organic chemistry but their utility in inorganic chemistry is limited to all but the most simple molecules encountered. Now that personal computers are generally accessible and multimedia tools are starting to make an appearance in chemistry lecture halls (1), we can make our inorganic and bioinorganic chemistry and crystallography lectures come alive with the aid of the computer-based resources, which are the essence of this project. As part of this project we are accumulating a database of representative crystal structures of main group molecules, coordination complexes, organometallic compounds, small metalloproteins, bioinorganic model complexes, clusters, and solid state materials in Chem3D Plus format to be viewed with Chem3D Viewer, which is free software from Cambridge Scientific Computing. We are also generating a library of high-quality graphic images of these same molecules and structures using Cerius2 package from Molecular Simulations. These include polyhedral representations of clusters and solid state structures (see Fig. 1). Figure 1. Representation of the user interface: the title page and an example of polyhedral and ball-and-stick representation of an octanuclear iron-oxo cluster. The

A Titanium–Organic Framework as an Exemplar of Combining the Chemistry of Metal– and Covalent–Organic Frameworks

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

Nguyen, Ha L.; Gándara, Felipe; Furukawa, Hiroyasu

A crystalline material with a two-dimensional structure, termed metal–organic framework-901 (MOF-901), was prepared using a strategy that combines the chemistry of MOFs and covalent–organic frameworks (COFs). This strategy involves in situ generation of an amine-functionalized titanium oxo cluster, Ti6O6(OCH3)6(AB)6 (AB = 4-aminobenzoate), which was linked with benzene-1,4-dialdehyde using imine condensation reactions, typical of COFs. The crystal structure of MOF-901 is composed of hexagonal porous layers that are likely stacked in staggered conformation (hxl topology). This MOF represents the first example of combining metal cluster chemistry with dynamic organic covalent bond formation to give a new crystalline, extended framework of titaniummore » metal, which is rarely used in MOFs. The incorporation of Ti(IV) units made MOF-901 useful in the photocatalyzed polymerization of methyl methacrylate (MMA). The resulting polyMMA product was obtained with a high-number-average molar mass (26 850 g mol–1) and low polydispersity index (1.6), which in many respects are better than those achieved by the commercially available photocatalyst (P-25 TiO2). Additionally, the catalyst can be isolated, reused, and recycled with no loss in performance.« less

Comprehensive cluster analysis with Transitivity Clustering.

PubMed

Wittkop, Tobias; Emig, Dorothea; Truss, Anke; Albrecht, Mario; Böcker, Sebastian; Baumbach, Jan

2011-03-01

Transitivity Clustering is a method for the partitioning of biological data into groups of similar objects, such as genes, for instance. It provides integrated access to various functions addressing each step of a typical cluster analysis. To facilitate this, Transitivity Clustering is accessible online and offers three user-friendly interfaces: a powerful stand-alone version, a web interface, and a collection of Cytoscape plug-ins. In this paper, we describe three major workflows: (i) protein (super)family detection with Cytoscape, (ii) protein homology detection with incomplete gold standards and (iii) clustering of gene expression data. This protocol guides the user through the most important features of Transitivity Clustering and takes ∼1 h to complete.

Cluster Physics with Merging Galaxy Clusters

NASA Astrophysics Data System (ADS)

Molnar, Sandor

Collisions between galaxy clusters provide a unique opportunity to study matter in a parameter space which cannot be explored in our laboratories on Earth. In the standard ΛCDM model, where the total density is dominated by the cosmological constant (Λ) and the matter density by cold dark matter (CDM), structure formation is hierarchical, and clusters grow mostly by merging. Mergers of two massive clusters are the most energetic events in the universe after the Big Bang, hence they provide a unique laboratory to study cluster physics. The two main mass components in clusters behave differently during collisions: the dark matter is nearly collisionless, responding only to gravity, while the gas is subject to pressure forces and dissipation, and shocks and turbulence are developed during collisions. In the present contribution we review the different methods used to derive the physical properties of merging clusters. Different physical processes leave their signatures on different wavelengths, thus our review is based on a multifrequency analysis. In principle, the best way to analyze multifrequency observations of merging clusters is to model them using N-body/HYDRO numerical simulations. We discuss the results of such detailed analyses. New high spatial and spectral resolution ground and space based telescopes will come online in the near future. Motivated by these new opportunities, we briefly discuss methods which will be feasible in the near future in studying merging clusters.

Cluster-cluster correlations and constraints on the correlation hierarchy

NASA Technical Reports Server (NTRS)

Hamilton, A. J. S.; Gott, J. R., III

1988-01-01

The hypothesis that galaxies cluster around clusters at least as strongly as they cluster around galaxies imposes constraints on the hierarchy of correlation amplitudes in hierachical clustering models. The distributions which saturate these constraints are the Rayleigh-Levy random walk fractals proposed by Mandelbrot; for these fractal distributions cluster-cluster correlations are all identically equal to galaxy-galaxy correlations. If correlation amplitudes exceed the constraints, as is observed, then cluster-cluster correlations must exceed galaxy-galaxy correlations, as is observed.

A Quantum Chemistry Concept Inventory for Physical Chemistry Classes

ERIC Educational Resources Information Center

Dick-Perez, Marilu; Luxford, Cynthia J.; Windus, Theresa L.; Holme, Thomas

2016-01-01

A 14-item, multiple-choice diagnostic assessment tool, the quantum chemistry concept inventory or QCCI, is presented. Items were developed based on published student misconceptions and content coverage and then piloted and used in advanced physical chemistry undergraduate courses. In addition to the instrument itself, data from both a pretest,…

Green Chemistry and Education.

ERIC Educational Resources Information Center

Hjeresen, Dennis L.; Schutt, David L.; Boese, Janet M.

2000-01-01

Many students today are profoundly interested in the sustainability of their world. Introduces Green Chemistry and its principles with teaching materials. Green Chemistry is the use of chemistry for pollution prevention and the design of chemical products and processes that are environmentally benign. (ASK)

Studies of cluster-assembled materials: From gas phase to condensed phase

NASA Astrophysics Data System (ADS)

Gao, Lin

Clusters, defined as "a number of similar things that occur together" in Webster's dictionary, has different meanings depending on the given subject. To physicists and chemists, the word cluster means "a group of atoms or molecules formed by interactions ranging from very weak van der Waals interactions to strong ionic bonds." Unlike molecules, which are made by nature and are stable under ambient conditions, clusters discovered in a laboratory are often metastable. Molecules have specific stoichiometry, whereas the cluster's composition can usually be altered atom by atom. Thus, clusters can be taken as intrinsically "artificial molecules" with considerably more tunabilities in their properties. Research into the relative stability and instability of clusters has in recent years become a very active research area, especially following the study by Khanna and Castleman that first suggested that by varying size and composition, clusters can expand the periodic table to the 3 rd-dimension; that is, clusters can mimic the chemistry of atoms and may, therefore, be used as the building blocks of new materials. The discovery of Met-Cars has drawn worldwide interests and has been actively investigated by researchers from a variety of fields, including physics, chemistry and material science. However, the unsuccessful search for a solvent capable of isolating Met-Cars has impeded progress in characterizing the material in the condensed state and, hence, limited its potential applications as a novel nanoscale material. An alternative method involving the deposition of mass-gated species and the subsequent structural investigation via Transmission Electron Microscopy (TEM) has been employed. With particularly interesting results, soft-landed deposits of zirconium Met-Cars were found to form a face-centered-cubic (FCC) structure with a lattice parameter ˜ 15A. The production of Met-Cars is conducted with the direct laser vaporization (DLV) of metal/graphite composite pellets

Convex Clustering: An Attractive Alternative to Hierarchical Clustering

PubMed Central

Chen, Gary K.; Chi, Eric C.; Ranola, John Michael O.; Lange, Kenneth

2015-01-01

The primary goal in cluster analysis is to discover natural groupings of objects. The field of cluster analysis is crowded with diverse methods that make special assumptions about data and address different scientific aims. Despite its shortcomings in accuracy, hierarchical clustering is the dominant clustering method in bioinformatics. Biologists find the trees constructed by hierarchical clustering visually appealing and in tune with their evolutionary perspective. Hierarchical clustering operates on multiple scales simultaneously. This is essential, for instance, in transcriptome data, where one may be interested in making qualitative inferences about how lower-order relationships like gene modules lead to higher-order relationships like pathways or biological processes. The recently developed method of convex clustering preserves the visual appeal of hierarchical clustering while ameliorating its propensity to make false inferences in the presence of outliers and noise. The solution paths generated by convex clustering reveal relationships between clusters that are hidden by static methods such as k-means clustering. The current paper derives and tests a novel proximal distance algorithm for minimizing the objective function of convex clustering. The algorithm separates parameters, accommodates missing data, and supports prior information on relationships. Our program CONVEXCLUSTER incorporating the algorithm is implemented on ATI and nVidia graphics processing units (GPUs) for maximal speed. Several biological examples illustrate the strengths of convex clustering and the ability of the proximal distance algorithm to handle high-dimensional problems. CONVEXCLUSTER can be freely downloaded from the UCLA Human Genetics web site at http://www.genetics.ucla.edu/software/ PMID:25965340

Convex clustering: an attractive alternative to hierarchical clustering.

PubMed

Chen, Gary K; Chi, Eric C; Ranola, John Michael O; Lange, Kenneth

2015-05-01

The primary goal in cluster analysis is to discover natural groupings of objects. The field of cluster analysis is crowded with diverse methods that make special assumptions about data and address different scientific aims. Despite its shortcomings in accuracy, hierarchical clustering is the dominant clustering method in bioinformatics. Biologists find the trees constructed by hierarchical clustering visually appealing and in tune with their evolutionary perspective. Hierarchical clustering operates on multiple scales simultaneously. This is essential, for instance, in transcriptome data, where one may be interested in making qualitative inferences about how lower-order relationships like gene modules lead to higher-order relationships like pathways or biological processes. The recently developed method of convex clustering preserves the visual appeal of hierarchical clustering while ameliorating its propensity to make false inferences in the presence of outliers and noise. The solution paths generated by convex clustering reveal relationships between clusters that are hidden by static methods such as k-means clustering. The current paper derives and tests a novel proximal distance algorithm for minimizing the objective function of convex clustering. The algorithm separates parameters, accommodates missing data, and supports prior information on relationships. Our program CONVEXCLUSTER incorporating the algorithm is implemented on ATI and nVidia graphics processing units (GPUs) for maximal speed. Several biological examples illustrate the strengths of convex clustering and the ability of the proximal distance algorithm to handle high-dimensional problems. CONVEXCLUSTER can be freely downloaded from the UCLA Human Genetics web site at http://www.genetics.ucla.edu/software/.

[Ti8Zr2O12(COO)16] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks

PubMed Central

2017-01-01

Metal–organic frameworks (MOFs) based on Ti-oxo clusters (Ti-MOFs) represent a naturally self-assembled superlattice of TiO2 nanoparticles separated by designable organic linkers as antenna chromophores, epitomizing a promising platform for solar energy conversion. However, despite the vast, diverse, and well-developed Ti-cluster chemistry, only a scarce number of Ti-MOFs have been documented. The synthetic conditions of most Ti-based clusters are incompatible with those required for MOF crystallization, which has severely limited the development of Ti-MOFs. This challenge has been met herein by the discovery of the [Ti8Zr2O12(COO)16] cluster as a nearly ideal building unit for photoactive MOFs. A family of isoreticular photoactive MOFs were assembled, and their orbital alignments were fine-tuned by rational functionalization of organic linkers under computational guidance. These MOFs demonstrate high porosity, excellent chemical stability, tunable photoresponse, and good activity toward photocatalytic hydrogen evolution reactions. The discovery of the [Ti8Zr2O12(COO)16] cluster and the facile construction of photoactive MOFs from this cluster shall pave the way for the development of future Ti-MOF-based photocatalysts. PMID:29392182

SEDIMENT AND POREWATER CHEMISTRY

EPA Science Inventory

This chapter reviews sediment chemistry, its effect on porewater chemistry and how this chemistry changes from place to place. We focus on the overall chemical environment of the sediments, for which a great deal is known from studies on sediment diagenesis and from which some pr...

CHEMISTRY, A GUIDE FOR TEACHERS.

ERIC Educational Resources Information Center

WHEELER, HUBERT

THE VOLUME INCLUDES AN INTRODUCTION, THE COURSE CONTENT IN CHEMISTRY, AND FIVE APPENDIXES OF USEFUL INFORMATION. THE CHEMISTRY COURSE CONTENT IS FURTHER SUBDIVIDED INTO FIVE SECTIONS--(1) THE OVERVIEW, (2) CHEMICAL REACTIONS, (3) CHEMICAL BONDING AND MOLECULAR ARCHITECTURE, (4) DESCRIPTIVE CHEMISTRY, AND (5) ADVANCED CHEMISTRY. EACH OF THE FIVE…

Chemistry, Poetry, and Artistic Illustration: An Interdisciplinary Approach to Teaching and Promoting Chemistry

ERIC Educational Resources Information Center

Furlan, Ping Y.; Kitson, Herbert; Andes, Cynthia

2007-01-01

This article describes a successful interdisciplinary collaboration among chemistry, humanities and English faculty members, who utilized poetry and artistic illustration to help students learn, appreciate, and enjoy chemistry. Students taking general chemistry classes were introduced to poetry writing and museum-type poster preparation during one…

Synthesis and first use of pyridine-2,6-diylbis(pyrazine-2-ylmethanone) in metal cluster chemistry: a {Mn(III)3Na2} complex with an ideal trigonal bipyramidal geometry.

PubMed

Giannopoulos, Dimosthenis P; Wilson-Konderka, Cody; Gagnon, Kevin J; Teat, Simon J; Escuer, Albert; Metallinos, Costa; Stamatatos, Theocharis C

2015-03-07

The successful organic synthesis of a new dipyrazole/pyridine-dicarbonyl organic molecule, namely pyridine-2,6-diylbis(pyrazine-2-ylmethanone) [(pz)CO(py)CO(pz)], followed by its employment in Mn coordination chemistry has yielded the neutral cluster compound [Mn3Na2O(N3)3(L)3] (1), where L(2-) is the (pz)C(CH2COCH3)(O(-))(py)C(CH2COCH3)(O(-))(pz) dianion. The latter group was formed in situ, presumably by the nucleophilic attack of the carbanion (-)CH2COCH3 to the carbonyl carbon atoms of (pz)CO(py)CO(pz), in the presence of Mn(n+) ions under basic conditions and in solvent Me2CO. Complex 1 possesses an almost ideal trigonal bipyramidal topology, with the two Na(I) ions occupying the apical positions and the three Mn(III) ions residing in the equatorial trigonal plane. The bridging ligation about the metal ions is provided by a μ3-O(2-) ion and six μ-OR(-) groups from the L(2-) ligand, while peripheral ligation is completed by three terminal azido groups and the pyridine N and carbonyl O atoms of L(2-). Magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the paramagnetic Mn(III) centres; the use of an anisotropic, equilateral Mn(III)3 triangle model allowed us to fit the magnetic data and obtain the best-fit parameters: J = -10.8 cm(-1), D = -5.3 cm(-1), and g = 1.99. The combined results demonstrate the rich chemical reactivity of carbonyl groups and the ability of poly-ketone ligands to stabilize cluster compounds with unprecedented structural motifs and interesting architectures.

Cluster management.

PubMed

Katz, R

1992-11-01

Cluster management is a management model that fosters decentralization of management, develops leadership potential of staff, and creates ownership of unit-based goals. Unlike shared governance models, there is no formal structure created by committees and it is less threatening for managers. There are two parts to the cluster management model. One is the formation of cluster groups, consisting of all staff and facilitated by a cluster leader. The cluster groups function for communication and problem-solving. The second part of the cluster management model is the creation of task forces. These task forces are designed to work on short-term goals, usually in response to solving one of the unit's goals. Sometimes the task forces are used for quality improvement or system problems. Clusters are groups of not more than five or six staff members, facilitated by a cluster leader. A cluster is made up of individuals who work the same shift. For example, people with job titles who work days would be in a cluster. There would be registered nurses, licensed practical nurses, nursing assistants, and unit clerks in the cluster. The cluster leader is chosen by the manager based on certain criteria and is trained for this specialized role. The concept of cluster management, criteria for choosing leaders, training for leaders, using cluster groups to solve quality improvement issues, and the learning process necessary for manager support are described.

Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals

NASA Astrophysics Data System (ADS)

Garza, Alejandro J.; Sousa Alencar, Ana G.; Scuseria, Gustavo E.

2015-12-01

Singlet-paired coupled cluster doubles (CCD0) is a simplification of CCD that relinquishes a fraction of dynamic correlation in order to be able to describe static correlation. Combinations of CCD0 with density functionals that recover specifically the dynamic correlation missing in the former have also been developed recently. Here, we assess the accuracy of CCD0 and CCD0+DFT (and variants of these using Brueckner orbitals) as compared to well-established quantum chemical methods for describing ground-state properties of singlet actinide molecules. The f0 actinyl series (UO22+, NpO23+, PuO24+), the isoelectronic NUN, and thorium (ThO, ThO2+) and nobelium (NoO, NoO2) oxides are studied.

Self-organizing neural networks--an alternative way of cluster analysis in clinical chemistry.

PubMed

Reibnegger, G; Wachter, H

1996-04-15

Supervised learning schemes have been employed by several workers for training neural networks designed to solve clinical problems. We demonstrate that unsupervised techniques can also produce interesting and meaningful results. Using a data set on the chemical composition of milk from 22 different mammals, we demonstrate that self-organizing feature maps (Kohonen networks) as well as a modified version of error backpropagation technique yield results mimicking conventional cluster analysis. Both techniques are able to project a potentially multi-dimensional input vector onto a two-dimensional space whereby neighborhood relationships remain conserved. Thus, these techniques can be used for reducing dimensionality of complicated data sets and for enhancing comprehensibility of features hidden in the data matrix.

Assessment of interaction-strength interpolation formulas for gold and silver clusters

NASA Astrophysics Data System (ADS)

Giarrusso, Sara; Gori-Giorgi, Paola; Della Sala, Fabio; Fabiano, Eduardo

2018-04-01

The performance of functionals based on the idea of interpolating between the weak- and the strong-interaction limits the global adiabatic-connection integrand is carefully studied for the challenging case of noble-metal clusters. Different interpolation formulas are considered and various features of this approach are analyzed. It is found that these functionals, when used as a correlation correction to Hartree-Fock, are quite robust for the description of atomization energies, while performing less well for ionization potentials. Future directions that can be envisaged from this study and a previous one on main group chemistry are discussed.

Clustering cancer gene expression data by projective clustering ensemble

PubMed Central

Yu, Xianxue; Yu, Guoxian

2017-01-01

Gene expression data analysis has paramount implications for gene treatments, cancer diagnosis and other domains. Clustering is an important and promising tool to analyze gene expression data. Gene expression data is often characterized by a large amount of genes but with limited samples, thus various projective clustering techniques and ensemble techniques have been suggested to combat with these challenges. However, it is rather challenging to synergy these two kinds of techniques together to avoid the curse of dimensionality problem and to boost the performance of gene expression data clustering. In this paper, we employ a projective clustering ensemble (PCE) to integrate the advantages of projective clustering and ensemble clustering, and to avoid the dilemma of combining multiple projective clusterings. Our experimental results on publicly available cancer gene expression data show PCE can improve the quality of clustering gene expression data by at least 4.5% (on average) than other related techniques, including dimensionality reduction based single clustering and ensemble approaches. The empirical study demonstrates that, to further boost the performance of clustering cancer gene expression data, it is necessary and promising to synergy projective clustering with ensemble clustering. PCE can serve as an effective alternative technique for clustering gene expression data. PMID:28234920

Computational chemistry of modified [MFe3S4] and [M2Fe2S4] clusters: assessment of trends in electronic structure and properties.

PubMed

Jensen, Kasper P; Ooi, Bee-Lean; Christensen, Hans E M

2008-12-18

The aim of this work is to understand the molecular evolution of iron-sulfur clusters in terms of electronic structure and function. Metal-substituted models of biological [Fe(4)S(4)] clusters in oxidation states [M(x)Fe(4-x)S(4)](3+/2+/1+) have been studied by density functional theory (M = Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pd, with x = 1 or 2). Most of these clusters have not been characterized before. For those that have been characterized experimentally, very good agreement is obtained, implying that also the predicted structures and properties of new clusters are accurate. Mean absolute errors are 0.024 A for bond lengths ([Fe(4)S(4)], [NiFe(3)S(4)], [CoFe(3)S(4)]) and 0.09 V for shifts in reduction potentials relative to the [Fe(4)S(4)] cluster. All structures form cuboidal geometries similar to the all-iron clusters, except the Pd-substituted clusters, which instead form highly distorted trigonal and tetragonal local sites in compromised, pseudocuboidal geometries. In contrast to other electron-transfer sites, cytochromes, blue copper proteins, and smaller iron-sulfur clusters, we find that the [Fe(4)S(4)] clusters are very insensitive to metal substitution, displaying quite small changes in reorganization energies and reduction potentials upon substitution. Thus, the [Fe(4)S(4)] clusters have an evolutionary advantage in being robust to pollution from other metals, still retaining function. We analyze in detail the electronic structure of individual clusters and rationalize spin couplings and redox activity. Often, several configurations are very close in energy, implying possible use as spin-crossover systems, and spin states are predicted accurately in all but one case ([CuFe(3)S(4)]). The results are anticipated to be helpful in defining new molecular systems with catalytic and magnetic properties.

Seizure clustering.

PubMed

Haut, Sheryl R

2006-02-01

Seizure clusters, also known as repetitive or serial seizures, occur commonly in epilepsy. Clustering implies that the occurrence of one seizure may influence the probability of a subsequent seizure; thus, the investigation of the clustering phenomenon yields insights into both specific mechanisms of seizure clustering and more general concepts of seizure occurrence. Seizure clustering has been defined clinically as a number of seizures per unit time and, statistically, as a deviation from a random distribution, or interseizure interval dependence. This review explores the pathophysiology, epidemiology, and clinical implications of clustering, as well as other periodic patterns of seizure occurrence. Risk factors for experiencing clusters and potential precipitants of clustering are also addressed.

Relational Analysis of College Chemistry-Major Students' Conceptions of and Approaches to Learning Chemistry

ERIC Educational Resources Information Center

Li, Wei-Ting; Liang, Jyh-Chong; Tsai, Chin-Chung

2013-01-01

The purpose of this research was to examine the relationships between conceptions of learning and approaches to learning in chemistry. Two questionnaires, conceptions of learning chemistry (COLC) and approaches to learning chemistry (ALC), were developed to identify 369 college chemistry-major students' (220 males and 149 females) conceptions of…

Hot stars in young massive clusters: Mapping the current Galactic metallicity

NASA Astrophysics Data System (ADS)

de la Fuente, Diego; Najarro, Francisco; Davies, Ben; Trombley, Christine; Figer, Donald F.; Herrero, Artemio

2013-06-01

Young Massive Clusters (YMCs) with ages < 6 Myr are ideal tools for mapping the current chemical abundances in the Galactic disk for several reasons. First of all, the locations of these clusters can be known through spectrophotometric distances. Secondly, their young ages guarantee that these objects present the same chemical composition than the surrounding environment where they are recently born. Finally, the YMCs host very massive stars whose extreme luminosities allow to accomplish detailed spectroscopic analyses even in the most distant regions of the Milky Way. Our group has carried out ISAAC/VLT spectroscopic observations of hot massive stars belonging to several YMCs in different locations around the Galactic disk. As a result, high signal-to-noise, near-infrared spectra of dozens of blue massive stars (including many OB supergiants, Wolf-Rayet stars and a B hypergiant) have been obtained. These data are fully reduced, and NLTE spherical atmosphere modeling is in process. Several line diagnostics will be combined in order to calculate metal abundances accurately for each cluster. The diverse locations of the clusters will allow us to draw a two-dimensional chemical map of the Galactic disk for the first time. The study of the radial and azimuthal variations of elemental abundances will be crucial for understanding the chemical evolution of the Milky Way. Particularly, the ratio between Fe-peak and alpha elements will constitute a powerful tool to investigate the past stellar populations that originated the current Galactic chemistry.

Plasma chemistry as a tool for green chemistry, environmental analysis and waste management.

PubMed

Mollah, M Y; Schennach, R; Patscheider, J; Promreuk, S; Cocke, D L

2000-12-15

The applications of plasma chemistry to environmental problems and to green chemistry are emerging fields that offer unique opportunities for advancement. There has been substantial progress in the application of plasmas to analytical diagnostics and to waste reduction and waste management. This review discusses the chemistry and physics necessary to a basic understanding of plasmas, something that has been missing from recent technical reviews. The current status of plasmas in environmental chemistry is summarized and emerging areas of application for plasmas are delineated. Plasmas are defined and discussed in terms of their properties that make them useful for environmental chemistry. Information is drawn from diverse fields to illustrate the potential applications of plasmas in analysis, materials modifications and hazardous waste treatments.

Addressing the complexity of water chemistry in environmental fate modeling for engineered nanoparticles.

PubMed

Sani-Kast, Nicole; Scheringer, Martin; Slomberg, Danielle; Labille, Jérôme; Praetorius, Antonia; Ollivier, Patrick; Hungerbühler, Konrad

2015-12-01

Engineered nanoparticle (ENP) fate models developed to date - aimed at predicting ENP concentration in the aqueous environment - have limited applicability because they employ constant environmental conditions along the modeled system or a highly specific environmental representation; both approaches do not show the effects of spatial and/or temporal variability. To address this conceptual gap, we developed a novel modeling strategy that: 1) incorporates spatial variability in environmental conditions in an existing ENP fate model; and 2) analyzes the effect of a wide range of randomly sampled environmental conditions (representing variations in water chemistry). This approach was employed to investigate the transport of nano-TiO2 in the Lower Rhône River (France) under numerous sets of environmental conditions. The predicted spatial concentration profiles of nano-TiO2 were then grouped according to their similarity by using cluster analysis. The analysis resulted in a small number of clusters representing groups of spatial concentration profiles. All clusters show nano-TiO2 accumulation in the sediment layer, supporting results from previous studies. Analysis of the characteristic features of each cluster demonstrated a strong association between the water conditions in regions close to the ENP emission source and the cluster membership of the corresponding spatial concentration profiles. In particular, water compositions favoring heteroaggregation between the ENPs and suspended particulate matter resulted in clusters of low variability. These conditions are, therefore, reliable predictors of the eventual fate of the modeled ENPs. The conclusions from this study are also valid for ENP fate in other large river systems. Our results, therefore, shift the focus of future modeling and experimental research of ENP environmental fate to the water characteristic in regions near the expected ENP emission sources. Under conditions favoring heteroaggregation in these

Data Clustering

NASA Astrophysics Data System (ADS)

Wagstaff, Kiri L.

2012-03-01

On obtaining a new data set, the researcher is immediately faced with the challenge of obtaining a high-level understanding from the observations. What does a typical item look like? What are the dominant trends? How many distinct groups are included in the data set, and how is each one characterized? Which observable values are common, and which rarely occur? Which items stand out as anomalies or outliers from the rest of the data? This challenge is exacerbated by the steady growth in data set size [11] as new instruments push into new frontiers of parameter space, via improvements in temporal, spatial, and spectral resolution, or by the desire to "fuse" observations from different modalities and instruments into a larger-picture understanding of the same underlying phenomenon. Data clustering algorithms provide a variety of solutions for this task. They can generate summaries, locate outliers, compress data, identify dense or sparse regions of feature space, and build data models. It is useful to note up front that "clusters" in this context refer to groups of items within some descriptive feature space, not (necessarily) to "galaxy clusters" which are dense regions in physical space. The goal of this chapter is to survey a variety of data clustering methods, with an eye toward their applicability to astronomical data analysis. In addition to improving the individual researcher’s understanding of a given data set, clustering has led directly to scientific advances, such as the discovery of new subclasses of stars [14] and gamma-ray bursts (GRBs) [38]. All clustering algorithms seek to identify groups within a data set that reflect some observed, quantifiable structure. Clustering is traditionally an unsupervised approach to data analysis, in the sense that it operates without any direct guidance about which items should be assigned to which clusters. There has been a recent trend in the clustering literature toward supporting semisupervised or constrained

Metalloporphyrins as Oxidation Catalysts: Moving toward "Greener" Chemistry in the Inorganic Chemistry Laboratory

ERIC Educational Resources Information Center

Clark, Rose A.; Stock, Anne E.; Zovinka, Edward P.

2012-01-01

Training future chemists to be aware of the environmental impact of their work is of fundamental importance to global society. To convince chemists to embrace sustainability, the integration of green chemistry across the entire chemistry curriculum is a necessary step. This experiment expands the reach of green chemistry techniques into the…

Cocrystal Controlled Solid-State Synthesis: A Green Chemistry Experiment for Undergraduate Organic Chemistry

ERIC Educational Resources Information Center

Cheney, Miranda L.; Zaworotko, Michael J.; Beaton, Steve; Singer, Robert D.

2008-01-01

Green chemistry has become an important area of concern for all chemists from practitioners in the pharmaceutical industry to professors and the students they teach and is now being incorporated into lectures of general and organic chemistry courses. However, there are relatively few green chemistry experiments that are easily incorporated into…

Globular clusters and environmental effects in galaxy clusters

NASA Astrophysics Data System (ADS)

Sales, Laura

2016-10-01

Globular clusters are old compact stellar systems orbiting around galaxies of all types. Tens of thousands of them can also be found populating the intra-cluster regions of nearby galaxy clusters like Virgo and Coma. Thanks to the HST Frontier Fields program, GCs are starting now to be detected also in intermediate redshift clusters. Yet, despite their ubiquity, a theoretical model for the formation and evolution of GCs is still missing, especially within the cosmological context.Here we propose to use cosmological hydrodynamical simulations of 18 galaxy clusters coupled to a post-processing GC formation model to explore the assembly of galaxies in clusters together with their expected GC population. The method, which has already been implemented and tested, will allow us to characterize for the first time the number, radial distribution and kinematics of GCs in clusters, with products directly comparable to observational maps. We will explore cluster-to-cluster variations and also characterize the build up of the intra-cluster component of GCs with time.As the method relies on a detailed study of the star-formation history of galaxies, we will jointly constrain the predicted quenching time-scales for satellites and the occurrence of starburst events associated to infall and orbital pericenters of galaxies in massive clusters. This will inform further studies on the distribution, velocity and properties of post-starburst galaxies in past, ongoing and future HST programs.

First-principles energetics of water clusters and ice: A many-body analysis

NASA Astrophysics Data System (ADS)

Gillan, M. J.; Alfè, D.; Bartók, A. P.; Csányi, G.

2013-12-01

Standard forms of density-functional theory (DFT) have good predictive power for many materials, but are not yet fully satisfactory for cluster, solid, and liquid forms of water. Recent work has stressed the importance of DFT errors in describing dispersion, but we note that errors in other parts of the energy may also contribute. We obtain information about the nature of DFT errors by using a many-body separation of the total energy into its 1-body, 2-body, and beyond-2-body components to analyze the deficiencies of the popular PBE and BLYP approximations for the energetics of water clusters and ice structures. The errors of these approximations are computed by using accurate benchmark energies from the coupled-cluster technique of molecular quantum chemistry and from quantum Monte Carlo calculations. The systems studied are isomers of the water hexamer cluster, the crystal structures Ih, II, XV, and VIII of ice, and two clusters extracted from ice VIII. For the binding energies of these systems, we use the machine-learning technique of Gaussian Approximation Potentials to correct successively for 1-body and 2-body errors of the DFT approximations. We find that even after correction for these errors, substantial beyond-2-body errors remain. The characteristics of the 2-body and beyond-2-body errors of PBE are completely different from those of BLYP, but the errors of both approximations disfavor the close approach of non-hydrogen-bonded monomers. We note the possible relevance of our findings to the understanding of liquid water.

Uncertainties in the cluster-cluster correlation function

NASA Astrophysics Data System (ADS)

Ling, E. N.; Frenk, C. S.; Barrow, J. D.

1986-12-01

The bootstrap resampling technique is applied to estimate sampling errors and significance levels of the two-point correlation functions determined for a subset of the CfA redshift survey of galaxies and a redshift sample of 104 Abell clusters. The angular correlation function for a sample of 1664 Abell clusters is also calculated. The standard errors in xi(r) for the Abell data are found to be considerably larger than quoted 'Poisson errors'. The best estimate for the ratio of the correlation length of Abell clusters (richness class R greater than or equal to 1, distance class D less than or equal to 4) to that of CfA galaxies is 4.2 + 1.4 or - 1.0 (68 percentile error). The enhancement of cluster clustering over galaxy clustering is statistically significant in the presence of resampling errors. The uncertainties found do not include the effects of possible systematic biases in the galaxy and cluster catalogs and could be regarded as lower bounds on the true uncertainty range.

The cluster-cluster correlation function. [of galaxies

NASA Technical Reports Server (NTRS)

Postman, M.; Geller, M. J.; Huchra, J. P.

1986-01-01

The clustering properties of the Abell and Zwicky cluster catalogs are studied using the two-point angular and spatial correlation functions. The catalogs are divided into eight subsamples to determine the dependence of the correlation function on distance, richness, and the method of cluster identification. It is found that the Corona Borealis supercluster contributes significant power to the spatial correlation function to the Abell cluster sample with distance class of four or less. The distance-limited catalog of 152 Abell clusters, which is not greatly affected by a single system, has a spatial correlation function consistent with the power law Xi(r) = 300r exp -1.8. In both the distance class four or less and distance-limited samples the signal in the spatial correlation function is a power law detectable out to 60/h Mpc. The amplitude of Xi(r) for clusters of richness class two is about three times that for richness class one clusters. The two-point spatial correlation function is sensitive to the use of estimated redshifts.

Local resonances in STM manipulation of chlorobenzene on Si(111)-7×7: performance of different cluster models and density functionals

NASA Astrophysics Data System (ADS)

Utecht, Manuel; Klamroth, Tillmann

2018-07-01

Hot localised charge carriers on the Si(111)-7×7 surface are modelled by small charged clusters. Such resonances induce non-local desorption, i.e. more than 10 nm away from the injection site, of chlorobenzene in scanning tunnelling microscope experiments. We used such a cluster model to characterise resonance localisation and vibrational activation for positive and negative resonances recently. In this work, we investigate to which extent the model depends on details of the used cluster or quantum chemistry methods and try to identify the smallest possible cluster suitable for a description of the neutral surface and the ion resonances. Furthermore, a detailed analysis for different chemisorption orientations is performed. While some properties, as estimates of the resonance energy or absolute values for atomic changes, show such a dependency, the main findings are very robust with respect to changes in the model and/or the chemisorption geometry.

Chemistry for Potters.

ERIC Educational Resources Information Center

Denio, Allen A.

1980-01-01

Relates pottery making to chemistry by providing chemical information about clay, its origin, composition, properties, and changes that occur during firing; also describes glaze compositions, examples of redox chemistry, salt glazing, crystalline glazes, and problems in toxicity. (CS)

Electron-Rich Carboranes. Studies of a Stereochemically Novel System, (CH3)4C4B7H9, and 11-Vertex Arachno Cluster.

DTIC Science & Technology

1981-01-01

FINSTER , R N GRIMES NOGOIR-75C-0305 UNCLASSIFIED TR-37 NL EOMEEEhE OFFICE OF NAVAL RESEARCH CONTRACT NO. i14.-7-C-31 q,4 TECHNICAL REPORT NO. 37L" 0...Electron-Rich Carboranes. Studies of a Stereochemically Novel System, (CH") 4C4 BH 9 , an 11-Vertex Arachno Cluster. .) David C./ Finster aad Russell N...System, (CH3 )4C4B7H9 , an l-Vertex Arachno Cluster 1 David C. Finster and Russell N. Grimes* Contribution from the Department of Chemistry University of

Benchmark CCSD(T) and DFT study of binding energies in Be7 - 12: in search of reliable DFT functional for beryllium clusters

NASA Astrophysics Data System (ADS)

Labanc, Daniel; Šulka, Martin; Pitoňák, Michal; Černušák, Ivan; Urban, Miroslav; Neogrády, Pavel

2018-05-01

We present a computational study of the stability of small homonuclear beryllium clusters Be7 - 12 in singlet electronic states. Our predictions are based on highly correlated CCSD(T) coupled cluster calculations. Basis set convergence towards the complete basis set limit as well as the role of the 1s core electron correlation are carefully examined. Our CCSD(T) data for binding energies of Be7 - 12 clusters serve as a benchmark for performance assessment of several density functional theory (DFT) methods frequently used in beryllium cluster chemistry. We observe that, from Be10 clusters on, the deviation from CCSD(T) benchmarks is stable with respect to size, and fluctuating within 0.02 eV error bar for most examined functionals. This opens up the possibility of scaling the DFT binding energies for large Be clusters using CCSD(T) benchmark values for smaller clusters. We also tried to find analogies between the performance of DFT functionals for Be clusters and for the valence-isoelectronic Mg clusters investigated recently in Truhlar's group. We conclude that it is difficult to find DFT functionals that perform reasonably well for both beryllium and magnesium clusters. Out of 12 functionals examined, only the M06-2X functional gives reasonably accurate and balanced binding energies for both Be and Mg clusters.

Compact dry chemistry instruments.

PubMed

Terashima, K; Tatsumi, N

1999-01-01

Compact dry chemistry instruments are designed for use in point-of-care-testing (POCT). These instruments have a number of advantages, including light weight, compactness, ease of operation, and the ability to provide accurate results in a short time with a very small sample volume. On the other hand, reagent costs are high compared to liquid method. Moreover, differences in accuracy have been found between dry chemistry and the liquid method in external quality assessment scheme. This report examines reagent costs and shows how the total running costs associated with dry chemistry are actually lower than those associated with the liquid method. This report also describes methods for minimizing differences in accuracy between dry chemistry and the liquid method. Use of these measures is expected to increase the effectiveness of compact dry chemistry instruments in POCT applications.

Are clusters of dietary patterns and cluster membership stable over time? Results of a longitudinal cluster analysis study.

PubMed

Walthouwer, Michel Jean Louis; Oenema, Anke; Soetens, Katja; Lechner, Lilian; de Vries, Hein

2014-11-01

Developing nutrition education interventions based on clusters of dietary patterns can only be done adequately when it is clear if distinctive clusters of dietary patterns can be derived and reproduced over time, if cluster membership is stable, and if it is predictable which type of people belong to a certain cluster. Hence, this study aimed to: (1) identify clusters of dietary patterns among Dutch adults, (2) test the reproducibility of these clusters and stability of cluster membership over time, and (3) identify sociodemographic predictors of cluster membership and cluster transition. This study had a longitudinal design with online measurements at baseline (N=483) and 6 months follow-up (N=379). Dietary intake was assessed with a validated food frequency questionnaire. A hierarchical cluster analysis was performed, followed by a K-means cluster analysis. Multinomial logistic regression analyses were conducted to identify the sociodemographic predictors of cluster membership and cluster transition. At baseline and follow-up, a comparable three-cluster solution was derived, distinguishing a healthy, moderately healthy, and unhealthy dietary pattern. Male and lower educated participants were significantly more likely to have a less healthy dietary pattern. Further, 251 (66.2%) participants remained in the same cluster, 45 (11.9%) participants changed to an unhealthier cluster, and 83 (21.9%) participants shifted to a healthier cluster. Men and people living alone were significantly more likely to shift toward a less healthy dietary pattern. Distinctive clusters of dietary patterns can be derived. Yet, cluster membership is unstable and only few sociodemographic factors were associated with cluster membership and cluster transition. These findings imply that clusters based on dietary intake may not be suitable as a basis for nutrition education interventions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Measurement of the spectral signature of small carbon clusters at near and far infrared wavelengths

NASA Technical Reports Server (NTRS)

Tarter, J.; Saykally, R.

1991-01-01

A significant percentage of the carbon inventory of the circumstellar and interstellar media may be in the form of large refractory molecules (or small grains) referred to as carbon clusters. At the small end, uneven numbers of carbon atoms seem to be preferred, whereas above 12 atoms, clusters containing an even number of carbon atoms appear to be preferred in laboratory chemistry. In the lab, the cluster C-60 appears to be a particularly stable form and has been nicknamed Bucky Balls because of its resemblance to a soccer ball and to geodesic domes designed by Buckminster Fuller. In order to investigate the prevalence of these clusters, and their relationship to the polycyclic aromatic hydrocarbons (PAHs) that have become the newest focus of IR astronomy, it is necessary to determine the spectroscopic characteristics of these clusters at near and far infrared wavelengths. Described here is the construction of a near to far IR laser magnetic resonance spectrometer that has been built at the University of California Berkeley in order to detect and characterize these spectra. The equipment produces carbon clusters by laser evaporation of a graphitic target. The clusters are then cooled in a supersonic expansion beam in order to simulate conditions in the interstellar medium (ISM). The expansion beam feeds into the spectrometer chamber and permits concentrations of clusters sufficiently high as to permit ultra-high resolution spectroscopy at near and far IR wavelengths. The first successful demonstration of this apparatus occurred last year when the laboratory studies permitted the observational detection of C-5 in the stellar outflow surrounding IRC+10216 in the near-IR. Current efforts focus on reducing the temperature of the supersonic expansion beam that transport the C clusters evaporated from a graphite target into the spectrometer down to temperatures as low as 1 K.

Theoretical research program to predict the properties of molecules and clusters containing transition metal atoms

NASA Technical Reports Server (NTRS)

Walch, S.

1984-01-01

The primary focus of this research has been the theoretical study of transition metal (TM) chemistry. A major goal of this work is to provide reliable information about the interaction of H atoms with iron metal. This information is needed to understand the effect of H atoms on the processes of embrittlement and crack propagation in iron. The method in the iron hydrogen studies is the cluster method in which the bulk metal is modelled by a finite number of iron atoms. There are several difficulties in the application of this approach to the hydrogen iron system. First the nature of TM-TM and TM-H bonding for even diatomic molecules was not well understood when these studies were started. Secondly relatively large iron clusters are needed to provide reasonable results.

Chemistry in Context: Analysis of Thematic Chemistry Videos Available Online

ERIC Educational Resources Information Center

Christensson, Camilla; Sjöström, Jesper

2014-01-01

United Nations declared 2011 to be the International Year of Chemistry. The Swedish Chemical Society chose twelve themes, one for each month, to highlight the connection of chemistry with everyday life. Examples of themes were fashion, climate change, love, sports, communication, health issues, and food. From the themes various context-based…

Is coccolithophore distribution in the Mediterranean Sea related to seawater carbonate chemistry?

NASA Astrophysics Data System (ADS)

Oviedo, A. M.; Ziveri, P.; Álvarez, M.; Tanhua, T.

2014-02-01

The Mediterranean Sea is considered a "hot-spot" for climate change, being characterized by oligotrophic to ultra-oligotrophic waters and rapidly changing carbonate chemistry. Coccolithophores are considered a dominant phytoplankton group in these waters. As a marine calcifying organism they are expected to respond to the ongoing changes in seawater CO2 systems parameters. However, very few studies have covered the entire Mediterranean physiochemical gradients from the Strait of Gibraltar to the Eastern Mediterranean Levantine Basin. We provide here an updated state of knowledge of the coccolithophore distribution in the Mediterranean Sea and relate this to a broad set of in situ measured environmental variables. Samples were taken during the Meteor (M84/3) oceanographic cruise in April 2011, between 0-100 m water depth from 28 stations. Total diatom, dinoflagellate and silicoflagellate cell concentrations are also presented. Our results highlight the importance of seawater carbonate chemistry, especially CO32-, in unraveling the distribution of heterococcolithophores, the most abundant coccolithophore life phase. Holo- and hetero-coccolithophores respond differently to environmental factors. For instance, changes in heterococcolithophore assemblages were best linked to the combination of [CO32-], pH, and salinity (ρ = 0.57) although salinity might be not functionally related to coccolithophore assemblage distribution. Holococcolithophores, on the other hand, were preferentially distributed and showed higher species diversity in oligotrophic areas (Best fit, ρ = 0.32 for nutrients), thriving in nutrient depleted waters. Clustering of heterococcolithophores revealed three groups of species sharing more than 65% similarities. These clusters could be assigned to the eastern and western basins, and deeper layers (below 50 m), respectively. In addition, the species Gephyrocapsa oceanica, G. muellerae and Emiliania huxleyi morphotype B/C are spatially distributed

Chemistry of americium

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

Schulz, W.W.

1976-01-01

Essential features of the descriptive chemistry of americium are reviewed. Chapter titles are: discovery, atomic and nuclear properties, collateral reading, production and uses, chemistry in aqueous solution, metal, alloys, and compounds, and, recovery, separation, purification. Author and subject indexes are included. (JCB)

National Chemistry Teacher Safety Survey

NASA Astrophysics Data System (ADS)

Plohocki, Barbra A.

This study evaluated the status of secondary school instructional chemistry laboratory safety using a survey instrument which focused on Teacher background Information, Laboratory Safety Equipment, Facility Safety, General Safety, and a Safety Content Knowledge Survey. A fifty question survey instrument based on recent research and questions developed by the researcher was mailed to 500 secondary school chemistry teachers who participated in the 1993 one-week Woodrow Wilson National Fellowship Foundation Chemistry Institute conducted at Princeton University, New Jersey. The data received from 303 respondents was analyzed by t tests and Analysis of Variance (ANOVA). The level of significance for the study was set at ~\\ <.05. There was no significant mean difference in test performance on the Safety Content Knowledge Survey and secondary school chemistry teachers who have had undergraduate and/or graduate safety training and those who have not had undergraduate and/or graduate safety training. Secondary school chemistry teachers who attended school district sponsored safety inservices did not score higher on the Safety Content Knowledge Survey than teachers who did not attend school district sponsored safety inservice sessions. The type of school district (urban, suburban, or rural) had no significant correlation to the type of laboratory safety equipment found in the instructional chemistry laboratory. The certification area (chemistry or other type of certificate which may or may not include chemistry) of the secondary school teacher had no significant correlation to the type of laboratory equipment found in the instructional chemistry laboratory. Overall, this study indicated a majority of secondary school chemistry teachers were interested in attending safety workshops applicable to chemistry safety. Throughout this research project, many teachers indicated they were not adequately instructed on the collegiate level in science safety and had to rely on common

Promoting Chemistry Learning through Undergraduate Work Experience in the Chemistry Lab: A Practical Approach

ERIC Educational Resources Information Center

Yu, Hong-Bin

2015-01-01

Hiring undergraduate lab assistants in chemistry departments is common in college. However, few studies have focused on promoting undergraduate chemistry learning and thinking skills through this work experience in chemistry teaching laboratories. This article discusses the strategy we implemented in the lab assistant program. The…

Derivatized gold clusters and antibody-gold cluster conjugates

DOEpatents

Hainfeld, James F.; Furuya, Frederic R.

1994-11-01

Antibody- or antibody fragment-gold cluster conjugates are shown wherein the conjugate size can be as small as 5.0 nm. Methods and reagents are disclosed in which antibodies, Fab' or F(ab').sub.2 fragments thereof are covalently bound to a stable cluster of gold atoms. The gold clusters may contain 6, 8, 9, 11, 13, 55 or 67 gold atoms in their inner core. The clusters may also contain radioactive gold. The antibody-cluster conjugates are useful in electron microscopy applications as well as in clinical applications that include imaging, diagnosis and therapy.

Undergraduate Chemistry Laboratory

ERIC Educational Resources Information Center

Bretz, Stacey Lowery; Fay, Michael; Bruck, Laura B.; Towns, Marcy H.

2013-01-01

Forty chemistry faculty from American Chemical Society-approved departments were interviewed to determine their goals for undergraduate chemistry laboratory. Faculty were stratified by type of institution, departmental success with regard to National Science Foundation funding for laboratory reform, and level of laboratory course. Interview…

Cooking with Chemistry.

ERIC Educational Resources Information Center

Grosser, Arthur E.

1984-01-01

Suggests chemistry of cooking and analysis of culinary recipes as subject matter for introducing chemistry to an audience, especially to individuals with neutral or negative attitudes toward science. Includes sample recipes and experiments and a table listing scientific topics with related cooking examples. (JN)

Chemistry from Issues.

ERIC Educational Resources Information Center

Harding, Jan; Donaldson, Jim

1986-01-01

Describes the "Chemistry from Issues" project at Chelsea College. Provides the background information, rationale, and overall structure of a proposed course about the importance of chemistry to common culture. Outlines one module about the British steel industry that has been taught at King's College. (TW)

The quadruple bottom line: the advantages of incorporating Green Chemistry into the undergraduate chemistry major

NASA Astrophysics Data System (ADS)

Bodner, George M.

2017-08-01

When the author first became involved with the Green Chemistry movement, he noted that his colleagues in industry who were involved in one of the ACS Green Chemistry Institute® industrial roundtables emphasized the take-home message they described as the "triple bottom line." They noted that introducing Green Chemistry in industrial settings had economic, social, and environmental benefits. As someone who first went to school at age 5, and has been "going to school" most days for 65 years, it was easy for the author to see why introducing Green Chemistry into academics had similar beneficial effects within the context of economic, social and environmental domains at the college/university level. He was prepared to understand why faculty who had taught traditional courses often saw the advantage of incorporating Green Chemistry into the courses they teach. What was not as obvious is why students who were encountering chemistry for the first time were often equally passionate about the Green Chemistry movement. Recent attention has been paid, however, to a model that brings clarity to the hitherto vague term of "relevance" that might explain why integrating Green Chemistry into the undergraduate chemistry classroom can achieve a "quadruple bottom-line" for students because of potentially positive effects of adding a domain of "relevance" to the existing economic, social, and environmental domains.

Solid state, thermal synthesis of site-specific protein-boron cluster conjugates and their physicochemical and biochemical properties.

PubMed

Goszczyński, Tomasz M; Kowalski, Konrad; Leśnikowski, Zbigniew J; Boratyński, Janusz

2015-02-01

Boron clusters represent a vast family of boron-rich compounds with extraordinary properties that provide the opportunity of exploitation in different areas of chemistry and biology. In addition, boron clusters are clinically used in boron neutron capture therapy (BNCT) of tumors. In this paper, a novel, in solid state (solvent free), thermal method for protein modification with boron clusters has been proposed. The method is based on a cyclic ether ring opening in oxonium adduct of cyclic ether and a boron cluster with nucleophilic centers of the protein. Lysozyme was used as the model protein, and the physicochemical and biological properties of the obtained conjugates were characterized. The main residues of modification were identified as arginine-128 and threonine-51. No significant changes in the secondary or tertiary structures of the protein after tethering of the boron cluster were found using mass spectrometry and circular dichroism measurements. However, some changes in the intermolecular interactions and hydrodynamic and catalytic properties were observed. To the best of our knowledge, we have described the first example of an application of cyclic ether ring opening in the oxonium adducts of a boron cluster for protein modification. In addition, a distinctive feature of the proposed approach is performing the reaction in solid state and at elevated temperature. The proposed methodology provides a new route to protein modification with boron clusters and extends the range of innovative molecules available for biological and medical testing. Copyright © 2014 Elsevier B.V. All rights reserved.

The Journal of Kitchen Chemistry: A Tool for Instructing the Preparation of a Chemistry Journal Article

ERIC Educational Resources Information Center

Meyers, Jonathan K.; LeBaron, Tyler W.; Collins, David C.

2014-01-01

Writing assignments are typically incorporated into chemistry courses in an attempt to enhance the learning of chemistry or to teach technical writing to chemistry majors. This work addresses the development of chemistry-major writing skills by focusing on the rigorous guidelines and conventions associated with the preparation of a journal…

Analysis of NFU-1 metallocofactor binding-site substitutions-impacts on iron-sulfur cluster coordination and protein structure and function.

PubMed

Wesley, Nathaniel A; Wachnowsky, Christine; Fidai, Insiya; Cowan, J A

2017-11-01

Iron-sulfur (Fe/S) clusters are ancient prosthetic groups found in numerous metalloproteins and are conserved across all kingdoms of life due to their diverse, yet essential functional roles. Genetic mutations to a specific subset of mitochondrial Fe/S cluster delivery proteins are broadly categorized as disease-related under multiple mitochondrial dysfunction syndrome (MMDS), with symptoms indicative of a general failure of the metabolic system. Multiple mitochondrial dysfunction syndrome 1 (MMDS1) arises as a result of the missense mutation in NFU1, an Fe/S cluster scaffold protein, which substitutes a glycine near the Fe/S cluster-binding pocket to a cysteine (p.Gly208Cys). This substitution has been shown to promote protein dimerization such that cluster delivery to NFU1 is blocked, preventing downstream cluster trafficking. However, the possibility of this additional cysteine, located adjacent to the cluster-binding site, serving as an Fe/S cluster ligand has not yet been explored. To fully understand the consequences of this Gly208Cys replacement, complementary substitutions at the Fe/S cluster-binding pocket for native and Gly208Cys NFU1 were made, along with six other variants. Herein, we report the results of an investigation on the effect of these substitutions on both cluster coordination and NFU1 structure and function. The data suggest that the G208C substitution does not contribute to cluster binding. Rather, replacement of the glycine at position 208 changes the oligomerization state as a result of global structural alterations that result in the downstream effects manifest as MMDS1, but does not perturb the coordination chemistry of the Fe-S cluster. © 2017 Federation of European Biochemical Societies.

Diametrical clustering for identifying anti-correlated gene clusters.

PubMed

Dhillon, Inderjit S; Marcotte, Edward M; Roshan, Usman

2003-09-01

Clustering genes based upon their expression patterns allows us to predict gene function. Most existing clustering algorithms cluster genes together when their expression patterns show high positive correlation. However, it has been observed that genes whose expression patterns are strongly anti-correlated can also be functionally similar. Biologically, this is not unintuitive-genes responding to the same stimuli, regardless of the nature of the response, are more likely to operate in the same pathways. We present a new diametrical clustering algorithm that explicitly identifies anti-correlated clusters of genes. Our algorithm proceeds by iteratively (i). re-partitioning the genes and (ii). computing the dominant singular vector of each gene cluster; each singular vector serving as the prototype of a 'diametric' cluster. We empirically show the effectiveness of the algorithm in identifying diametrical or anti-correlated clusters. Testing the algorithm on yeast cell cycle data, fibroblast gene expression data, and DNA microarray data from yeast mutants reveals that opposed cellular pathways can be discovered with this method. We present systems whose mRNA expression patterns, and likely their functions, oppose the yeast ribosome and proteosome, along with evidence for the inverse transcriptional regulation of a number of cellular systems.

Green Chemistry: Progress and Barriers

NASA Astrophysics Data System (ADS)

Green, Sarah A.

2016-10-01

Green chemistry can advance both the health of the environment and the primary objectives of the chemical enterprise: to understand the behavior of chemical substances and to use that knowledge to make useful substances. We expect chemical research and manufacturing to be done in a manner that preserves the health and safety of workers; green chemistry extends that expectation to encompass the health and safety of the planet. While green chemistry may currently be treated as an independent branch of research, it should, like safety, eventually become integral to all chemistry activities. While enormous progress has been made in shifting from "brown" to green chemistry, much more effort is needed to effect a sustainable economy. Implementation of new, greener paradigms in chemistry is slow because of lack of knowledge, ends-justify-the-means thinking, systems inertia, and lack of financial or policy incentives.

Synthesis, characterization and optical properties of an amino-functionalized gold thiolate cluster: Au10(SPh-pNH2)10.

PubMed

Lavenn, Christophe; Albrieux, Florian; Tuel, Alain; Demessence, Aude

2014-03-15

Research interest in ultra small gold thiolate clusters has been rising in recent years for the challenges they offer to bring together properties of nanoscience and well-defined materials from molecular chemistry. Here, a new atomically well-defined Au10 gold nanocluster surrounded by ten 4-aminothiophenolate ligands is reported. Its synthesis followed the similar conditions reported for the elaboration of Au144(SR)60, but because the reactivity of thiophenol ligands is different from alkanethiol derivates, smaller Au10 clusters were formed. Different techniques, such as ESI-MS, elemental analysis, XRD, TGA, XPS and UV-vis-NIR experiments, have been carried out to determine the Au10(SPh-pNH2)10 formula. Photoemission experiment has been done and reveals that the Au10 clusters are weakly luminescent as opposed to the amino-based ultra-small gold clusters. This observation points out that the emission of gold thiolate clusters is highly dependent on both the structure of the gold core and the type of the ligands at the surface. In addition, ultra-small amino-functionalized clusters offer the opportunity for extended work on self-assembling networks or deposition on substrates for nanotechnologies or catalytic applications. Copyright © 2013 Elsevier Inc. All rights reserved.

Life's Biological Chemistry: A Destiny or Destination Starting from Prebiotic Chemistry?

PubMed

Krishnamurthy, Ramanarayanan

2018-06-05

Research into understanding the origins -and evolution- of life has long been dominated by the concept of taking clues from extant biology and extrapolating its molecules and pathways backwards in time. This approach has also guided the search for solutions to the problem of how contemporary biomolecules would have arisen directly from prebiotic chemistry on early earth. However, the continuing difficulties in finding universally convincing solutions in connecting prebiotic chemistry to biological chemistry should give us pause, and prompt us to rethink this concept of treating extant life's chemical processes as the sole end goal and, therefore, focusing only -and implicitly- on the respective extant chemical building blocks. Rather, it may be worthwhile "to set aside the goal" and begin with what would have been plausible prebiotic reaction mixtures (which may have no obvious or direct connection to life's chemical building blocks and processes) - and allow their chemistries and interactions, under different geochemical constraints, to guide and illuminate as to what processes and systems can emerge. Such a conceptual approach gives rise to the prospect that chemistry of life-as-we-know-it is not the only result (not a "destiny"), but one that has emerged among many potential possibilities (a "destination"). This postulate, in turn, could impact the way we think about chemical signatures and criteria used in the search for alternative and extraterrestrial "life". As a bonus, we may discover the chemistries and pathways naturally that led to the emergence of life as we know it. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Supramolecular analytical chemistry.

PubMed

Anslyn, Eric V

2007-02-02

A large fraction of the field of supramolecular chemistry has focused in previous decades upon the study and use of synthetic receptors as a means of mimicking natural receptors. Recently, the demand for synthetic receptors is rapidly increasing within the analytical sciences. These classes of receptors are finding uses in simple indicator chemistry, cellular imaging, and enantiomeric excess analysis, while also being involved in various truly practical assays of bodily fluids. Moreover, one of the most promising areas for the use of synthetic receptors is in the arena of differential sensing. Although many synthetic receptors have been shown to yield exquisite selectivities, in general, this class of receptor suffers from cross-reactivities. Yet, cross-reactivity is an attribute that is crucial to the success of differential sensing schemes. Therefore, both selective and nonselective synthetic receptors are finding uses in analytical applications. Hence, a field of chemistry that herein is entitled "Supramolecular Analytical Chemistry" is emerging, and is predicted to undergo increasingly rapid growth in the near future.

The HectoMAP Cluster Survey. II. X-Ray Clusters

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

Sohn, Jubee; Chon, Gayoung; Bohringer, Hans

Here, we apply a friends-of-friends algorithm to the HectoMAP redshift survey and cross-identify associated X-ray emission in the ROSAT All-Sky Survey data (RASS). The resulting flux-limited catalog of X-ray cluster surveys is complete to a limiting flux of ~3 × 10 –13 erg s –1 cm –2 and includes 15 clusters (7 newly discovered) with redshifts z ≤ 0.4. HectoMAP is a dense survey (~1200 galaxies deg –2) that provides ~50 members (median) in each X-ray cluster. We provide redshifts for the 1036 cluster members. Subaru/Hyper Suprime-Cam imaging covers three of the X-ray systems and confirms that they are impressivemore » clusters. The HectoMAP X-ray clusters have an L X–σ cl scaling relation similar to that of known massive X-ray clusters. The HectoMAP X-ray cluster sample predicts ~12,000 ± 3000 detectable X-ray clusters in RASS to the limiting flux, comparable with previous estimates.« less

The HectoMAP Cluster Survey. II. X-Ray Clusters

DOE PAGES

Sohn, Jubee; Chon, Gayoung; Bohringer, Hans; ...

2018-03-10

Here, we apply a friends-of-friends algorithm to the HectoMAP redshift survey and cross-identify associated X-ray emission in the ROSAT All-Sky Survey data (RASS). The resulting flux-limited catalog of X-ray cluster surveys is complete to a limiting flux of ~3 × 10 –13 erg s –1 cm –2 and includes 15 clusters (7 newly discovered) with redshifts z ≤ 0.4. HectoMAP is a dense survey (~1200 galaxies deg –2) that provides ~50 members (median) in each X-ray cluster. We provide redshifts for the 1036 cluster members. Subaru/Hyper Suprime-Cam imaging covers three of the X-ray systems and confirms that they are impressivemore » clusters. The HectoMAP X-ray clusters have an L X–σ cl scaling relation similar to that of known massive X-ray clusters. The HectoMAP X-ray cluster sample predicts ~12,000 ± 3000 detectable X-ray clusters in RASS to the limiting flux, comparable with previous estimates.« less

Chemistry for Whom? Gender Awareness in Teaching and Learning Chemistry

ERIC Educational Resources Information Center

Andersson, Kristina

2017-01-01

Marie Ståhl and Anita Hussénius have defined what discourses dominate national tests in chemistry for Grade 9 in Sweden by using feminist, critical didactic perspectives. This response seeks to expand the results in Ståhl and Hussénius's article "Chemistry inside an epistemological community box!--Discursive exclusions and inclusions in the…

Derivatized gold clusters and antibody-gold cluster conjugates

DOEpatents

Hainfeld, J.F.; Furuya, F.R.

1994-11-01

Antibody- or antibody fragment-gold cluster conjugates are shown wherein the conjugate size can be as small as 5.0 nm. Methods and reagents are disclosed in which antibodies, Fab' or F(ab')[sub 2] fragments are covalently bound to a stable cluster of gold atoms. The gold clusters may contain 6, 8, 9, 11, 13, 55 or 67 gold atoms in their inner core. The clusters may also contain radioactive gold. The antibody-cluster conjugates are useful in electron microscopy applications as well as in clinical applications that include imaging, diagnosis and therapy. 7 figs.

Young Star Cluster Found Aglow With Mysterious X-Ray Cloud

NASA Astrophysics Data System (ADS)

2002-12-01

A mysterious cloud of high-energy electrons enveloping a young cluster of stars has been discovered by astronomers using NASA's Chandra X-ray Observatory. These extremely high-energy particles could cause dramatic changes in the chemistry of the disks that will eventually form planets around stars in the cluster. Known as RCW 38, the star cluster covers a region about 5 light years across. It contains thousands of stars formed less than a million years ago and appears to be forming new stars even today. The crowded environment of a star cluster is thought to be conducive to the production of hot gas, but not high-energy particles. Such particles are typically produced by exploding stars, or in the strong magnetic fields around neutron stars or black holes, none of which is evident in RCW 38. "The RCW 38 observation doesn't agree with the conventional picture," said Scott Wolk of the Harvard-Smithsonian Center for Astrophysics in Cambridge, MA, lead author of an Astrophysical Journal Letters paper describing the Chandra observation. "The data show that somehow extremely high-energy electrons are being produced there, although it is not clear how." RCW 38 RCW 38 X-ray, Radio, Infrared Composite Electrons accelerated to energies of trillions of volts are required to account for the observed X-ray spectrum of the gas cloud surrounding the ensemble of stars, which shows an excess of high-energy X-rays. As these electrons move in the magnetic field that threads the cluster, they produce X-rays. One possible origin for the high-energy electrons is a previously undetected supernova that occurred in the cluster. Although direct evidence for the supernova could have faded away thousands of years ago, a shock wave or a rapidly rotating neutron star produced by the outburst could be acting in concert with stellar winds to produce the high-energy electrons. "Regardless of the origin of the energetic electrons," said Wolk, "their presence would change the chemistry of proto

Reaction-Map of Organic Chemistry

ERIC Educational Resources Information Center

Murov, Steven

2007-01-01

The Reaction-Map of Organic Chemistry lists all the most commonly studied reactions in organic chemistry on one page. The discussed Reaction-Map will act as another learning aide for the students, making the study of organic chemistry much easier.

Forensic Chemistry--A Symposium Collection.

ERIC Educational Resources Information Center

Journal of Chemical Education, 1985

1985-01-01

Presents a collection of articles to provide chemistry teachers with resource materials to add forensic chemistry units to their chemistry courses. Topics range from development of forensic science laboratory courses and mock-crime scenes to forensic serology and analytical techniques. (JN)

Effects of meteoric smoke particles on the D region ion chemistry

NASA Astrophysics Data System (ADS)

Baumann, Carsten; Rapp, Markus; Anttila, Milla; Kero, Antti; Verronen, Pekka T.

2015-12-01

This study focuses on meteor smoke particle (MSP) induced effects on the D region ion chemistry. Hereby, MSPs, represented with an 11 bin size distribution, have been included as an active component into the Sodankyä Ion and Neutral Chemistry model. By doing that, we model the diurnal variation of the negatively and positively charged MSPs as well as ions and the electron density under quiet ionospheric conditions. Two distinct points in time are studied in more detail, i.e., one for sunlit conditions (Solar zenith angle is 72°) and one for dark conditions (Solar zenith angle is 103°). We find nightly decrease of free electrons and negative ions, the positive ion density is enhanced at altitudes above 80 km and reduced below. During sunlit conditions the electron density is enhanced between 60 and 70 km altitude, while there is a reduction in negative and positive ions densities. In general, the MSP influence on the ion chemistry is caused by changes in the electron density. On the one hand, these changes occur due to nightly electron scavenging by MSPs resulting in a reduced electron-ion recombination. As a consequence positive ion density increase, especially water cluster ions are highly affected. On the other hand, the electron density is slightly increased during daytime by a MSP-related production due to solar radiation. Thus, more electrons attach to neutrals and short-lived negative ions increase in number density. The direct attachment of ions to MSPs is a minor process, but important for long living ions.

Turkish Chemistry Teachers' Views about Secondary School Chemistry Curriculum: A Perspective from Environmental Education

ERIC Educational Resources Information Center

Icoz, Omer Faruk

2015-01-01

Teachers' views about environmental education (EE) have been regarded as one of the most important concerns in education for sustainability. In secondary school chemistry curriculum, there are several subjects about EE embedded in the chemistry subjects in Turkey. This study explores three chemistry teachers' views about to what extent the…

Developing an online chemistry laboratory for non-chemistry majors

NASA Astrophysics Data System (ADS)

Poole, Jacqueline H.

Distance education, also known as online learning, is student-centered/self-directed educational opportunities. This style of learning is expanding in scope and is increasingly being accepted throughout the academic curriculum as a result of its flexibility for the student as well as the cost-effectiveness for the institution. Nevertheless, the introduction of online science courses including chemistry and physics have lagged behind due to the challenge of re-creation of the hands-on laboratory learning experience. This dissertation looks at the effectiveness of the design of a series of chemistry laboratory experiments for possible online delivery that provide students with simulated hands-on experiences. One class of college Chemistry 101 students conducted chemistry experiments inside and outside of the physical laboratory using instructions on Blackboard and Late Nite Labs(TM). Learning outcomes measured by (a) pretests, (b) written laboratory reports, (c) posttest assessments, (d) student reactions as determined by a questionnaire, and (e) a focus group interview were utilized to compare both types of laboratory experiences. The research findings indicated learning outcomes achieved by students outside of the traditional physical laboratory were statistically greater than the equivalent face-to-face instruction in the traditional laboratory. Evidence from student reactions comparing both types of laboratory formats (online and traditional face-to-face) indicated student preference for the online laboratory format. The results are an initial contribution to the design of a complete sequence of experiments that can be performed independently by online students outside of the traditional face-to-face laboratory that will satisfy the laboratory requirement for the two-semester college Chemistry 101 laboratory course.

Chemistry and Biology

ERIC Educational Resources Information Center

Wigston, David L.

1970-01-01

Discusses the relationship between chemisty and biology in the science curriculum. Points out the differences in perception of the disciplines, which the physical scientists favoring reductionism. Suggests that biology departments offer a special course for chemistry students, just as the chemistry departments have done for biology students.…

A nonparametric clustering technique which estimates the number of clusters

NASA Technical Reports Server (NTRS)

Ramey, D. B.

1983-01-01

In applications of cluster analysis, one usually needs to determine the number of clusters, K, and the assignment of observations to each cluster. A clustering technique based on recursive application of a multivariate test of bimodality which automatically estimates both K and the cluster assignments is presented.

Understanding the Impact of a General Chemistry Course on Students' Transition to Organic Chemistry

ERIC Educational Resources Information Center

Collins-Webb, Alexandra; Jeffery, Kathleen A.; Sweeder, Ryan D.

2016-01-01

The move from general chemistry to organic chemistry can be a challenge for students as it often involves a transition from quantitatively-oriented to mechanistically-oriented thinking. This study found that the design of the general chemistry course can change the student experience of this transition as assessed by a reflective survey. The…

42 CFR 493.839 - Condition: Chemistry.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 42 Public Health 5 2010-10-01 2010-10-01 false Condition: Chemistry. 493.839 Section 493.839... These Tests § 493.839 Condition: Chemistry. The specialty of chemistry includes for the purposes of proficiency testing the subspecialties of routine chemistry, endocrinology, and toxicology. ...

42 CFR 493.839 - Condition: Chemistry.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 42 Public Health 5 2014-10-01 2014-10-01 false Condition: Chemistry. 493.839 Section 493.839... These Tests § 493.839 Condition: Chemistry. The specialty of chemistry includes for the purposes of proficiency testing the subspecialties of routine chemistry, endocrinology, and toxicology. ...

42 CFR 493.839 - Condition: Chemistry.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 42 Public Health 5 2013-10-01 2013-10-01 false Condition: Chemistry. 493.839 Section 493.839... These Tests § 493.839 Condition: Chemistry. The specialty of chemistry includes for the purposes of proficiency testing the subspecialties of routine chemistry, endocrinology, and toxicology. ...

42 CFR 493.839 - Condition: Chemistry.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 42 Public Health 5 2011-10-01 2011-10-01 false Condition: Chemistry. 493.839 Section 493.839... These Tests § 493.839 Condition: Chemistry. The specialty of chemistry includes for the purposes of proficiency testing the subspecialties of routine chemistry, endocrinology, and toxicology. ...

42 CFR 493.839 - Condition: Chemistry.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 42 Public Health 5 2012-10-01 2012-10-01 false Condition: Chemistry. 493.839 Section 493.839... These Tests § 493.839 Condition: Chemistry. The specialty of chemistry includes for the purposes of proficiency testing the subspecialties of routine chemistry, endocrinology, and toxicology. ...

Virtually going green: The role of quantum computational chemistry in reducing pollution and toxicity in chemistry

NASA Astrophysics Data System (ADS)

Stevens, Jonathan

2017-07-01

Continuing advances in computational chemistry has permitted quantum mechanical calculation to assist in research in green chemistry and to contribute to the greening of chemical practice. Presented here are recent examples illustrating the contribution of computational quantum chemistry to green chemistry, including the possibility of using computation as a green alternative to experiments, but also illustrating contributions to greener catalysis and the search for greener solvents. Examples of applications of computation to ambitious projects for green synthetic chemistry using carbon dioxide are also presented.

A machine learning approach to graph-theoretical cluster expansions of the energy of adsorbate layers

NASA Astrophysics Data System (ADS)

Vignola, Emanuele; Steinmann, Stephan N.; Vandegehuchte, Bart D.; Curulla, Daniel; Stamatakis, Michail; Sautet, Philippe

2017-08-01

The accurate description of the energy of adsorbate layers is crucial for the understanding of chemistry at interfaces. For heterogeneous catalysis, not only the interaction of the adsorbate with the surface but also the adsorbate-adsorbate lateral interactions significantly affect the activation energies of reactions. Modeling the interactions of the adsorbates with the catalyst surface and with each other can be efficiently achieved in the cluster expansion Hamiltonian formalism, which has recently been implemented in a graph-theoretical kinetic Monte Carlo (kMC) scheme to describe multi-dentate species. Automating the development of the cluster expansion Hamiltonians for catalytic systems is challenging and requires the mapping of adsorbate configurations for extended adsorbates onto a graphical lattice. The current work adopts machine learning methods to reach this goal. Clusters are automatically detected based on formalized, but intuitive chemical concepts. The corresponding energy coefficients for the cluster expansion are calculated by an inversion scheme. The potential of this method is demonstrated for the example of ethylene adsorption on Pd(111), for which we propose several expansions, depending on the graphical lattice. It turns out that for this system, the best description is obtained as a combination of single molecule patterns and a few coupling terms accounting for lateral interactions.

Electrochemical applications. How click chemistry brought biomimetic models to the next level: electrocatalysis under controlled rate of electron transfer.

PubMed

Decréau, Richard A; Collman, James P; Hosseini, Ali

2010-04-01

This tutorial review discusses the immobilization of alkyne-terminated cytochrome c oxidase models on azide-functionalized self-assembled monolayers (SAM) coated gold electrodes that was made possible by click chemistry. The rate of electron delivery from the electrode to the model could be tuned by changing the nature of the SAM. Biologically relevant electron transfer rates (2-4 s(-1)) were obtained on slow SAMs allowing the model to turn over catalytically under steady-state conditions. Hence, click chemistry was a crucial tool to demonstrate, through electrocatalytic studies: (1) the role played by several features present in the distal side of the model, such as the Cu(B)-Tyr244 pair, the distal pocket, and the stabilizing role of a distal water cluster; (2) the reversible inhibition of O(2) reduction by H(2)S.

Galaxy Clusters

NASA Astrophysics Data System (ADS)

Miller, Christopher J. Miller

2012-03-01

There are many examples of clustering in astronomy. Stars in our own galaxy are often seen as being gravitationally bound into tight globular or open clusters. The Solar System's Trojan asteroids cluster at the gravitational Langrangian in front of Jupiter’s orbit. On the largest of scales, we find gravitationally bound clusters of galaxies, the Virgo cluster (in the constellation of Virgo at a distance of ˜50 million light years) being a prime nearby example. The Virgo cluster subtends an angle of nearly 8◦ on the sky and is known to contain over a thousand member galaxies. Galaxy clusters play an important role in our understanding of theUniverse. Clusters exist at peaks in the three-dimensional large-scale matter density field. Their sky (2D) locations are easy to detect in astronomical imaging data and their mean galaxy redshifts (redshift is related to the third spatial dimension: distance) are often better (spectroscopically) and cheaper (photometrically) when compared with the entire galaxy population in large sky surveys. Photometric redshift (z) [Photometric techniques use the broad band filter magnitudes of a galaxy to estimate the redshift. Spectroscopic techniques use the galaxy spectra and emission/absorption line features to measure the redshift] determinations of galaxies within clusters are accurate to better than delta_z = 0.05 [7] and when studied as a cluster population, the central galaxies form a line in color-magnitude space (called the the E/S0 ridgeline and visible in Figure 16.3) that contains galaxies with similar stellar populations [15]. The shape of this E/S0 ridgeline enables astronomers to measure the cluster redshift to within delta_z = 0.01 [23]. The most accurate cluster redshift determinations come from spectroscopy of the member galaxies, where only a fraction of the members need to be spectroscopically observed [25,42] to get an accurate redshift to the whole system. If light traces mass in the Universe, then the locations

Chemistry Cube Game - Exploring Basic Principles of Chemistry by Turning Cubes.

PubMed

Müller, Markus T

2018-02-01

The Chemistry Cube Game invites students at secondary school level 1 and 2 to explore basic concepts of chemistry in a playful way, either as individuals or in teams. It consists of 15 different cubes, 9 cubes for different acids, their corresponding bases and precursors, and 6 cubes for different reducing and oxidising agents. The cubes can be rotated in those directions indicated. Each 'allowed' vertical or horizontal rotation of 90° stands for a chemical reaction or a physical transition. Two different games and playing modes are presented here: First, redox chemistry is introduced for the formation of salts from elementary metals and non-metals. Second, the speciation of acids and bases at different pH-values is shown. The cubes can be also used for games about environmental chemistry such as the carbon and sulphur cycle, covering the topic of acid rain, or the nitrogen cycle including ammoniac synthesis, nitrification and de-nitrification.

Science Update: Inorganic Chemistry.

ERIC Educational Resources Information Center

Rawls, Rebecca

1981-01-01

Describes areas of inorganic chemistry which have changed dramatically in the past year or two, including photochemistry, electrochemistry, organometallic complexes, inorganic reaction theory, and solid state chemistry. (DS)

Puzzling through General Chemistry: A Light-Hearted Approach to Engaging Students with Chemistry Content

ERIC Educational Resources Information Center

Boyd, Susan L.

2007-01-01

Several puzzles are designed to be used by chemistry students as learning tools and teach them basic chemical concepts. The topics of the puzzles are based on the chapters from Chemistry, The Central Science used in general chemistry course and the puzzles are in various forms like crosswords, word searches, number searches, puzzles based on…

Chemistry beyond positivism.

PubMed

Brandt, Werner W

2003-05-01

Chemistry is often thought to be quite factual, and therefore might be considered close to the "positivist" ideal of a value-free science. A closer look, however, reveals that the field is coupled to the invisible realm of values, meanings, and purpose in various ways, and chemists interact with that realm loosely and unevenly. Tacit knowledge is one important locus of such interactions. We are concerned in this essay with two questions. What is the nature of the knowledge when we are in the early stages of discovery? and In what ways does the hidden reality we are seeking affect our search for an understanding of it? The first question is partly answered by Polanyi's theory of tacit knowledge, while the second one leads us to realize the limitations of our language when discussing "reality"-or certain chemical experimental results. A strictly positivist approach is of little use, but so is the opposite, the complete disregard of facts. The contrast between positivism and non-formulable aspects of scientific reasoning amounts to a paradox that needs to be analyzed and can lead to a "connected" chemistry. This in turn resembles networks described by Schweber and is more concerned than the chemistry "as it is" with aspects such as the image of chemistry, the challenges chemists face as citizens, and chemistry in liberal education.

ClusterViz: A Cytoscape APP for Cluster Analysis of Biological Network.

PubMed

Wang, Jianxin; Zhong, Jiancheng; Chen, Gang; Li, Min; Wu, Fang-xiang; Pan, Yi

2015-01-01

Cluster analysis of biological networks is one of the most important approaches for identifying functional modules and predicting protein functions. Furthermore, visualization of clustering results is crucial to uncover the structure of biological networks. In this paper, ClusterViz, an APP of Cytoscape 3 for cluster analysis and visualization, has been developed. In order to reduce complexity and enable extendibility for ClusterViz, we designed the architecture of ClusterViz based on the framework of Open Services Gateway Initiative. According to the architecture, the implementation of ClusterViz is partitioned into three modules including interface of ClusterViz, clustering algorithms and visualization and export. ClusterViz fascinates the comparison of the results of different algorithms to do further related analysis. Three commonly used clustering algorithms, FAG-EC, EAGLE and MCODE, are included in the current version. Due to adopting the abstract interface of algorithms in module of the clustering algorithms, more clustering algorithms can be included for the future use. To illustrate usability of ClusterViz, we provided three examples with detailed steps from the important scientific articles, which show that our tool has helped several research teams do their research work on the mechanism of the biological networks.

Effective Chemistry Communication in Informal Environments

ERIC Educational Resources Information Center

National Academies Press, 2016

2016-01-01

Chemistry plays a critical role in daily life, impacting areas such as medicine and health, consumer products, energy production, the ecosystem, and many other areas. Communicating about chemistry in informal environments has the potential to raise public interest and understanding of chemistry around the world. However, the chemistry community…

GibbsCluster: unsupervised clustering and alignment of peptide sequences.

PubMed

Andreatta, Massimo; Alvarez, Bruno; Nielsen, Morten

2017-07-03

Receptor interactions with short linear peptide fragments (ligands) are at the base of many biological signaling processes. Conserved and information-rich amino acid patterns, commonly called sequence motifs, shape and regulate these interactions. Because of the properties of a receptor-ligand system or of the assay used to interrogate it, experimental data often contain multiple sequence motifs. GibbsCluster is a powerful tool for unsupervised motif discovery because it can simultaneously cluster and align peptide data. The GibbsCluster 2.0 presented here is an improved version incorporating insertion and deletions accounting for variations in motif length in the peptide input. In basic terms, the program takes as input a set of peptide sequences and clusters them into meaningful groups. It returns the optimal number of clusters it identified, together with the sequence alignment and sequence motif characterizing each cluster. Several parameters are available to customize cluster analysis, including adjustable penalties for small clusters and overlapping groups and a trash cluster to remove outliers. As an example application, we used the server to deconvolute multiple specificities in large-scale peptidome data generated by mass spectrometry. The server is available at http://www.cbs.dtu.dk/services/GibbsCluster-2.0. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Making Sense of the Arrow-Pushing Formalism among Chemistry Majors Enrolled in Organic Chemistry

ERIC Educational Resources Information Center

Ferguson, Robert; Bodner, George M.

2008-01-01

This paper reports results of a qualitative study of sixteen students enrolled in a second year organic chemistry course for chemistry and chemical engineering majors. The focus of the study was student use of the arrow-pushing formalism that plays a central role in both the teaching and practice of organic chemistry. The goal of the study was to…

Growing your green chemistry mindset

NASA Astrophysics Data System (ADS)

Kosmas, Steven

2017-08-01

The purpose of this article is not to delineate the steps to move across the continuum to being a greener chemist, but to analyse the cognitive processes involved in fostering a green chemistry growth mindset (GCGM) [Dweck C. (2006) Mindset: The New Psychology of Success. New York, NY: Ballatine]. The focus is on changing the mindset, which inevitably will lead to a more mindful approach to chemistry practices before the laboratory begins. A green chemistry fixed mindset (GCFM) is closed to making improvements, since the attitude is that the techniques and processes in the laboratory are already employing a green chemistry mindset [Dweck C. (2006) Mindset: The New Psychology of Success. New York, NY: Ballatine]. The problem with the GCFM is that it precludes the possibility of making improvements. However, the GCGM employs a continuous, intentional focus on the attitude towards green chemistry, with the ultimate goal being a change in chemistry practices that is greener. The focus of this article will be on the GCGM.

Is Fractal 1/f Scaling in Stream Chemistry Universal?

NASA Astrophysics Data System (ADS)

Hrachowitz, M.

2016-12-01

Stream water chemistry data from catchments worldwide suggest that catchments act as filters that transform white noise, i.e. random input signals such as in precipitation, into 1/fαnoise whose slope in a power spectrum typically ranges between -0.5>α> -1.5. This previously lead to the hypothesis that catchments act as fractal filters, i.e. a slope of α=-1 may be a universal and intrinsic property of catchments. That would have considerable implications on the predictability of stream water chemistry, as both, temporal short- and long-range interdependence control the system response. While short memories and thus flatter slopes with α closer to 0 indicate poor short term but good long-term predictability, steeper slopes (α <<-1) indicate the opposite. In fractal systems, i.e. α=-1, this therefore leads to inherent problems of predicting both, short and long-term response patterns. The hypothesis of catchments acting as fractal filters remains to be tested more profoundly. It is not yet clear, if observed inter-catchment variations in α need to be interpreted as noise in the signal or if the variations underlie a systematic pattern and can be explained by some characteristic of catchment function. Here we will test the hypothesis that the spectral slope of stream water chemistry is not necessarily α=-1 and that catchments therefore do not inherently act as fractal filters. Further, it will be tested if closer links between the variations in spectral slope and hydrological function of catchments can be identified. The combined data-analysis and modelling study uses hydrochemical data (i.e. Cl-) from a wide range of catchments worldwide. The study catchments are physically contrasting, from distinct climate zones, and with distinct landscapes and vegetation. To identify patterns in the variations of α, firstly the power spectra of observed stream chemistry are compared with physical catchment characteristics using methods such as cluster analysis. In a

Supplemental instruction in chemistry

NASA Astrophysics Data System (ADS)

Lundeberg, Mary A.

This study was designed to measure some effects of supplemental instruction in chemistry. Supplemental instruction is a peer-led cooperative learning program that encourages students to develop conceptual understanding by articulating both understandings and misconceptions in a think-aloud fashion. Supplemental instruction was offered three hours weekly outside of class and lab time for students in four classes of General Organic and Biological Chemistry. Over a two-year period 108 students volunteered to participate in this program; 45 students did not participate. As measured by final grades in chemistry and responses to a questionnaire, supplemental instruction was effective in increasing students' achievement in chemistry. Further research is needed to determine the in-depth effects of supplemental instruction on students' learning, problem solving, and self-esteem.

Expanding Radical SAM Chemistry by Using Radical Addition Reactions and SAM Analogues.

PubMed

Ji, Xinjian; Li, Yongzhen; Xie, Liqi; Lu, Haojie; Ding, Wei; Zhang, Qi

2016-09-19

Radical S-adenosyl-l-methionine (SAM) enzymes utilize a [4Fe-4S] cluster to bind SAM and reductively cleave its carbon-sulfur bond to produce a highly reactive 5'-deoxyadenosyl (dAdo) radical. In almost all cases, the dAdo radical abstracts a hydrogen atom from the substrates or from enzymes, thereby initiating a highly diverse array of reactions. Herein, we report a change of the dAdo radical-based chemistry from hydrogen abstraction to radical addition in the reaction of the radical SAM enzyme NosL. This change was achieved by using a substrate analogue containing an olefin moiety. We also showed that two SAM analogues containing different nucleoside functionalities initiate the radical-based reactions with high efficiencies. The radical adduct with the olefin produced in the reaction was found to undergo two divergent reactions, and the mechanistic insights into this process were investigated in detail. Our study demonstrates a promising strategy in expanding radical SAM chemistry, providing an effective way to access nucleoside-containing compounds by using radical SAM-dependent reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

42 CFR 493.929 - Chemistry.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 42 Public Health 5 2010-10-01 2010-10-01 false Chemistry. 493.929 Section 493.929 Public Health... Proficiency Testing Programs by Specialty and Subspecialty § 493.929 Chemistry. The subspecialties under the specialty of chemistry for which a proficiency testing program may offer proficiency testing are routine...

42 CFR 493.929 - Chemistry.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 42 Public Health 5 2012-10-01 2012-10-01 false Chemistry. 493.929 Section 493.929 Public Health... Proficiency Testing Programs by Specialty and Subspecialty § 493.929 Chemistry. The subspecialties under the specialty of chemistry for which a proficiency testing program may offer proficiency testing are routine...

42 CFR 493.929 - Chemistry.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 42 Public Health 5 2014-10-01 2014-10-01 false Chemistry. 493.929 Section 493.929 Public Health... Proficiency Testing Programs by Specialty and Subspecialty § 493.929 Chemistry. The subspecialties under the specialty of chemistry for which a proficiency testing program may offer proficiency testing are routine...

42 CFR 493.929 - Chemistry.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 42 Public Health 5 2013-10-01 2013-10-01 false Chemistry. 493.929 Section 493.929 Public Health... Proficiency Testing Programs by Specialty and Subspecialty § 493.929 Chemistry. The subspecialties under the specialty of chemistry for which a proficiency testing program may offer proficiency testing are routine...

42 CFR 493.929 - Chemistry.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 42 Public Health 5 2011-10-01 2011-10-01 false Chemistry. 493.929 Section 493.929 Public Health... Proficiency Testing Programs by Specialty and Subspecialty § 493.929 Chemistry. The subspecialties under the specialty of chemistry for which a proficiency testing program may offer proficiency testing are routine...

Opportunities in Chemistry.

ERIC Educational Resources Information Center

National Academy of Sciences - National Research Council, Washington, DC.

Because of the changes occurring in the chemical sciences, a new survey of chemistry and its intellectual and economic impact was clearly needed. This report presents a current assessment of the status of chemistry and of the future opportunities in the field. This analysis contains: (1) an introductory chapter (establishing the need for the…

Iridium Clusters Encapsulated in Carbon Nanospheres as Nanocatalysts for Methylation of (Bio)Alcohols.

PubMed

Liu, Qiang; Xu, Guoqiang; Wang, Zhendong; Liu, Xiaoran; Wang, Xicheng; Dong, Linlin; Mu, Xindong; Liu, Huizhou

2017-12-08

C-H methylation is an attractive chemical transformation for C-C bonds construction in organic chemistry, yet efficient methylation of readily available (bio)alcohols in water using methanol as sustainable C1 feedstock is limited. Herein, iridium nanocatalysts encapsulated in yolk-shell-structured mesoporous carbon nanospheres (Ir@YSMCNs) were synthesized for this transformation. Monodispersed Ir clusters (ca. 1.0 nm) were encapsulated in situ and spatially isolated within YSMCNs by a silica-assisted sol-gel emulsion strategy. A selection of (bio)alcohols (19 examples) was selectively methylated in aqueous phase with good-to-high yields over the developed Ir@YSMCNs. The improved catalytic efficiencies in terms of activity and selectivity together with the good stability and recyclability were contributable to the ultrasmall Ir clusters with oxidation chemical state as a consequence of the confinement effect of YSMCNs with interconnected nanostructures. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Perceptions of Chemistry: Why Is the Common Perception of Chemistry, the Most Visual of Sciences, So Distorted?

ERIC Educational Resources Information Center

Habraken, Clarisse L.

1996-01-01

Highlights the need to reinvigorate chemistry education by means of the visual-spatial approach, an approach wholly in conformance with the way modern chemistry is thought about and practiced. Discusses the changing world, multiple intelligences, imagery, chemistry's pictorial language, and perceptions in chemistry. Presents suggestions on how to…

Contribution from philosophy of chemistry to chemistry education: In a case of ionic liquids as technochemistry

NASA Astrophysics Data System (ADS)

Mudzakir, Ahmad; Hernani, Widhiyanti, Tuszie; Sudrajat, Devi Pratiwi

2017-08-01

Traditional chemistry education is commonly handing down of concepts, principles, and theories, such as mechanical properties, the relationship between structure and properties as well as chemical structure and chemical bonding theory, to students without engaging them in the processes of chemical inquiry. This practice leads to the lack of opportunity for the students to construct an appropriate understanding of these concepts, principles, and theories. Students are also rarely facilitated in modeling the structure and function of matter themselves. This situation shows that the philosophy of chemistry has not received as much attention from chemistry educators. The main idea of this paper is to embed philosophy of chemistry through the implementation of technochemistry in chemistry education. One of the most interesting and rapidly developing areas of modern chemistry, technologies and engineering is Ionic Liquids (ILs) as an emerging knowledge on technochemistry which can be applied to chemistry education. The developments between academic researchers and industrial developments in the ILs area are conducted in parallel. In order to overcome the existing problems of scientific development in chemistry education, the science and technology of ILs can be used for reconceptualizing the teaching and learning of chemistry to embrace the epistemology in chemistry. This study promises a potential contribution by philosophy of chemistry. The main objectives of this study are to develop: (i) a perspective based on philosophy of science considerations (rational reconstruction) in order to understand ionic liquids and (ii) teaching materials that can be used to enhance pre-service teacher's view of nature of science and technology (VNOST). The method used in the study is analytical-descriptive (elementarization), i.e. the first step in the model of educational reconstruction (MER). This study concludes that the development of the concepts and their applications of ionic

Membership determination of open clusters based on a spectral clustering method

NASA Astrophysics Data System (ADS)

Gao, Xin-Hua

2018-06-01

We present a spectral clustering (SC) method aimed at segregating reliable members of open clusters in multi-dimensional space. The SC method is a non-parametric clustering technique that performs cluster division using eigenvectors of the similarity matrix; no prior knowledge of the clusters is required. This method is more flexible in dealing with multi-dimensional data compared to other methods of membership determination. We use this method to segregate the cluster members of five open clusters (Hyades, Coma Ber, Pleiades, Praesepe, and NGC 188) in five-dimensional space; fairly clean cluster members are obtained. We find that the SC method can capture a small number of cluster members (weak signal) from a large number of field stars (heavy noise). Based on these cluster members, we compute the mean proper motions and distances for the Hyades, Coma Ber, Pleiades, and Praesepe clusters, and our results are in general quite consistent with the results derived by other authors. The test results indicate that the SC method is highly suitable for segregating cluster members of open clusters based on high-precision multi-dimensional astrometric data such as Gaia data.

Photoelectron Spectroscopy Study of [Ta2B6]-: a Hexagonal Bipyramdial Cluster

NASA Astrophysics Data System (ADS)

Jian, Tian; Li, Weili; Romanescu, Constantin; Wang, Lai-Sheng

2014-06-01

It has been a long-sought goal in cluster science to discover stable atomic clusters as building blocks for cluster-assembled nanomaterials, as exemplified by the fullerenes and their subsequent bulk syntheses.[1,2] Clusters have also been considered as models to understand bulk properties, providing a bridge between molecular and solid-state chemistry.[3] Herein we report a joint photoelectron spectroscopy and theoretical study on the [Ta2B6]- and [Ta2B6] clusters.[4] The photoelectron spectrum of [Ta2B6]- displays a simple spectral pattern and a large HOMO-LUMO gap, suggesting its high symmetry. Theoretical calculations show that both the neutral and anion are D6h pyramidal. The chemical bonding analyses for [Ta2B6] revealed the nature of the B6 and Ta interactions and uncovered strong covalent bonding between B6 and Ta. The D6h-[TaB6Ta] gaseous cluster is reminiscent of the structural pattern in the ReB6X6Re core in the [(Cp*Re)2B6H4Cl2] and the TiB6Ti motif in the newly synthesized Ti7Rh4Ir2B8 solid-state compound.[5,6] The current work provides an intrinsic link between a gaseous cluster and motifs for solid materials. Continued investigations of the transition-metal boron clusters may lead to the discovery of new structural motifs involving pure boron clusters for the design of novel boride materials. Reference [1] H.W. Kroto, J. R. Heath, S. C. OBrien, R. F. Curl, R. E. Smalley, Nature 1985, 318, 162 - 163. [2] W. Krtschmer, L. D. Lamb, K. Fostiropoulos, D. R. Huffman, Nature 1990, 347, 354 - 358. [3] T. P. Fehlner, J.-F. Halet, J.-Y. Saillard, Molecular Clusters: A Bridge to Solid-State Chemitry, Cambridge University Press, UK, 2007. [4] W. L. Li, L. Xie, T. Jian, C. Romanescu, X. Huang, L.-S. Wang, Angew. Chem. Int. Ed. 2014, 126, 1312 - 1316. [5] B. Le Guennic, H. Jiao, S. Kahlal, J.-Y. Saillard, J.-F. Halet, S. Ghosh, M. Shang, A. M. Beatty, A. L. Rheingold, T. P. Fehlner, J. Am. Chem. Soc. 2004, 126, 3203 - 3217. [6] B. P. T. Fokwa, M. Hermus, Angew

Chemistry 200, 300 Interim Guide.

ERIC Educational Resources Information Center

Manitoba Dept. of Education, Winnipeg.

This guide, developed for the chemistry 200, 300 program in Manitoba, is designed to articulate with previous science courses, provide concepts, processes, and skills which will enable students to continue in chemistry-related areas, and relate chemistry to practical applications in everyday life. It includes a program overview (with program goals…

Ferromagnetic bond of Li{sub 10} cluster: An alternative approach in terms of effective ferromagnetic sites

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

Donoso, Roberto; Fuentealba, Patricio, E-mail: pfuentea@hotmail.es, E-mail: cardena@macul.ciencias.uchile.cl; Cárdenas, Carlos, E-mail: pfuentea@hotmail.es, E-mail: cardena@macul.ciencias.uchile.cl

In this work, a model to explain the unusual stability of atomic lithium clusters in their highest spin multiplicity is presented and used to describe the ferromagnetic bonding of high-spin Li{sub 10} and Li{sub 8} clusters. The model associates the (lack of-)fitness of Heisenberg Hamiltonian with the degree of (de-)localization of the valence electrons in the cluster. It is shown that a regular Heisenberg Hamiltonian with four coupling constants cannot fully explain the energy of the different spin states. However, a more simple model in which electrons are located not at the position of the nuclei but at the positionmore » of the attractors of the electron localization function succeeds in explaining the energy spectrum and, at the same time, explains the ferromagnetic bond found by Shaik using arguments of valence bond theory. In this way, two different points of view, one more often used in physics, the Heisenberg model, and the other in chemistry, valence bond, come to the same answer to explain those atypical bonds.« less

Revitalizing chemistry laboratory instruction

NASA Astrophysics Data System (ADS)

McBride, Phil Blake

This dissertation involves research in three major domains of chemical education as partial fulfillment of the requirements for the Ph.D. program in chemistry at Miami University with a major emphasis on chemical education, and concurrent study in organic chemistry. Unit I, Development and Assessment of a Column Chromatography Laboratory Activity, addresses the domain of Instructional Materials Development and Testing. This unit outlines the process of developing a publishable laboratory activity, testing and revising that activity, and subsequently sharing that activity with the chemical education community. A laboratory activity focusing on the separation of methylene blue and sodium fluorescein was developed to demonstrate the effects of both the stationary and mobile phase in conducting a separation. Unit II, Bringing Industry to the Laboratory, addresses the domain of Curriculum Development and Testing. This unit outlines the development of the Chemistry of Copper Mining module, which is intended for use in high school or undergraduate college chemistry. The module uses the learning cycle approach to present the chemistry of the industrial processes of mining copper to the students. The module includes thirteen investigations (three of which are web-based and ten which are laboratory experiments) and an accompanying interactive CD-ROM, which provides an explanation of the chemistry used in copper mining with a virtual tour of an operational copper mine. Unit III, An Alternative Method of Teaching Chemistry. Integrating Lecture and the Laboratory, is a project that addresses the domain of Research in Student Learning. Fundamental Chemistry was taught at Eastern Arizona College as an integrated lecture/laboratory course that met in two-hour blocks on Monday, Wednesday, and Friday. The students taking this integrated course were compared with students taking the traditional 1-hour lectures held on Monday, Wednesday, and Friday, with accompanying 3-hour lab on

WordCluster: detecting clusters of DNA words and genomic elements

PubMed Central

2011-01-01

Background Many k-mers (or DNA words) and genomic elements are known to be spatially clustered in the genome. Well established examples are the genes, TFBSs, CpG dinucleotides, microRNA genes and ultra-conserved non-coding regions. Currently, no algorithm exists to find these clusters in a statistically comprehensible way. The detection of clustering often relies on densities and sliding-window approaches or arbitrarily chosen distance thresholds. Results We introduce here an algorithm to detect clusters of DNA words (k-mers), or any other genomic element, based on the distance between consecutive copies and an assigned statistical significance. We implemented the method into a web server connected to a MySQL backend, which also determines the co-localization with gene annotations. We demonstrate the usefulness of this approach by detecting the clusters of CAG/CTG (cytosine contexts that can be methylated in undifferentiated cells), showing that the degree of methylation vary drastically between inside and outside of the clusters. As another example, we used WordCluster to search for statistically significant clusters of olfactory receptor (OR) genes in the human genome. Conclusions WordCluster seems to predict biological meaningful clusters of DNA words (k-mers) and genomic entities. The implementation of the method into a web server is available at http://bioinfo2.ugr.es/wordCluster/wordCluster.php including additional features like the detection of co-localization with gene regions or the annotation enrichment tool for functional analysis of overlapped genes. PMID:21261981

Six Pillars of Organic Chemistry

ERIC Educational Resources Information Center

Mullins, Joseph J.

2008-01-01

This article describes an approach to teaching organic chemistry, which is to have students build their knowledge of organic chemistry upon a strong foundation of the fundamental concepts of the subject. Specifically, the article focuses upon a core set of concepts that I call "the six pillars of organic chemistry": electronegativity, polar…

Environmental chemistry: Volume A

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

Yen, T.F.

1999-08-01

This is an extensive introduction to environmental chemistry for engineering and chemical professionals. The contents of Volume A include a brief review of basic chemistry prior to coverage of litho, atmo, hydro, pedo, and biospheres.

Seeing the Chemistry around Me--Helping Students Identify the Relevance of Chemistry to Everyday Life

ERIC Educational Resources Information Center

Moore, Tracy Lynn

2012-01-01

The study attempted to determine whether the use of a series of reading and response assignments decreased students' perceptions of chemistry difficulty and enhanced students' perceptions of the relevance of chemistry in their everyday lives. Informed consent volunteer students enrolled in General Chemistry II at a community college in the…

Chemodynamical Clustering Applied to APOGEE Data: Rediscovering Globular Clusters

NASA Astrophysics Data System (ADS)

Chen, Boquan; D’Onghia, Elena; Pardy, Stephen A.; Pasquali, Anna; Bertelli Motta, Clio; Hanlon, Bret; Grebel, Eva K.

2018-06-01

We have developed a novel technique based on a clustering algorithm that searches for kinematically and chemically clustered stars in the APOGEE DR12 Cannon data. As compared to classical chemical tagging, the kinematic information included in our methodology allows us to identify stars that are members of known globular clusters with greater confidence. We apply our algorithm to the entire APOGEE catalog of 150,615 stars whose chemical abundances are derived by the Cannon. Our methodology found anticorrelations between the elements Al and Mg, Na and O, and C and N previously identified in the optical spectra in globular clusters, even though we omit these elements in our algorithm. Our algorithm identifies globular clusters without a priori knowledge of their locations in the sky. Thus, not only does this technique promise to discover new globular clusters, but it also allows us to identify candidate streams of kinematically and chemically clustered stars in the Milky Way.

Comparison of orbital chemistry with crustal thickness and lunar sample chemistry

NASA Technical Reports Server (NTRS)

Schonfeld, E.

1977-01-01

A correlation between orbital chemistry (FeO, Al2O3, Mg/Al, MgO/FeO, Th) and the lunar crustal thickness is examined. The correlation suggests either lack of complete homogenization by lateral or vertical mixing, or lateral variation in the differentiation process. In addition, links between orbital chemistry and lunar sample chemistry are investigated. In regions with crustal thickness between 100 and 110 km, gabbroic anorthosites are very abundant, while in regions with crustal thickness of about 80 km anorthositic gabbros are frequent. Special attention is given to the distribution of low-potassium Fra Mauro basalt, found in high concentrations in regions with 50 to 60 km crustal thickness.

International Symposium on Clusters and Nanostructures (Energy, Environment, and Health)

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

Jena, Puru

The international Symposium on Clusters and Nanostructures was held in Richmond, Virginia during November 7-10, 2011. The symposium focused on the roles clusters and nanostructures play in solving outstanding problems in clean and sustainable energy, environment, and health; three of the most important issues facing science and society. Many of the materials issues in renewable energies, environmental impacts of energy technologies as well as beneficial and toxicity issues of nanoparticles in health are intertwined. Realizing that both fundamental and applied materials issues require a multidisciplinary approach the symposium provided a forum by bringing researchers from physics, chemistry, materials science, andmore » engineering fields to share their ideas and results, identify outstanding problems, and develop new collaborations. Clean and sustainable energy sessions addressed challenges in production, storage, conversion, and efficiency of renewable energies such as solar, wind, bio, thermo-electric, and hydrogen. Environmental issues dealt with air- and water-pollution and conservation, environmental remediation and hydrocarbon processing. Topics in health included therapeutic and diagnostic methods as well as health hazards attributed to nanoparticles. Cross-cutting topics such as reactions, catalysis, electronic, optical, and magnetic properties were also covered.« less

Aromatic Polyketide GTRI-02 is a Previously Unidentified Product of the act Gene Cluster in Streptomyces coelicolor A3(2).

PubMed

Wu, Changsheng; Ichinose, Koji; Choi, Young Hae; van Wezel, Gilles P

2017-07-18

The biosynthesis of aromatic polyketides derived from type II polyketide synthases (PKSs) is complex, and it is not uncommon that highly similar gene clusters give rise to diverse structural architectures. The act biosynthetic gene cluster (BGC) of the model actinomycete Streptomyces coelicolor A3(2) is an archetypal type II PKS. Here we show that the act BGC also specifies the aromatic polyketide GTRI-02 (1) and propose a mechanism for the biogenesis of its 3,4-dihydronaphthalen-1(2H)-one backbone. Polyketide 1 was also produced by Streptomyces sp. MBT76 after activation of the act-like qin gene cluster by overexpression of the pathway-specific activator. Mining of this strain also identified dehydroxy-GTRI-02 (2), which most likely originated from dehydration of 1 during the isolation process. This work shows that even extensively studied model gene clusters such as act of S. coelicolor can still produce new chemistry, offering new perspectives for drug discovery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Creating a Context for Chemistry

NASA Astrophysics Data System (ADS)

Truman Schwartz, A.

Until relatively recently, the teaching of chemistry at the college and university level in the United States has been quite traditional and oriented primarily toward the preparation of chemists. Students not concentrating in the sciences have often been poorly served by existing courses. Chemistry in Context: Applying Chemistry to Society, a textbook for nonscience majors developed under the sponsorship of the American Chemical Society, is an effort to address the needs and interests of this audience. The book introduces the phenomena and principles of chemistry within the context of socially significant issues such as global warming, ozone depletion, alternate energy sources, nutrition, and genetic engineering. The chemistry is presented as needed to inform an understanding of the central topics, and the text features student-centered activities designed to promote critical thinking and risk-benefit analysis as well as an understanding of chemical principles. This paper summarizes the origin, development, content, pedagogy, evaluation, and influence of Chemistry in Context and considers its potential implications for other disciplines and the instruction of science majors.

Primordial binary populations in low-density star clusters as seen by Chandra: globular clusters versus old open clusters

NASA Astrophysics Data System (ADS)

van den Berg, Maureen C.

2015-08-01

The binaries in the core of a star cluster are the energy source that prevents the cluster from experiencing core collapse. To model the dynamical evolution of a cluster, it is important to have constraints on the primordial binary content. X-ray observations of old star clusters are very efficient in detecting the close interacting binaries among the cluster members. The X-ray sources in star clusters are a mix of binaries that were dynamically formed and primordial binaries. In massive, dense star clusters, dynamical encounters play an important role in shaping the properties and numbers of the binaries. In contrast, in the low-density clusters the impact of dynamical encounters is presumed to be very small, and the close binaries detected in X-rays represent a primordial population. The lowest density globular clusters have current masses and central densities similar to those of the oldest open clusters in our Milky Way. I will discuss the results of studies with the Chandra X-ray Observatory that have nevertheless revealed a clear dichotomy: far fewer (if any at all) X-ray sources are detected in the central regions of the low-density globular clusters compared to the number of secure cluster members that have been detected in old open clusters (above a limiting X-ray luminosity of typically 4e30 erg/s). The low stellar encounter rates imply that dynamical destruction of binaries can be ignored at present, therefore an explanation must be sought elsewhere. I will discuss several factors that can shed light on the implied differences between the primordial close binary populations in the two types of star clusters.

Thermodynamics and proton activities of protic ionic liquids with quantum cluster equilibrium theory

NASA Astrophysics Data System (ADS)

Ingenmey, Johannes; von Domaros, Michael; Perlt, Eva; Verevkin, Sergey P.; Kirchner, Barbara

2018-05-01

We applied the binary Quantum Cluster Equilibrium (bQCE) method to a number of alkylammonium-based protic ionic liquids in order to predict boiling points, vaporization enthalpies, and proton activities. The theory combines statistical thermodynamics of van-der-Waals-type clusters with ab initio quantum chemistry and yields the partition functions (and associated thermodynamic potentials) of binary mixtures over a wide range of thermodynamic phase points. Unlike conventional cluster approaches that are limited to the prediction of thermodynamic properties, dissociation reactions can be effortlessly included into the bQCE formalism, giving access to ionicities, as well. The method is open to quantum chemical methods at any level of theory, but combination with low-cost composite density functional theory methods and the proposed systematic approach to generate cluster sets provides a computationally inexpensive and mostly parameter-free way to predict such properties at good-to-excellent accuracy. Boiling points can be predicted within an accuracy of 50 K, reaching excellent accuracy for ethylammonium nitrate. Vaporization enthalpies are predicted within an accuracy of 20 kJ mol-1 and can be systematically interpreted on a molecular level. We present the first theoretical approach to predict proton activities in protic ionic liquids, with results fitting well into the experimentally observed correlation. Furthermore, enthalpies of vaporization were measured experimentally for some alkylammonium nitrates and an excellent linear correlation with vaporization enthalpies of their respective parent amines is observed.

Active Learning Applications in the History of Chemistry: Pre-Service Chemistry Teachers' Level of Knowledge and Views

ERIC Educational Resources Information Center

Sendur, Gülten; Polat, Merve; Toku, Abdullah; Kazanci, Coskun

2014-01-01

This study aims to investigate the effects of a History and Philosophy of Chemistry-I course based on active learning applications on the level of knowledge of pre-service chemistry teachers about the history of chemistry. The views of pre-service chemistry teachers about these activities were also investigated. The study was carried out with 38…

Iridium clusters in KLTL zeolite: Synthesis, structural characterization, and catalysis of toluene hydrogenation and n-hexane dehydrocyclization

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

Zhao, A.; Jentoft, R.E.; Gates, B.C.

Iridium clusters incorporating about six atoms each, on average, were prepared in KLTL zeolite by decarbonylation (in H{sub 2} at 400{degrees}C) of iridium carbonyl clusters formed by treatment of adsorbed [Ir(CO){sub 2}(acac)] in CO at 1 atm and 175{degrees}C. The supported species were characterized by infrared and extended X-ray absorption fine structure (EXAFS) spectroscopies. The iridium carbonyls formed from [Ir(CO){sub 2}(acac)] were predominantly [HIr{sub 4}(CO){sub 11}]{sup -} with a small amount of [Ir(CO){sub 4}]{sup -}. The synthesis chemistry of iridium carbonyls in the basic KLTL zeolite parallels that in basic solutions. Shifts of the {nu}{sub CO} bands of the iridiummore » carbonyl clusters relative to those of the same clusters in solution indicate strong interactions between the clusters and zeolite cations. The decarbonylated sample, approximated as Ir{sub 6}/KLTL zeolite, is catalytically active for toluene hydrogenation at 60-100{degrees}C, with the activity being approximately the same as those of Ir{sub 4} and Ir{sub 6} clusters supported on metal oxides, but an order of magnitude less than that of a conventional supported iridium catalyst consisting of aggregates of about 50 atoms each, on average. The catalyst is also active for conversion of n-hexane + H{sub 2} at 340-420{degrees}C, but the selectivity for aromatization is low and that for hydrogenolysis is high, consistent with earlier results for conventionally prepared (salt-derived) iridium clusters of about the same size supported in KLTL zeolite. The zeolite-supported iridium clusters are the first prepared from both salt and organometallic precursors; the results indicate that the organometallic and conventional preparation routes lead to supported iridium clusters having similar structures and catalytic properties. 59 refs., 6 figs., 7 tabs.« less

The Status of Chemistry in Two-Year Colleges: Results from a Survey of Chemistry Departments.

ERIC Educational Resources Information Center

Ryan, Mary Ann; Wesemann, Jodi L.; Boese, Janet M.; Neuschatz, Michael

In the fall of 2001, the American Chemical Society (ACS) conducted a survey of two-year college chemistry departments to obtain basic data on chemistry faculty and chemistry courses taught at college. A questionnaire sent to appropriate representatives (department chairs, program heads, or deans) from 1195 campuses generated a 77% response rate.…

Micro-Raman and SEM-EDS analyses to evaluate the nature of salt clusters present in secondary marine aerosol.

PubMed

Morillas, Héctor; Marcaida, Iker; García-Florentino, Cristina; Maguregui, Maite; Arana, Gorka; Madariaga, Juan Manuel

2018-02-15

Marine aerosol is a complex inorganic and organic chemistry system which contains several salts, mainly forming different type of salt clusters. Different meteorological parameters have a key role in the formation of these aggregates. The relative humidity (%RH), temperature, CO, SO 2 and NO x levels and even the O 3 levels can promote different chemical reactions giving rise to salt clusters with different morphology and sizes. Sulfates, nitrates and chlorides and even mixed chlorosulfates or nitrosulfates are the final compounds which can be found in environments with a direct influence of marine aerosol. In order to collect and analyze these types of compounds, the use of adequate samplers is crucial. In this work, salt clusters were collected thanks to the use of a self-made passive sampler (SMPS) installed in a 20th century historic building (Punta Begoña Galleries, Getxo, Basque Country, Spain) which is surrounded by a beach and a sportive port. These salt clusters were finally analyzed directly by micro-Raman spectroscopy and Scanning Electron microscopy coupled to Energy Dispersive X-ray spectrometry (SEM-EDS). Copyright © 2017 Elsevier B.V. All rights reserved.

Chemistry Experiments

NASA Technical Reports Server (NTRS)

Brasseur, Guy; Remsberg, Ellis; Purcell, Patrick; Bhatt, Praful; Sage, Karen H.; Brown, Donald E.; Scott, Courtney J.; Ko, Malcolm K. W.; Tie, Xue-Xi; Huang, Theresa

1999-01-01

The purpose of the chemistry component of the model comparison is to assess to what extent differences in the formulation of chemical processes explain the variance between model results. Observed concentrations of chemical compounds are used to estimate to what degree the various models represent realistic situations. For readability, the materials for the chemistry experiment are reported in three separate sections. This section discussed the data used to evaluate the models in their simulation of the source gases and the Nitrogen compounds (NO(y)) and Chlorine compounds (Cl(y)) species.

Fast Constrained Spectral Clustering and Cluster Ensemble with Random Projection

PubMed Central

Liu, Wenfen

2017-01-01

Constrained spectral clustering (CSC) method can greatly improve the clustering accuracy with the incorporation of constraint information into spectral clustering and thus has been paid academic attention widely. In this paper, we propose a fast CSC algorithm via encoding landmark-based graph construction into a new CSC model and applying random sampling to decrease the data size after spectral embedding. Compared with the original model, the new algorithm has the similar results with the increase of its model size asymptotically; compared with the most efficient CSC algorithm known, the new algorithm runs faster and has a wider range of suitable data sets. Meanwhile, a scalable semisupervised cluster ensemble algorithm is also proposed via the combination of our fast CSC algorithm and dimensionality reduction with random projection in the process of spectral ensemble clustering. We demonstrate by presenting theoretical analysis and empirical results that the new cluster ensemble algorithm has advantages in terms of efficiency and effectiveness. Furthermore, the approximate preservation of random projection in clustering accuracy proved in the stage of consensus clustering is also suitable for the weighted k-means clustering and thus gives the theoretical guarantee to this special kind of k-means clustering where each point has its corresponding weight. PMID:29312447

Cluster Dynamical Mass from Magellan Multi-Object Spectroscopy for SGAS Clusters

NASA Astrophysics Data System (ADS)

Murray, Katherine; Sharon, Keren; Johnson, Traci; Gifford, Daniel; Gladders, Michael; Bayliss, Matthew; Florian, Michael; Rigby, Jane R.; Miller, Christopher J.

2016-01-01

Galaxy clusters are giant structures in space consisting of hundreds or thousands of galaxies, interstellar matter, and dark matter, all bound together by gravity. We analyze the spectra of the cluster members of several strong lensing clusters from a large program, the Sloan Giant Arcs Survey, to determine the total mass of the lensing clusters. From spectra obtained with the LDSS3 and IMACS cameras on the Magellan 6.5m telescopes, we measure the spectroscopic redshifts of about 50 galaxies in each cluster, and calculate the velocity distributions within the galaxy clusters, as well as their projected cluster-centric radii. From these two pieces of information, we measure the size and total dynamical mass of each cluster. We can combine this calculation with other measurements of mass of the same galaxy clusters (like measurements from strong lensing or X-ray) to determine the spatial distribution of luminous and dark matter out to the virial radius of the cluster.

The Chemistry of Population III Supernova Ejecta. II. The Nucleation of Molecular Clusters as a Diagnostic for Dust in the Early Universe

NASA Astrophysics Data System (ADS)

Cherchneff, Isabelle; Dwek, Eli

2010-04-01

We study the formation of molecular precursors to dust in the ejecta of Population III supernovae (Pop. III SNe) using a chemical kinetic approach to follow the evolution of small dust cluster abundances from day 100 to day 1000 after explosion. Our work focuses on zero-metallicity 20 M sun and 170 M sun progenitors, and we consider fully macroscopically mixed and unmixed ejecta. The dust precursors comprise molecular chains, rings, and small clusters of chemical composition relevant to the initial elemental composition of the ejecta under study. The nucleation stage for small silica, metal oxides and sulfides, pure metal, and carbon clusters is described with a new chemical reaction network highly relevant to the kinetic description of dust formation in hot circumstellar environments. We consider the effect of the pressure dependence of critical nucleation rates and test the impact of microscopically mixed He+ on carbon dust formation. Two cases of metal depletion on silica clusters (full and no depletion) are considered to derive upper limits to the amounts of dust produced in SN ejecta at 1000 days, while the chemical composition of clusters gives a prescription for the type of dust formed in Pop. III SNe. We show that the cluster mass produced in the fully mixed ejecta of a 170 M sun progenitor is ~ 25 M sun whereas its 20 M sun counterpart forms ~ 0.16 M sun of clusters. The unmixed ejecta of a 170 M sun progenitor SN synthesize ~5.6 M sun of small clusters, while its 20 M sun counterpart produces ~0.103 M sun. Our results point to smaller amounts of dust formed in the ejecta of Pop. III SNe by a factor of ~ 5 compared to values derived by previous studies, and to different dust chemical compositions. Such deviations result from some erroneous assumptions made, the inappropriate use of classical nucleation theory to model dust formation, and the omission of the synthesis of molecules in SN ejecta. We also find that the unmixed ejecta of massive Pop. III SNe

11(th) National Meeting of Organic Chemistry and 4(th) Meeting of Therapeutic Chemistry.

PubMed

Sousa, Maria Emília; Araújo, Maria João; do Vale, Maria Luísa; Andrade, Paula B; Branco, Paula; Gomes, Paula; Moreira, Rui; Pinho E Melo, Teresa M V D; Freitas, Victor

2016-03-17

For the first time under the auspices of Sociedade Portuguesa de Química, the competences of two important fields of Chemistry are brought together into a single event, the 11st National Organic Chemistry Meeting and the the 4th National Medicinal Chemistry Meeting, to highlight complementarities and to promote new synergies. Abstracts of plenary lectures, oral communications, and posters presented during the meeting are collected in this report.

Spitzer Clusters

NASA Astrophysics Data System (ADS)

Krick, Kessica

This proposal is a specific response to the strategic goal of NASA's research program to "discover how the universe works and explore how the universe evolved into its present form." Towards this goal, we propose to mine the Spitzer archive for all observations of galaxy groups and clusters for the purpose of studying galaxy evolution in clusters, contamination rates for Sunyaev Zeldovich cluster surveys, and to provide a database of Spitzer observed clusters to the broader community. Funding from this proposal will go towards two years of support for a Postdoc to do this work. After searching the Spitzer Heritage Archive, we have found 194 unique galaxy groups and clusters that have data from both the Infrared array camera (IRAC; Fazio et al. 2004) at 3.6 - 8 microns and the multiband imaging photometer for Spitzer (MIPS; Rieke et al. 2004) at 24microns. This large sample will add value beyond the individual datasets because it will be a larger sample of IR clusters than ever before and will have sufficient diversity in mass, redshift, and dynamical state to allow us to differentiate amongst the effects of these cluster properties. An infrared sample is important because it is unaffected by dust extinction while at the same time is an excellent measure of both stellar mass (IRAC wavelengths) and star formation rate (MIPS wavelengths). Additionally, IRAC can be used to differentiate star forming galaxies (SFG) from active galactic nuclei (AGN), due to their different spectral shapes in this wavelength regime. Specifically, we intend to identify SFG and AGN in galaxy groups and clusters. Groups and clusters differ from the field because the galaxy densities are higher, there is a large potential well due mainly to the mass of the dark matter, and there is hot X-ray gas (the intracluster medium; ICM). We will examine the impact of these differences in environment on galaxy formation by comparing cluster properties of AGN and SFG to those in the field. Also, we will

Complex Autocatalysis in Simple Chemistries.

PubMed

Virgo, Nathaniel; Ikegami, Takashi; McGregor, Simon

2016-01-01

Life on Earth must originally have arisen from abiotic chemistry. Since the details of this chemistry are unknown, we wish to understand, in general, which types of chemistry can lead to complex, lifelike behavior. Here we show that even very simple chemistries in the thermodynamically reversible regime can self-organize to form complex autocatalytic cycles, with the catalytic effects emerging from the network structure. We demonstrate this with a very simple but thermodynamically reasonable artificial chemistry model. By suppressing the direct reaction from reactants to products, we obtain the simplest kind of autocatalytic cycle, resulting in exponential growth. When these simple first-order cycles are prevented from forming, the system achieves superexponential growth through more complex, higher-order autocatalytic cycles. This leads to nonlinear phenomena such as oscillations and bistability, the latter of which is of particular interest regarding the origins of life.

Universal dynamical properties preclude standard clustering in a large class of biochemical data.

PubMed

Gomez, Florian; Stoop, Ralph L; Stoop, Ruedi

2014-09-01

Clustering of chemical and biochemical data based on observed features is a central cognitive step in the analysis of chemical substances, in particular in combinatorial chemistry, or of complex biochemical reaction networks. Often, for reasons unknown to the researcher, this step produces disappointing results. Once the sources of the problem are known, improved clustering methods might revitalize the statistical approach of compound and reaction search and analysis. Here, we present a generic mechanism that may be at the origin of many clustering difficulties. The variety of dynamical behaviors that can be exhibited by complex biochemical reactions on variation of the system parameters are fundamental system fingerprints. In parameter space, shrimp-like or swallow-tail structures separate parameter sets that lead to stable periodic dynamical behavior from those leading to irregular behavior. We work out the genericity of this phenomenon and demonstrate novel examples for their occurrence in realistic models of biophysics. Although we elucidate the phenomenon by considering the emergence of periodicity in dependence on system parameters in a low-dimensional parameter space, the conclusions from our simple setting are shown to continue to be valid for features in a higher-dimensional feature space, as long as the feature-generating mechanism is not too extreme and the dimension of this space is not too high compared with the amount of available data. For online versions of super-paramagnetic clustering see http://stoop.ini.uzh.ch/research/clustering. Supplementary data are available at Bioinformatics online. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Comparing Chemistry to Outcome: The Development of a Chemical Distance Metric, Coupled with Clustering and Hierarchal Visualization Applied to Macromolecular Crystallography

PubMed Central

Bruno, Andrew E.; Ruby, Amanda M.; Luft, Joseph R.; Grant, Thomas D.; Seetharaman, Jayaraman; Montelione, Gaetano T.; Hunt, John F.; Snell, Edward H.

2014-01-01

Many bioscience fields employ high-throughput methods to screen multiple biochemical conditions. The analysis of these becomes tedious without a degree of automation. Crystallization, a rate limiting step in biological X-ray crystallography, is one of these fields. Screening of multiple potential crystallization conditions (cocktails) is the most effective method of probing a proteins phase diagram and guiding crystallization but the interpretation of results can be time-consuming. To aid this empirical approach a cocktail distance coefficient was developed to quantitatively compare macromolecule crystallization conditions and outcome. These coefficients were evaluated against an existing similarity metric developed for crystallization, the C6 metric, using both virtual crystallization screens and by comparison of two related 1,536-cocktail high-throughput crystallization screens. Hierarchical clustering was employed to visualize one of these screens and the crystallization results from an exopolyphosphatase-related protein from Bacteroides fragilis, (BfR192) overlaid on this clustering. This demonstrated a strong correlation between certain chemically related clusters and crystal lead conditions. While this analysis was not used to guide the initial crystallization optimization, it led to the re-evaluation of unexplained peaks in the electron density map of the protein and to the insertion and correct placement of sodium, potassium and phosphate atoms in the structure. With these in place, the resulting structure of the putative active site demonstrated features consistent with active sites of other phosphatases which are involved in binding the phosphoryl moieties of nucleotide triphosphates. The new distance coefficient, CDcoeff, appears to be robust in this application, and coupled with hierarchical clustering and the overlay of crystallization outcome, reveals information of biological relevance. While tested with a single example the potential applications

Putting a Human Face on Chemistry: A Project for Liberal Arts Chemistry.

ERIC Educational Resources Information Center

Kriz, George; Popejoy, Kate

A collaborative project in liberal arts chemistry, involving faculty in chemistry and science education, is described. The project includes various components: an introductory test (DAST) to examine students' perceptions of scientists, a group library research exercise, oral and written presentation of the results of the library research, a…

Research for the advancement of green chemistry practice: Studies in atmospheric and educational chemistry

NASA Astrophysics Data System (ADS)

Cullipher, Steven Gene

Green chemistry is a philosophy of chemistry that emphasizes a decreasing dependence on limited non-renewable resources and an increasing focus on preventing pollution byproducts of the chemical industry. In short, it is the discipline of chemistry practiced through the lens of environmental stewardship. In an effort to advance the practice of green chemistry, three studies will be described that have ramifications for the practice. The first study examines the atmospheric oxidation of a hydrofluorinated ether, a third-generation CFC replacement compound with primarily unknown atmospheric degradation products. Determination of these products has the potential to impact decisions on refrigerant usage in the future. The second study examines chemistry students' development of understanding benefits-costs-risks analysis when presented with two real-world scenarios: refrigerant choice and fuel choice. By studying how benefits-costs-risks thinking develops, curricular materials and instructional approaches can be designed to better foster the development of an ability that is both necessary for green chemists and important in daily decision-making for non-chemists. The final study uses eye tracking technology to examine students' abilities to interpret molecular properties from structural information in the context of global warming. Such abilities are fundamental if chemists are to appropriately assess risks and hazards of chemistry practice.

Infrared Lasers in Chemistry.

ERIC Educational Resources Information Center

John, Phillip

1982-01-01

Selected infrared laser chemistry topics are discussed including carbon dioxide lasers, infrared quanta and molecules, laser-induced chemistry, structural isomerization (laser purification, sensitized reactions, and dielectric breakdown), and fundamental principles of laser isotope separation, focusing on uranium isotope separation. (JN)

Using Cluster Bootstrapping to Analyze Nested Data With a Few Clusters.

PubMed

Huang, Francis L

2018-04-01

Cluster randomized trials involving participants nested within intact treatment and control groups are commonly performed in various educational, psychological, and biomedical studies. However, recruiting and retaining intact groups present various practical, financial, and logistical challenges to evaluators and often, cluster randomized trials are performed with a low number of clusters (~20 groups). Although multilevel models are often used to analyze nested data, researchers may be concerned of potentially biased results due to having only a few groups under study. Cluster bootstrapping has been suggested as an alternative procedure when analyzing clustered data though it has seen very little use in educational and psychological studies. Using a Monte Carlo simulation that varied the number of clusters, average cluster size, and intraclass correlations, we compared standard errors using cluster bootstrapping with those derived using ordinary least squares regression and multilevel models. Results indicate that cluster bootstrapping, though more computationally demanding, can be used as an alternative procedure for the analysis of clustered data when treatment effects at the group level are of primary interest. Supplementary material showing how to perform cluster bootstrapped regressions using R is also provided.

The 2013 Clusters, Nanocrystals & Nanostructures Gordon Research Conference/Gordon Research Seminar

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

Krauss, Todd D.

The fundamental properties of small particles and their potential for groundbreaking applications are among the most exciting areas of study in modern physics, chemistry, and materials science. The Clusters, Nanocrystals & Nanostructures Gordon ResearchConference and Gordon Research Seminar synthesize contributions from these inter-related fields that reflect the pivotal role of nano-particles at the interface between these disciplines. Size-dependent optical, electronic, magnetic and catalytic properties offer prospects for applications in many fields, and possible solutions for many of the grand challenges facing energy generation, consumption, delivery, and storage in the 21st century. The goal of the 2013 Clusters, Nanocrystals & Nanostructuresmore » Gordon Research Conference and Gordon Research Seminar is to continue the historical interdisciplinary tradition of this series and discuss the most recent advances, basic scientific questions, and emerging applications of clusters, nanocrystals, and nanostructures. The Clusters, Nanocrystals & Nanostructures GRC/GRS traditionally brings together the leading scientific groups that have made significant recent advances in one or more fundamental nanoscience or nanotechnology areas. Broad interests of the DOE BES and Solar Photochemistry Program addressed by this meeting include the areas of solar energy to fuels conversion, new photovoltaic systems, fundamental characterization of nanomaterials, magnetism, catalysis, and quantum physics. The vast majority of speakers and attendees will address either directly the topic of nanotechnology for photoinduced charge transfer, charge transport, and catalysis, or will have made significant contributions to related areas that will impact these fields indirectly. These topics have direct relevance to the mission of the DOE BES since it is this cutting-edge basic science that underpins our energy future.« less

Supramolecular chemistry-general principles and selected examples from anion recognition and metallosupramolecular chemistry.

PubMed

Albrecht, Markus

2007-12-01

This review gives an introduction into supramolecular chemistry describing in the first part general principles, focusing on terms like noncovalent interaction, molecular recognition, self-assembly, and supramolecular function. In the second part those will be illustrated by simple examples from our laboratories. Supramolecular chemistry is the science that bridges the gap between the world of molecules and nanotechnology. In supramolecular chemistry noncovalent interactions occur between molecular building blocks, which by molecular recognition and self-assembly form (functional) supramolecular entities. It is also termed the "chemistry of the noncovalent bond." Molecular recognition is based on geometrical complementarity based on the "key-and-lock" principle with nonshape-dependent effects, e.g., solvatization, being also highly influential. Self-assembly leads to the formation of well-defined aggregates. Hereby the overall structure of the target ensemble is controlled by the symmetry features of the certain building blocks. Finally, the aggregates can possess special properties or supramolecular functions, which are only found in the ensemble but not in the participating molecules. This review gives an introduction on supramolecular chemistry and illustrates the fundamental principles by recent examples from our group.

Does a Course on the History and Philosophy of Chemistry Have Any Effect on Prospective Chemistry Teachers' Perceptions? The Case of Chemistry and the Chemist

ERIC Educational Resources Information Center

Sendur, G.; Polat, M.; Kazanci, C.

2017-01-01

The creative comparisons prospective chemistry teachers make about "chemistry" and the "chemist" may reflect how they perceive these concepts. In this sense, it seems important to determine which creative comparisons prospective teachers make with respect to these and how these can change after the history of chemistry is…

11th National Meeting of Organic Chemistry and 4th Meeting of Therapeutic Chemistry

PubMed Central

Sousa, Maria Emília; Araújo, Maria João; do Vale, Maria Luísa; Andrade, Paula B.; Branco, Paula; Gomes, Paula; Moreira, Rui; Pinho e Melo, Teresa M.V.D.; Freitas, Victor

2016-01-01

For the first time under the auspices of Sociedade Portuguesa de Química, the competences of two important fields of Chemistry are brought together into a single event, the 11st National Organic Chemistry Meeting and the the 4th National Medicinal Chemistry Meeting, to highlight complementarities and to promote new synergies. Abstracts of plenary lectures, oral communications, and posters presented during the meeting are collected in this report. PMID:27102166

The future of discovery chemistry: quo vadis? Academic to industrial--the maturation of medicinal chemistry to chemical biology.

PubMed

Hoffmann, Torsten; Bishop, Cheryl

2010-04-01

At Roche, we set out to think about the future role of medicinal chemistry in drug discovery in a project involving both Roche internal stakeholders and external experts in drug discovery chemistry. To derive a coherent strategy, selected scientists were asked to take extreme positions and to derive two orthogonal strategic options: chemistry as the traditional mainstream science and chemistry as the central entrepreneurial science. We believe today's role of medicinal chemistry in industry has remained too narrow. To provide the innovation that industry requires, medicinal chemistry must play its part and diversify at pace with our increasing understanding of chemical biology and network pharmacology. 2010 Elsevier Ltd. All rights reserved.

A model of CO-CH4 global transport/chemistry. I - Chemistry model

NASA Technical Reports Server (NTRS)

Peters, L. K.; Kitada, T.

1980-01-01

A simplified chemistry model was developed to incorporate the CO-CH4 chemistry into the global transport model of these compounds. CO is important because of its effects on atmospheric chemistry and is partly responsible for controlling the hydroxyl radical (OH) concentration in the troposphere. The model includes the photodissociation rate coefficients expressed as functions of solar zenith angle and altitude, and it was applied to determine the sensitivity of the OH concentration to trace gaseous species, such as NOx, O3, and H2O. Also, the concentrations and diurnal variations of OH and HO2, and the contribution of individual reactions to OH generation and consumption were calculated.

Reconsidering Learning Difficulties and Misconceptions in Chemistry: Emergence in Chemistry and Its Implications for Chemical Education

ERIC Educational Resources Information Center

Tümay, Halil

2016-01-01

Identifying students' misconceptions and learning difficulties and finding effective ways of addressing them has been one of the major concerns in chemistry education. However, the chemistry education community has paid little attention to determining discipline-specific aspects of chemistry that can lead to learning difficulties and…

Intelligent Chemistry Management System (ICMS)--A new approach to steam generator chemistry control

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

Barto, R.J.; Farrell, D.M.; Noto, F.A.

1986-04-01

The Intelligent Chemistry Management System (ICMS) is a new tool which assists in steam generator chemistry control. Utilizing diagnostic capabilities, the ICMS will provide utility and industrial boiler operators, system chemists, and plant engineers with a tool for monitoring, diagnosing, and controlling steam generator system chemistry. By reducing the number of forced outages through early identification of potentially detrimental conditions, suggestion of possible causes, and execution of corrective actions, improvements in unit availability and reliability will result. The system monitors water and steam quality at a number of critical locations in the plant.

Rapid Characterization of Molecular Chemistry, Nutrient Make-Up and Microlocation of Internal Seed Tissue

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

Yu,P.; Block, H.; Niu, Z.

2007-01-01

Wheat differs from corn in biodegradation kinetics and fermentation characteristics. Wheat exhibits a relatively high rate (23% h{sup 01}) and extent (78% DM) of biodegradation, which can lead to metabolic problems such as acidosis and bloat in ruminants. The objective of this study was to rapidly characterize the molecular chemistry of the internal structure of wheat (cv. AC Barrie) and reveal both its structural chemical make-up and nutrient component matrix by analyzing the intensity and spatial distribution of molecular functional groups within the intact seed using advanced synchrotron-powered Fourier transform infrared (FTIR) microspectroscopy. The experiment was performed at the U2Bmore » station of the National Synchrotron Light Source at Brookhaven National Laboratory, New York, USA. The wheat tissue was imaged systematically from the pericarp, seed coat, aleurone layer and endosperm under the peaks at {approx}1732 (carbonyl C{double_bond}O ester), 1515 (aromatic compound of lignin), 1650 (amide I), 1025 (non-structural CHO), 1550 (amide II), 1246 (cellulosic material), 1160, 1150, 1080, 930, 860 (all CHO), 3350 (OH and NH stretching), 2928 (CH{sub 2} stretching band) and 2885 cm{sup -1} (CH{sub 3} stretching band). Hierarchical cluster analysis and principal component analysis were applied to analyze the molecular FTIR spectra obtained from the different inherent structures within the intact wheat tissues. The results showed that, with synchrotron-powered FTIR microspectroscopy, images of the molecular chemistry of wheat could be generated at an ultra-spatial resolution. The features of aromatic lignin, structural and non-structural carbohydrates, as well as nutrient make-up and interactions in the seeds, could be revealed. Both principal component analysis and hierarchical cluster analysis methods are conclusive in showing that they can discriminate and classify the different inherent structures within the seed tissue. The wheat exhibited

Scientific Cluster Deployment and Recovery - Using puppet to simplify cluster management

NASA Astrophysics Data System (ADS)

Hendrix, Val; Benjamin, Doug; Yao, Yushu

2012-12-01

Deployment, maintenance and recovery of a scientific cluster, which has complex, specialized services, can be a time consuming task requiring the assistance of Linux system administrators, network engineers as well as domain experts. Universities and small institutions that have a part-time FTE with limited time for and knowledge of the administration of such clusters can be strained by such maintenance tasks. This current work is the result of an effort to maintain a data analysis cluster (DAC) with minimal effort by a local system administrator. The realized benefit is the scientist, who is the local system administrator, is able to focus on the data analysis instead of the intricacies of managing a cluster. Our work provides a cluster deployment and recovery process (CDRP) based on the puppet configuration engine allowing a part-time FTE to easily deploy and recover entire clusters with minimal effort. Puppet is a configuration management system (CMS) used widely in computing centers for the automatic management of resources. Domain experts use Puppet's declarative language to define reusable modules for service configuration and deployment. Our CDRP has three actors: domain experts, a cluster designer and a cluster manager. The domain experts first write the puppet modules for the cluster services. A cluster designer would then define a cluster. This includes the creation of cluster roles, mapping the services to those roles and determining the relationships between the services. Finally, a cluster manager would acquire the resources (machines, networking), enter the cluster input parameters (hostnames, IP addresses) and automatically generate deployment scripts used by puppet to configure it to act as a designated role. In the event of a machine failure, the originally generated deployment scripts along with puppet can be used to easily reconfigure a new machine. The cluster definition produced in our CDRP is an integral part of automating cluster deployment

Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

DOE PAGES

Kim, Michelle J.; Zoerb, Matthew C.; Campbell, Nicole R.; ...

2016-04-05

Here, benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (> 1 ncps ppt −1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through amore » combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (< 25 %) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated ( R 2 > 0.95, 10 s averages) over a wide range of sampling conditions.« less

Cluster-lensing: A Python Package for Galaxy Clusters and Miscentering

NASA Astrophysics Data System (ADS)

Ford, Jes; VanderPlas, Jake

2016-12-01

We describe a new open source package for calculating properties of galaxy clusters, including Navarro, Frenk, and White halo profiles with and without the effects of cluster miscentering. This pure-Python package, cluster-lensing, provides well-documented and easy-to-use classes and functions for calculating cluster scaling relations, including mass-richness and mass-concentration relations from the literature, as well as the surface mass density {{Σ }}(R) and differential surface mass density {{Δ }}{{Σ }}(R) profiles, probed by weak lensing magnification and shear. Galaxy cluster miscentering is especially a concern for stacked weak lensing shear studies of galaxy clusters, where offsets between the assumed and the true underlying matter distribution can lead to a significant bias in the mass estimates if not accounted for. This software has been developed and released in a public GitHub repository, and is licensed under the permissive MIT license. The cluster-lensing package is archived on Zenodo. Full documentation, source code, and installation instructions are available at http://jesford.github.io/cluster-lensing/.

Clusters, Assemble: Growth of Intermetallic Compounds from Metal Flux Reactions.

PubMed

Latturner, Susan E

2018-01-16

Metal flux synthesis involves the reaction of metals and metalloids in a large excess of a low-melting metal that acts as a solvent. This technique makes use of an unusual temperature regime (above the temperatures used for solvothermal methods and below the temperatures used in traditional solid state synthesis) and facilitates the growth of products as large crystals. It has proven to be a fruitful method to discover new intermetallic compounds. However, little is known about the chemistry occurring within a molten metal solvent; without an understanding of the nature of precursor formation and assembly, it is difficult to predict product structures and target properties. Organic chemists have a vast toolbox of well-known reagents and reaction mechanisms to use in directing their synthesis toward a desired molecular structure. This is not yet the case for the synthesis of inorganic extended structures. We have carried out extensive explorations of the growth of new magnetic intermetallic compounds from a variety of metal fluxes. This Account presents a review of some of our results and recent reports by other groups; this work indicates that products with common building blocks and homologous series with identical structural motifs are repeatedly seen in metal flux chemistry. For instance, fluorite-type layers comprised of transition metals coordinated by eight main group metal atoms are found in the Th 2 (Au x Si 1-x )[AuAl 2 ] n Si 2 and R[AuAl 2 ] n Al 2 (Au x Si 1-x ) 2 series grown from aluminum flux, the Ce n PdIn 3n+2 series grown from indium flux, and CePdGa 6 and Ce 2 PdGa 10 grown from gallium flux. Similarly, our investigations of reactions of heavy main group metals, M, in rare earth/transition metal eutectic fluxes reveal that the R/T/M/M' products usually feature M-centered rare earth clusters M@R 8-12 , which share faces to form layers and networks that surround transition metal building blocks. These structural trends, temperature dependence of

Ab Initio Studies of Fluorine and Chlorine Oxide and Nitrogen Oxide Species of Interest in Stratospheric Chemistry

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

The quality of fundamental vibrational frequencies determined using the CCSD(T) method (singles and doubles coupled-cluster theory plus a perturbational estimate of the effects of connected triple excitations) is shown to be very good, usually predicting band centers to within plus or minus 8 per centimeter. This approach is applied to several molecules of interest in atmospheric chemistry, such as HNO, cis-FONO, cis-ClONO, and ClOOH. The HNO molecule displays a large and unusual anharmonicity in the H-N stretch. For the calculation of ultraviolet (UV) spectra, the linear response CCSD (LRCCSD) approach (which is equivalent to EOM-CCSD) has been shown to yield vertical excitation energies that are accurate to approximately equal to 0.1 eV for singly excited electronic states. This method together with more approximate methods is used to examine the UV spectra of several molecules important in stratospheric chemistry, including HOCl, Cl2O, ClONO2, HONO2, ClOOCl, ClOOH, and HOOH.

Chemical analysis of eight giant stars of the globular cluster NGC 6366

NASA Astrophysics Data System (ADS)

Puls, Arthur A.; Alves-Brito, Alan; Campos, Fabíola; Dias, Bruno; Barbuy, Beatriz

2018-05-01

The metal-rich Galactic globular cluster NGC 6366 is the fifth closest to the Sun. Despite its interest, it has received scarce attention, and little is known about its internal structure. Its kinematics suggests a link to the halo, but its metallicity indicates otherwise. We present a detailed chemical analysis of eight giant stars of NGC 6366, using high-resolution and high-quality spectra (R > 40 000, S/N > 60) obtained at the VLT (8.2 m) and CFHT (3.6 m) telescopes. We attempted to characterize its chemistry and to search for evidence of multiple stellar populations. The atmospheric parameters were derived using the method of excitation and ionization equilibrium of Fe I and Fe II lines and from those atmospheric parameters we calculated the abundances for other elements and found that none of the elements measured presents star-to-star variation greater than the uncertainties. We compared the derived abundances with those of other globular clusters and field stars available in the literature. We determined a mean [Fe/H] = -0.60 ± 0.03 for NGC 6366 and found some similarity of this object with M 71, another inner halo globular cluster. The Na-O anticorrelation extension is short and no star-to-star variation in Al is found. The presence of second generation stars is not evident in NGC 6366.

Brushing Up on Chemistry.

ERIC Educational Resources Information Center

Trantow, Ashley

2002-01-01

Presents an activity designed for use during National Chemistry Week 2002 with the theme "Chemistry Keeps Us Clean". Allows students to discover more about a cleaning product they use everyday. Students make their own toothpaste and compare its properties with those of commercial toothpaste. (MM)

WATER CHEMISTRY ASSESSMENT METHODS

EPA Science Inventory

This section summarizes and evaluates the surfce water column chemistry assessment methods for USEPA/EMAP-SW, USGS-NAQA, USEPA-RBP, Oho EPA, and MDNR-MBSS. The basic objective of surface water column chemistry assessment is to characterize surface water quality by measuring a sui...

“Ligands-with-Benefits”: Naphthalene-Substituted Schiff Bases Yielding New Ni II Metal Clusters with Ferromagnetic and Emissive Properties and Undergoing Exciting Transformations

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

Perlepe, Panagiota S.; Cunha-Silva, Luis; Gagnon, Kevin J.

The initial employment of the fluorescent bridging ligand N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH 2) in metal cluster chemistry has led to new Ni 12 (1) and Ni 5 (2) clusters with wheel-like and molecular-chain topologies, respectively. The doubly-deprotonated nacb 2- ligands were found to adopt four different coordination modes within 1 and 2. The nature of the ligand has also allowed unexpected organic transformations to occur and ferromagnetic and emission behaviors to emerge. The combined work presented here demonstrates the ability of some "ligands-with-benefits" to yield beautiful structures with exciting topologies and interesting physicochemical properties.

“Ligands-with-Benefits”: Naphthalene-Substituted Schiff Bases Yielding New Ni II Metal Clusters with Ferromagnetic and Emissive Properties and Undergoing Exciting Transformations

DOE PAGES

Perlepe, Panagiota S.; Cunha-Silva, Luis; Gagnon, Kevin J.; ...

2016-01-20

The initial employment of the fluorescent bridging ligand N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH 2) in metal cluster chemistry has led to new Ni 12 (1) and Ni 5 (2) clusters with wheel-like and molecular-chain topologies, respectively. The doubly-deprotonated nacb 2- ligands were found to adopt four different coordination modes within 1 and 2. The nature of the ligand has also allowed unexpected organic transformations to occur and ferromagnetic and emission behaviors to emerge. The combined work presented here demonstrates the ability of some "ligands-with-benefits" to yield beautiful structures with exciting topologies and interesting physicochemical properties.

Merging Clusters, Cluster Outskirts, and Large Scale Filaments

NASA Astrophysics Data System (ADS)

Randall, Scott; Alvarez, Gabriella; Bulbul, Esra; Jones, Christine; Forman, William; Su, Yuanyuan; Miller, Eric D.; Bourdin, Herve; Scott Randall

2018-01-01

Recent X-ray observations of the outskirts of clusters show that entropy profiles of the intracluster medium (ICM) generally flatten and lie below what is expected from purely gravitational structure formation near the cluster's virial radius. Possible explanations include electron/ion non-equilibrium, accretion shocks that weaken during cluster formation, and the presence of unresolved cool gas clumps. Some of these mechanisms are expected to correlate with large scale structure (LSS), such that the entropy is lower in regions where the ICM interfaces with LSS filaments and, presumably, the warm-hot intergalactic medium (WHIM). Major, binary cluster mergers are expected to take place at the intersection of LSS filaments, with the merger axis initially oriented along a filament. We present results from deep X-ray observations of the virialization regions of binary, early-stage merging clusters, including a possible detection of the dense end of the WHIM along a LSS filament.

Chemistry inside an Epistemological Community Box! Discursive Exclusions and Inclusions in Swedish National Tests in Chemistry

ERIC Educational Resources Information Center

Ståhl, Marie; Hussénius, Anita

2017-01-01

This study examined the Swedish national tests in chemistry for implicit and explicit values. The chemistry subject is understudied compared to biology and physics and students view chemistry as their least interesting science subject. The Swedish national science assessments aim to support equitable and fair evaluation of students, to concretize…

Changing cluster composition in cluster randomised controlled trials: design and analysis considerations

PubMed Central

2014-01-01

Background There are many methodological challenges in the conduct and analysis of cluster randomised controlled trials, but one that has received little attention is that of post-randomisation changes to cluster composition. To illustrate this, we focus on the issue of cluster merging, considering the impact on the design, analysis and interpretation of trial outcomes. Methods We explored the effects of merging clusters on study power using standard methods of power calculation. We assessed the potential impacts on study findings of both homogeneous cluster merges (involving clusters randomised to the same arm of a trial) and heterogeneous merges (involving clusters randomised to different arms of a trial) by simulation. To determine the impact on bias and precision of treatment effect estimates, we applied standard methods of analysis to different populations under analysis. Results Cluster merging produced a systematic reduction in study power. This effect depended on the number of merges and was most pronounced when variability in cluster size was at its greatest. Simulations demonstrate that the impact on analysis was minimal when cluster merges were homogeneous, with impact on study power being balanced by a change in observed intracluster correlation coefficient (ICC). We found a decrease in study power when cluster merges were heterogeneous, and the estimate of treatment effect was attenuated. Conclusions Examples of cluster merges found in previously published reports of cluster randomised trials were typically homogeneous rather than heterogeneous. Simulations demonstrated that trial findings in such cases would be unbiased. However, simulations also showed that any heterogeneous cluster merges would introduce bias that would be hard to quantify, as well as having negative impacts on the precision of estimates obtained. Further methodological development is warranted to better determine how to analyse such trials appropriately. Interim recommendations

A Comparison of Secondary Chemistry Courses and Chemistry Teacher Preparation Programs in Iowa and Saint Petersburg, Russia

NASA Astrophysics Data System (ADS)

Sanger, Michael J.; Brincks, Erik L.; Phelps, Amy J.; Pak, Maria S.; Lyovkin, Antony N.

2001-09-01

This paper, which is a result of the collaboration between the University of Northern Iowa (UNI) in Cedar Falls, Iowa, and Herzen State Pedagogical University of Russia in Saint Petersburg, compares the 7-12 chemistry courses in Iowa and Saint Petersburg and the chemistry teacher preparation programs at UNI and Herzen. Differences in the 7-12 chemistry courses include curriculum design (spiral versus layer cake), students' extracurricular activities, and access to technology in the classroom. Differences in the chemistry teacher preparation programs include the number of methods and chemistry content courses required, the number of chemistry teaching majors, the proportion of teaching majors enrolled in the different natural science programs, and the typical minors and endorsements received by these majors. Although we noted many differences in chemistry instruction between Iowa and Saint Petersburg, the secondary and college instructors still face many similar issues, which include overcoming student chemophobia, improving students' algorithmic and problem-solving skills, improving students' conceptual understanding at the particulate level, and dealing with shortages in qualified secondary science teachers.

On Study of New Progress and Application of Coordination Chemistry in Chemistry and Chemical Industry in Recent Years

NASA Astrophysics Data System (ADS)

Zhang, Yunshen

2017-12-01

Coordination chemistry refers to a branch of chemistry, and its research results are widely used in industry and people's daily life. Many edge disciplines emerge during the development, which propels the process of disciplines and technology. This paper briefly discusses new progress of coordination chemistry and its application in chemistry and chemical industry in recent years.

ENVIRONMENTAL CHEMISTRY CAREERS IN GOVERNMENT AGENCIES

EPA Science Inventory

Careers in chemistry and chemistry related fields can be very rewarding and enriching. Being an environmental chemist for a government agency requires a broad background in the field of chemistry. A knowledge of the operation of several analytical and preparatory instruments is...

NUCLEAR CHEMISTRY ANNUAL REPORT 1970

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

Authors, Various

Papers are presented for the following topics: (1) Nuclear Structure and Nuclear Properties - (a) Nuclear Spectroscopy and Radioactivity; (b) Nuclear Reactions and Scattering; (c) Nuclear Theory; and (d) Fission. (2) Chemical and Atomic Physics - (a) Atomic and Molecular Spectroscopy; and (b) Hyperfine Interactions. (3) Physical, Inorganic, and Analytical Chemistry - (a) X-Ray Crystallography; (b) Physical and Inorganic Chemistry; (c) Radiation Chemistry; and (d) Chemical Engineering. (4) Instrumentation and Systems Development.

Eleventh international symposium on radiopharmaceutical chemistry

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

NONE

This document contains abstracts of papers which were presented at the Eleventh International Symposium on Radiopharmaceutical Chemistry. Sessions included: radiopharmaceuticals for the dopaminergic system, strategies for the production and use of labelled reactive small molecules, radiopharmaceuticals for measuring metabolism, radiopharmaceuticals for the serotonin and sigma receptor systems, labelled probes for molecular biology applications, radiopharmaceuticals for receptor systems, radiopharmaceuticals utilizing coordination chemistry, radiolabelled antibodies, radiolabelling methods for small molecules, analytical techniques in radiopharmaceutical chemistry, and analytical techniques in radiopharmaceutical chemistry.

Ab initio characterization of ClOOH - Implications for atmospheric chemistry

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Rendell, Alistair P.

1993-01-01

The equilibrium structure, dipole moment, harmonic vibrational frequencies, and infrared intensities of ClOOH are determined using the CCSD(T) (singles and doubles coupled-cluster theory plus a perturbational estimate of the effects of connected triple excitations) electronic structure method in conjunction with a TZ2P (triple xi plus double polarization) basis set. The heat of formation of CIOOH is determined (using two different isodesmic reactions) to be +1.5 +/- 1 kcal/mol at 0 K or +0.2 +/- 1 kcal/mol at 298.15 K. Using the computed heat of formation, we examined the stability of ClOOH with respect to the ClO + OH, ClOO + H, and HOO + Cl dissociation limits. Since ClOOH is found to be quite stable, it is argued that the chemistry of ClOOH should be included in any accurate modeling of the stratosphere.

Mini-clusters

NASA Technical Reports Server (NTRS)

Chinellato, J. A.; Dobrigkeit, C.; Bellandifilho, J.; Lattes, C. M. G.; Menon, M. J.; Navia, C. E.; Pamilaju, A.; Sawayanagi, K.; Shibuya, E. H.; Turtelli, A., Jr.

1985-01-01

Experimental results of mini-clusters observed in Chacaltaya emulsion chamber no.19 are summarized. The study was made on 54 single core shower upper and 91 shower clusters of E(gamma) 10 TeV from 30 families which are visible energy greater than 80 TeV and penetrate through both upper and lower detectors of the two-story chamber. The association of hadrons in mini-cluster is made clear from their penetrative nature and microscopic observation of shower continuation in lower chamber. Small P sub t (gamma) of hadrons in mini-clusters remained in puzzle.

Fuzzy Subspace Clustering

NASA Astrophysics Data System (ADS)

Borgelt, Christian

In clustering we often face the situation that only a subset of the available attributes is relevant for forming clusters, even though this may not be known beforehand. In such cases it is desirable to have a clustering algorithm that automatically weights attributes or even selects a proper subset. In this paper I study such an approach for fuzzy clustering, which is based on the idea to transfer an alternative to the fuzzifier (Klawonn and Höppner, What is fuzzy about fuzzy clustering? Understanding and improving the concept of the fuzzifier, In: Proc. 5th Int. Symp. on Intelligent Data Analysis, 254-264, Springer, Berlin, 2003) to attribute weighting fuzzy clustering (Keller and Klawonn, Int J Uncertain Fuzziness Knowl Based Syst 8:735-746, 2000). In addition, by reformulating Gustafson-Kessel fuzzy clustering, a scheme for weighting and selecting principal axes can be obtained. While in Borgelt (Feature weighting and feature selection in fuzzy clustering, In: Proc. 17th IEEE Int. Conf. on Fuzzy Systems, IEEE Press, Piscataway, NJ, 2008) I already presented such an approach for a global selection of attributes and principal axes, this paper extends it to a cluster-specific selection, thus arriving at a fuzzy subspace clustering algorithm (Parsons, Haque, and Liu, 2004).

Organotin Selenide Clusters and Hybrid Capsules.

PubMed

Dehnen, Stefanie; Hanau, Katharina; Rinn, Niklas; Argentari, Mario

2018-05-22

Several compounds with unique structural motifs that have already been known from organotin sulfide chemistry, but remained unprecedented in organotin selenide chemistry so far, have been synthesized. The reaction of [(R1Sn)4Se6] (R1 = CMe2CH2C(O)Me) with N2H4·H2O/(SiMe3)2Se and with PhN2H3/(SiMe3)2Se led to the formation of [{(R2Sn)2SnSe4}2(µ-Se)2] (1) and [{(R3Sn)2SnSe4}2(µ-Se)2] (2) (R2 = CMe2CH2C(Me)NNH2, R3 = CMe2CH2C(Me)NNPhH), respectively. Addition of o-phthalaldehyde to [(R2Sn)4Se6] yielded a cluster with intramolecular bridging of the organic groups, [(R4Sn2)2Se6] (3, R4 = (CMe2CH2C(Me)NNCH)2C6H4). The introduction of organic ligands with longer chains finally allowed the isolation of inorganic-organic capsules of the type [(µ-R)3(Sn3Se4)2]X2, with R = (CMe2CH2C(Me)NNHC(O))2(CH2)4, X = [SnC3], Cl (4a, 4b) or R = CMe2CH2C(Me)NNH)2, X = [SnCl3] (5). The capsules enclose solvent molecules and/or anions as guests. All compounds were characterized via single-crystal X-ray diffraction, NMR spectroscopy and mass spectrometry. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Student academic achievement in college chemistry

NASA Astrophysics Data System (ADS)

Tabibzadeh, Kiana S.

General Chemistry is required for variety of baccalaureate degrees, including all medical related fields, engineering, and science majors. Depending on the institution, the prerequisite requirement for college level General Chemistry varies. The success rate for this course is low. The purpose of this study is to examine the factors influencing student academic achievement and retention in General Chemistry at the college level. In this study student achievement is defined by those students who earned grades of "C" or better. The dissertation contains in-depth studies on influence of Intermediate Algebra as a prerequisite compared to Fundamental Chemistry for student academic achievement and student retention in college General Chemistry. In addition the study examined the extent and manner in which student self-efficacy influences student academic achievement in college level General Chemistry. The sample for this part of the study is 144 students enrolled in first semester college level General Chemistry. Student surveys determined student self-efficacy level. The statistical analyses of study demonstrated that Fundamental Chemistry is a better prerequisite for student academic achievement and student retention. The study also found that student self-efficacy has no influence on student academic achievement. The significance of this study will be to provide data for the purpose of establishing a uniform and most suitable prerequisite for college level General Chemistry. Finally the variables identified to influence student academic achievement and enhance student retention will support educators' mission to maximize the students' ability to complete their educational goal at institutions of higher education.

About the Clusters Program

EPA Pesticide Factsheets

The Environmental Technology Innovation Clusters Program advises cluster organizations, encourages collaboration between clusters, tracks U.S. environmental technology clusters, and connects EPA programs to cluster needs.

Electron correlation in the interacting quantum atoms partition via coupled-cluster lagrangian densities.

PubMed

Holguín-Gallego, Fernando José; Chávez-Calvillo, Rodrigo; García-Revilla, Marco; Francisco, Evelio; Pendás, Ángel Martín; Rocha-Rinza, Tomás

2016-07-15

The electronic energy partition established by the Interacting Quantum Atoms (IQA) approach is an important method of wavefunction analyses which has yielded valuable insights about different phenomena in physical chemistry. Most of the IQA applications have relied upon approximations, which do not include either dynamical correlation (DC) such as Hartree-Fock (HF) or external DC like CASSCF theory. Recently, DC was included in the IQA method by means of HF/Coupled-Cluster (CC) transition densities (Chávez-Calvillo et al., Comput. Theory Chem. 2015, 1053, 90). Despite the potential utility of this approach, it has a few drawbacks, for example, it is not consistent with the calculation of CC properties different from the total electronic energy. To improve this situation, we have implemented the IQA energy partition based on CC Lagrangian one- and two-electron orbital density matrices. The development presented in this article is tested and illustrated with the H2 , LiH, H2 O, H2 S, N2 , and CO molecules for which the IQA results obtained under the consideration of (i) the CC Lagrangian, (ii) HF/CC transition densities, and (iii) HF are critically analyzed and compared. Additionally, the effect of the DC in the different components of the electronic energy in the formation of the T-shaped (H2 )2 van der Waals cluster and the bimolecular nucleophilic substitution between F(-) and CH3 F is examined. We anticipate that the approach put forward in this article will provide new understandings on subjects in physical chemistry wherein DC plays a crucial role like molecular interactions along with chemical bonding and reactivity. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Chemistry Education Research Trends: 2004-2013

ERIC Educational Resources Information Center

Teo, Tang Wee; Goh, Mei Ting; Yeo, Leck Wee

2014-01-01

This paper presents findings from a content analysis of 650 empirical chemistry education research papers published in two top-tiered chemistry education journals "Chemistry Education Research and Practice" and "Journal of Chemical Education," and four top-tiered science education journals "International Journal of Science…

40 CFR 158.2290 - Residue chemistry.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Residue chemistry. 158.2290 Section... REQUIREMENTS FOR PESTICIDES Antimicrobial Pesticide Data Requirements § 158.2290 Residue chemistry. (a) General... determine the residue chemistry data requirements for antimicrobial pesticide products. Notes that apply to...

40 CFR 158.2290 - Residue chemistry.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Residue chemistry. 158.2290 Section... REQUIREMENTS FOR PESTICIDES Antimicrobial Pesticide Data Requirements § 158.2290 Residue chemistry. (a) General... determine the residue chemistry data requirements for antimicrobial pesticide products. Notes that apply to...

Chemistry Outreach Project to High Schools Using a Mobile Chemistry Laboratory, ChemKits, and Teacher Workshops

ERIC Educational Resources Information Center

Long, Gary L.; Bailey, Carol A.; Bunn, Barbara B.; Slebodnick, Carla; Johnson, Michael R.; Derozier, Shad

2012-01-01

The Chemistry Outreach Program (ChOP) of Virginia Tech was a university-based outreach program that addressed the needs of high school chemistry classes in underfunded rural and inner-city school districts. The primary features of ChOP were a mobile chemistry laboratory (MCL), a shipping-based outreach program (ChemKits), and teacher workshops.…

Using Chemistry Teaching Aids Based Local Wisdom as an Alternative Media for Chemistry Teaching and Learning

ERIC Educational Resources Information Center

Priyambodo, Erfan; Wulaningrum, Safira

2017-01-01

Students have difficulties in relating the chemistry phenomena they learned and the life around them. It is necessary to have teaching aids which can help them to relate between chemistry with the phenomena occurred in everyday life, which is chemistry's teaching aids based on local wisdom. There are 3 teaching aids which used in chemistry…

School Chemistry: The Need for Transgression

NASA Astrophysics Data System (ADS)

Talanquer, Vicente

2013-07-01

Studies of the philosophy of chemistry over the past 15 years suggest that chemistry is a hybrid science which mixes scientific pursuits with technological applications. Dominant universal characterizations of the nature of science thus fail to capture the essence of the discipline. The central goal of this position paper is to encourage reflection about the extent to which dominant views about quality science education based on universal views of scientific practices may constrain school chemistry. In particular, we discuss how these predominant ideas restrict the development of chemistry curricula and instructional approaches that may better support the learning of the ideas and practices that studies of the philosophy of chemistry suggest are at the core of the discipline. Our analysis suggests that philosophical studies about the nature of chemistry invite us to transgress traditional educational boundaries between science and technology, inquiry and design, content and process, and to reconceptualize school chemistry as a paradigmatic techno scientific subject. To support these changes, chemical education researchers should expand the scope of their investigations to better understand how students and teachers reason about and engage in more authentic ways of chemical thinking and doing.

Chemistry, College Level. Annotated Bibliography of Tests.

ERIC Educational Resources Information Center

Educational Testing Service, Princeton, NJ. Test Collection.

Most of the 30 tests cited in this bibliography are those of the American Chemical Society. Subjects covered include physical chemistry, organic chemistry, inorganic chemistry, analytical chemistry, and other specialized areas. The tests are designed only for advanced high school, and both bachelor/graduate degree levels of college students. This…

Major cluster mergers and the location of the brightest cluster galaxy

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

Martel, Hugo; Robichaud, Fidèle; Barai, Paramita, E-mail: Hugo.Martel@phy.ulaval.ca

Using a large N-body cosmological simulation combined with a subgrid treatment of galaxy formation, merging, and tidal destruction, we study the formation and evolution of the galaxy and cluster population in a comoving volume (100 Mpc){sup 3} in a ΛCDM universe. At z = 0, our computational volume contains 1788 clusters with mass M {sub cl} > 1.1 × 10{sup 12} M {sub ☉}, including 18 massive clusters with M {sub cl} > 10{sup 14} M {sub ☉}. It also contains 1, 088, 797 galaxies with mass M {sub gal} ≥ 2 × 10{sup 9} M {sub ☉} and luminositymore » L > 9.5 × 10{sup 5} L {sub ☉}. For each cluster, we identified the brightest cluster galaxy (BCG). We then computed two separate statistics: the fraction f {sub BNC} of clusters in which the BCG is not the closest galaxy to the center of the cluster in projection, and the ratio Δv/σ, where Δv is the difference in radial velocity between the BCG and the whole cluster and σ is the radial velocity dispersion of the cluster. We found that f {sub BNC} increases from 0.05 for low-mass clusters (M {sub cl} ∼ 10{sup 12} M {sub ☉}) to 0.5 for high-mass clusters (M {sub cl} > 10{sup 14} M {sub ☉}) with very little dependence on cluster redshift. Most of this result turns out to be a projection effect and when we consider three-dimensional distances instead of projected distances, f {sub BNC} increases only to 0.2 at high-cluster mass. The values of Δv/σ vary from 0 to 1.8, with median values in the range 0.03-0.15 when considering all clusters, and 0.12-0.31 when considering only massive clusters. These results are consistent with previous observational studies and indicate that the central galaxy paradigm, which states that the BCG should be at rest at the center of the cluster, is usually valid, but exceptions are too common to be ignored. We built merger trees for the 18 most massive clusters in the simulation. Analysis of these trees reveal that 16 of these clusters have experienced 1 or several major or

Tailoring Ion Charge State Distribution in Tetramethyltin Clusters under Influence of Moderate Intensity Picosecond Laser Pulse: Role of Laser Wavelength and Rate of Energy Deposition

NASA Astrophysics Data System (ADS)

Sharma, Pramod; Das, Soumitra; Vatsa, Rajesh K.

2017-07-01

Systematic manipulation of ionic-outcome in laser-cluster interaction process has been realized for studies carried out on tetramethyltin (TMT) clusters under picosecond laser conditions, determined by choice of laser wavelength and intensity. As a function of laser intensity, TMT clusters exhibit gradual enhancement in overall ionization of its cluster constituents, up to a saturation level of ionization, which was distinct for different wavelengths (266, 355, and 532 nm). Simultaneously, systematic appearance of higher multiply charged atomic ions and shift in relative abundance of multiply charged atomic ions towards higher charge state was observed, using time-of-flight mass spectrometer. At saturation level, multiply charged atomic ions up to (C2+, Sn2+) at 266 nm, (C4+, Sn4+) at 355 nm, and (C4+, Sn6+) at 532 nm were detected. In addition, at 355 nm intra-cluster ion chemistry within the ionized cluster leads to generation of molecular hydrogen ion (H2 +) and triatomic molecular hydrogen ion (H3 +). Generation of multiply charged atomic ions is ascribed to efficient coupling of laser pulse with the cluster media, facilitated by inner-ionized electrons produced within the cluster, at the leading edge of laser pulse. Role of inner-ionized electrons is authenticated by measuring kinetic energy distribution of electrons liberated upon disintegration of excessively ionized cluster, under the influence of picosecond laser pulse.

40 CFR 158.2210 - Product chemistry.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Product chemistry. 158.2210 Section... REQUIREMENTS FOR PESTICIDES Antimicrobial Pesticide Data Requirements § 158.2210 Product chemistry. The product chemistry data requirements of subpart D of this part apply to antimicrobial products covered by this...

40 CFR 158.2210 - Product chemistry.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Product chemistry. 158.2210 Section... REQUIREMENTS FOR PESTICIDES Antimicrobial Pesticide Data Requirements § 158.2210 Product chemistry. The product chemistry data requirements of subpart D of this part apply to antimicrobial products covered by this...

Dynamical evolution of globular-cluster systems in clusters of galaxies

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

Muzzio, J.C.

1987-04-01

The dynamical processes that affect globular-cluster systems in clusters of galaxies are analyzed. Two-body and impulsive approximations are utilized to study dynamical friction, drag force, tidal stripping, tidal radii, globular-cluster swapping, tidal accretion, and galactic cannibalism. The evolution of galaxies and the collision of galaxies are simulated numerically; the steps involved in the simulation are described. The simulated data are compared with observations. Consideration is given to the number of galaxies, halo extension, location of the galaxies, distribution of the missing mass, nonequilibrium initial conditions, mass dependence, massive central galaxies, globular-cluster distribution, and lost globular clusters. 116 references.

Query Results Clustering by Extending SPARQL with CLUSTER BY

NASA Astrophysics Data System (ADS)

Ławrynowicz, Agnieszka

The task of dynamic clustering of the search results proved to be useful in the Web context, where the user often does not know the granularity of the search results in advance. The goal of this paper is to provide a declarative way for invoking dynamic clustering of the results of queries submitted over Semantic Web data. To achieve this goal the paper proposes an approach that extends SPARQL by clustering abilities. The approach introduces a new statement, CLUSTER BY, into the SPARQL grammar and proposes semantics for such extension.

Locally Weighted Ensemble Clustering.

PubMed

Huang, Dong; Wang, Chang-Dong; Lai, Jian-Huang

2018-05-01

Due to its ability to combine multiple base clusterings into a probably better and more robust clustering, the ensemble clustering technique has been attracting increasing attention in recent years. Despite the significant success, one limitation to most of the existing ensemble clustering methods is that they generally treat all base clusterings equally regardless of their reliability, which makes them vulnerable to low-quality base clusterings. Although some efforts have been made to (globally) evaluate and weight the base clusterings, yet these methods tend to view each base clustering as an individual and neglect the local diversity of clusters inside the same base clustering. It remains an open problem how to evaluate the reliability of clusters and exploit the local diversity in the ensemble to enhance the consensus performance, especially, in the case when there is no access to data features or specific assumptions on data distribution. To address this, in this paper, we propose a novel ensemble clustering approach based on ensemble-driven cluster uncertainty estimation and local weighting strategy. In particular, the uncertainty of each cluster is estimated by considering the cluster labels in the entire ensemble via an entropic criterion. A novel ensemble-driven cluster validity measure is introduced, and a locally weighted co-association matrix is presented to serve as a summary for the ensemble of diverse clusters. With the local diversity in ensembles exploited, two novel consensus functions are further proposed. Extensive experiments on a variety of real-world datasets demonstrate the superiority of the proposed approach over the state-of-the-art.

Embedded Clusters

NASA Astrophysics Data System (ADS)

Ascenso, Joana

The past decade has seen an increase of star formation studies made at the molecular cloud scale, motivated mostly by the deployment of a wealth of sensitive infrared telescopes and instruments. Embedded clusters, long recognised as the basic units of coherent star formation in molecular clouds, are now seen to inhabit preferentially cluster complexes tens of parsecs across. This chapter gives an overview of some important properties of the embedded clusters in these complexes and of the complexes themselves, along with the implications of viewing star formation as a molecular-cloud scale process rather than an isolated process at the scale of clusters.

Chemistry in Microfluidic Channels

ERIC Educational Resources Information Center

Chia, Matthew C.; Sweeney, Christina M.; Odom, Teri W.

2011-01-01

General chemistry introduces principles such as acid-base chemistry, mixing, and precipitation that are usually demonstrated in bulk solutions. In this laboratory experiment, we describe how chemical reactions can be performed in a microfluidic channel to show advanced concepts such as laminar fluid flow and controlled precipitation. Three sets of…

Movies in Chemistry Education

ERIC Educational Resources Information Center

Pekdag, Bulent; Le Marechal, Jean-Francois

2010-01-01

This article reviews numerous studies on chemistry movies. Movies, or moving pictures, are important elements of multimedia and signify a privileged or motivating means of presenting knowledge. Studies on chemistry movies show that the first movie productions in this field were devoted to university lectures or documentaries. Shorter movies were…

Greener Approaches to Undergraduate Chemistry Experiments.

ERIC Educational Resources Information Center

Kirchhoff, Mary, Ed.; Ryan, Mary Ann, Ed.

This laboratory manual introduces the idea of Green Chemistry, which is the design of chemical products and processes that reduce or eliminate the use and generation of hazardous substances. Instructional samples are included to help teachers integrate green chemistry into the college chemistry curriculum. Each laboratory includes: (1) a…

42 CFR 493.931 - Routine chemistry.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 42 Public Health 5 2010-10-01 2010-10-01 false Routine chemistry. 493.931 Section 493.931 Public... Proficiency Testing Programs by Specialty and Subspecialty § 493.931 Routine chemistry. (a) Program content and frequency of challenge. To be approved for proficiency testing for routine chemistry, a program...

Supplemental Instruction in Physical Chemistry I

ERIC Educational Resources Information Center

Toby, Ellen; Scott, Timothy P.; Migl, David; Kolodzeji, Elizabeth

2016-01-01

Physical chemistry I at Texas A&M University is an upper division course requiring mathematical and analytical skills. As such, this course poses a major problem for many Chemistry, Engineering, Biochemistry and Genetics majors. Comparisons between participants and non-participants in Supplemental Instruction for physical chemistry were made…

42 CFR 493.931 - Routine chemistry.

Code of Federal Regulations, 2013 CFR

2013-10-01

... 42 Public Health 5 2013-10-01 2013-10-01 false Routine chemistry. 493.931 Section 493.931 Public... Proficiency Testing Programs by Specialty and Subspecialty § 493.931 Routine chemistry. (a) Program content and frequency of challenge. To be approved for proficiency testing for routine chemistry, a program...

42 CFR 493.931 - Routine chemistry.

Code of Federal Regulations, 2012 CFR

2012-10-01

... 42 Public Health 5 2012-10-01 2012-10-01 false Routine chemistry. 493.931 Section 493.931 Public... Proficiency Testing Programs by Specialty and Subspecialty § 493.931 Routine chemistry. (a) Program content and frequency of challenge. To be approved for proficiency testing for routine chemistry, a program...

42 CFR 493.931 - Routine chemistry.

Code of Federal Regulations, 2014 CFR

2014-10-01

... 42 Public Health 5 2014-10-01 2014-10-01 false Routine chemistry. 493.931 Section 493.931 Public... Proficiency Testing Programs by Specialty and Subspecialty § 493.931 Routine chemistry. (a) Program content and frequency of challenge. To be approved for proficiency testing for routine chemistry, a program...

42 CFR 493.931 - Routine chemistry.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 42 Public Health 5 2011-10-01 2011-10-01 false Routine chemistry. 493.931 Section 493.931 Public... Proficiency Testing Programs by Specialty and Subspecialty § 493.931 Routine chemistry. (a) Program content and frequency of challenge. To be approved for proficiency testing for routine chemistry, a program...

Atmospheric Chemistry Experiment (ACE) Measurements of Tropospheric and Stratospheric Chemistry and Long-Term Trends

NASA Technical Reports Server (NTRS)

Rinsland, Curtis P.; Bernath, Peter; Boone, Chris; Nassar, Ray

2007-01-01

We highlight chemistry and trend measurement results from the Atmospheric Chemistry Experiment (ACE) which is providing precise middle troposphere to the lower thermosphere measurements with a 0.02/cm resolution Fourier transform spectrometer covering 750-4400/cm

Green analytical chemistry--theory and practice.

PubMed

Tobiszewski, Marek; Mechlińska, Agata; Namieśnik, Jacek

2010-08-01

This tutorial review summarises the current state of green analytical chemistry with special emphasis on environmentally friendly sample preparation techniques. Green analytical chemistry is a part of the sustainable development concept; its history and origins are described. Miniaturisation of analytical devices and shortening the time elapsing between performing analysis and obtaining reliable analytical results are important aspects of green analytical chemistry. Solventless extraction techniques, the application of alternative solvents and assisted extractions are considered to be the main approaches complying with green analytical chemistry principles.

Polymer Chemistry

NASA Technical Reports Server (NTRS)

Williams, Martha; Roberson, Luke; Caraccio, Anne

2010-01-01

This viewgraph presentation describes new technologies in polymer and material chemistry that benefits NASA programs and missions. The topics include: 1) What are Polymers?; 2) History of Polymer Chemistry; 3) Composites/Materials Development at KSC; 4) Why Wiring; 5) Next Generation Wiring Materials; 6) Wire System Materials and Integration; 7) Self-Healing Wire Repair; 8) Smart Wiring Summary; 9) Fire and Polymers; 10) Aerogel Technology; 11) Aerogel Composites; 12) Aerogels for Oil Remediation; 13) KSC's Solution; 14) Chemochromic Hydrogen Sensors; 15) STS-130 and 131 Operations; 16) HyperPigment; 17) Antimicrobial Materials; 18) Conductive Inks Formulations for Multiple Applications; and 19) Testing and Processing Equipment.

Self-assembled mesoporous Co and Ni-ferrite spherical clusters consisting of spinel nanocrystals prepared using a template-free approach.

PubMed

Yu, Byong Yong; Kwak, Seung-Yeop

2011-10-21

Based on a self-assembly strategy, spherical mesoporous cobalt and nickel ferrite nanocrystal clusters with a large surface area and narrow size distribution were successfully synthesized for the first time via a template-free solvothermal process in ethylene glycol and subsequent heat treatment. In this work, the mesopores in the ferrite clusters were derived mainly from interior voids between aggregated primary nanoparticles (with crystallite size of less than 7 nm) and disordered particle packing domains. The concentration of sodium acetate is shown herein to play a crucial role in the formation of mesoporous ferrite spherical clusters. These ferrite clusters were characterized in detail using wide-angle X-ray diffraction, thermogravimetric-differential thermal analysis, (57)Fe Mössbauer spectroscopy, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy, standard and high-resolution transmission electron microscopy, and other techniques. The results confirmed the formation of both pure-phase ferrite clusters with highly crystalline spinel structure, uniform size (about 160 nm) and spherical morphology, and worm-like mesopore structures. The BET specific surface areas and mean pore sizes of the mesoporous Co and Ni-ferrite clusters were as high as 160 m(2) g(-1) and 182 m(2) g(-1), and 7.91 nm and 6.87 nm, respectively. A model for the formation of the spherical clusters in our system is proposed on the basis of the results. The magnetic properties of both samples were investigated at 300 K, and it was found that these materials are superparamagnetic. This journal is © The Royal Society of Chemistry 2011

Multi-Optimisation Consensus Clustering

NASA Astrophysics Data System (ADS)

Li, Jian; Swift, Stephen; Liu, Xiaohui

Ensemble Clustering has been developed to provide an alternative way of obtaining more stable and accurate clustering results. It aims to avoid the biases of individual clustering algorithms. However, it is still a challenge to develop an efficient and robust method for Ensemble Clustering. Based on an existing ensemble clustering method, Consensus Clustering (CC), this paper introduces an advanced Consensus Clustering algorithm called Multi-Optimisation Consensus Clustering (MOCC), which utilises an optimised Agreement Separation criterion and a Multi-Optimisation framework to improve the performance of CC. Fifteen different data sets are used for evaluating the performance of MOCC. The results reveal that MOCC can generate more accurate clustering results than the original CC algorithm.

Review of methods for handling confounding by cluster and informative cluster size in clustered data

PubMed Central

Seaman, Shaun; Pavlou, Menelaos; Copas, Andrew

2014-01-01

Clustered data are common in medical research. Typically, one is interested in a regression model for the association between an outcome and covariates. Two complications that can arise when analysing clustered data are informative cluster size (ICS) and confounding by cluster (CBC). ICS and CBC mean that the outcome of a member given its covariates is associated with, respectively, the number of members in the cluster and the covariate values of other members in the cluster. Standard generalised linear mixed models for cluster-specific inference and standard generalised estimating equations for population-average inference assume, in general, the absence of ICS and CBC. Modifications of these approaches have been proposed to account for CBC or ICS. This article is a review of these methods. We express their assumptions in a common format, thus providing greater clarity about the assumptions that methods proposed for handling CBC make about ICS and vice versa, and about when different methods can be used in practice. We report relative efficiencies of methods where available, describe how methods are related, identify a previously unreported equivalence between two key methods, and propose some simple additional methods. Unnecessarily using a method that allows for ICS/CBC has an efficiency cost when ICS and CBC are absent. We review tools for identifying ICS/CBC. A strategy for analysis when CBC and ICS are suspected is demonstrated by examining the association between socio-economic deprivation and preterm neonatal death in Scotland. PMID:25087978

Undergraduate Chemistry Education: A Workshop Summary

ERIC Educational Resources Information Center

Sawyer, Keegan; Alper, Joe

2014-01-01

"Undergraduate Chemistry Education" is the summary of a workshop convened in May 2013 by the Chemical Science Roundtable of the National Research Council to explore the current state of undergraduate chemistry education. Research and innovation in undergraduate chemistry education has been done for many years, and one goal of this…

Entangled quantum electronic wavefunctions of the Mn₄CaO₅ cluster in photosystem II.

PubMed

Kurashige, Yuki; Chan, Garnet Kin-Lic; Yanai, Takeshi

2013-08-01

It is a long-standing goal to understand the reaction mechanisms of catalytic metalloenzymes at an entangled many-electron level, but this is hampered by the exponential complexity of quantum mechanics. Here, by exploiting the special structure of physical quantum states and using the density matrix renormalization group, we compute near-exact many-electron wavefunctions of the Mn4CaO5 cluster of photosystem II, with more than 1 × 10(18) quantum degrees of freedom. This is the first treatment of photosystem II beyond the single-electron picture of density functional theory. Our calculations support recent modifications to the structure determined by X-ray crystallography. We further identify multiple low-lying energy surfaces associated with the structural distortion seen using X-ray crystallography, highlighting multistate reactivity in the chemistry of the cluster. Direct determination of Mn spin-projections from our wavefunctions suggests that current candidates that have been recently distinguished using parameterized spin models should be reassessed. Through entanglement maps, we reveal rich information contained in the wavefunctions on bonding changes in the cycle.

Choosing the Number of Clusters in K-Means Clustering

ERIC Educational Resources Information Center

Steinley, Douglas; Brusco, Michael J.

2011-01-01

Steinley (2007) provided a lower bound for the sum-of-squares error criterion function used in K-means clustering. In this article, on the basis of the lower bound, the authors propose a method to distinguish between 1 cluster (i.e., a single distribution) versus more than 1 cluster. Additionally, conditional on indicating there are multiple…

A Wet Chemistry Laboratory Cell

NASA Image and Video Library

2008-06-26

This picture of NASA Phoenix Mars Lander Wet Chemistry Laboratory WCL cell is labeled with components responsible for mixing Martian soil with water from Earth, adding chemicals and measuring the solution chemistry.

A Discovery Chemistry Experiment on Buffers

ERIC Educational Resources Information Center

Kulevich, Suzanne E.; Herrick, Richard S.; Mills, Kenneth V.

2014-01-01

The Holy Cross Chemistry Department has designed and implemented an experiment on buffers as part of our Discovery Chemistry curriculum. The pedagogical philosophy of Discovery Chemistry is to make the laboratory the focal point of learning for students in their first two years of undergraduate instruction. We first pose questions in prelaboratory…

One-world chemistry and systems thinking

NASA Astrophysics Data System (ADS)

Matlin, Stephen A.; Mehta, Goverdhan; Hopf, Henning; Krief, Alain

2016-05-01

The practice and overarching mission of chemistry need a major overhaul in order to be fit for purpose in the twenty-first century and beyond. The concept of 'one-world' chemistry takes a systems approach that brings together many factors, including ethics and sustainability, that are critical to the future role of chemistry.

THE SWIFT AGN AND CLUSTER SURVEY. II. CLUSTER CONFIRMATION WITH SDSS DATA

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

Griffin, Rhiannon D.; Dai, Xinyu; Kochanek, Christopher S.

2016-01-15

We study 203 (of 442) Swift AGN and Cluster Survey extended X-ray sources located in the SDSS DR8 footprint to search for galaxy over-densities in three-dimensional space using SDSS galaxy photometric redshifts and positions near the Swift cluster candidates. We find 104 Swift clusters with a >3σ galaxy over-density. The remaining targets are potentially located at higher redshifts and require deeper optical follow-up observations for confirmation as galaxy clusters. We present a series of cluster properties including the redshift, brightest cluster galaxy (BCG) magnitude, BCG-to-X-ray center offset, optical richness, and X-ray luminosity. We also detect red sequences in ∼85% ofmore » the 104 confirmed clusters. The X-ray luminosity and optical richness for the SDSS confirmed Swift clusters are correlated and follow previously established relations. The distribution of the separations between the X-ray centroids and the most likely BCG is also consistent with expectation. We compare the observed redshift distribution of the sample with a theoretical model, and find that our sample is complete for z ≲ 0.3 and is still 80% complete up to z ≃ 0.4, consistent with the SDSS survey depth. These analysis results suggest that our Swift cluster selection algorithm has yielded a statistically well-defined cluster sample for further study of cluster evolution and cosmology. We also match our SDSS confirmed Swift clusters to existing cluster catalogs, and find 42, 23, and 1 matches in optical, X-ray, and Sunyaev–Zel’dovich catalogs, respectively, and so the majority of these clusters are new detections.« less

General chemistry courses that can affect achievement: An action research study in developing a plan to improve undergraduate chemistry courses

NASA Astrophysics Data System (ADS)

Shweikeh, Eman

Over the past 50 years, considerable research has been dedicated to chemistry education. In evaluating principal chemistry courses in higher education, educators have noted the learning process for first-year general chemistry courses may be challenging. The current study investigated perceptions of faculty, students and administrators on chemistry education at three institutions in Southern California. Via action research, the study sought to develop a plan to improve student engagement in general chemistry courses. A mixed method was utilized to analyze different perceptions on key factors determining the level of commitment and engagement in general chemistry education. The approach to chemistry learning from both a faculty and student perspective was examined including good practices, experiences and extent of active participation. The research study considered well-known measures of effective education with an emphasis on two key components: educational practices and student behavior. Institutional culture was inclusively assessed where cognitive expectations of chemistry teaching and learning were communicated. First, the extent in which faculty members are utilizing the "Seven Principles for Good Practice in Undergraduate Education" in their instruction was explored. Second, student attitudes and approaches toward chemistry learning were examined. The focus was on investigating student understanding of the learning process and the structure of chemistry knowledge. The seven categories used to measure students' expectations for learning chemistry were: effort, concepts, math link, reality link, outcome, laboratory, and visualization. This analysis represents the views of 16 faculty and 140 students. The results validated the assertion that students need some competencies and skills to tackle the challenges of the chemistry learning process to deeply engage in learning. A mismatch exists between the expectations of students and those of the faculty

Quantum Chemistry in Great Britain: Developing a Mathematical Framework for Quantum Chemistry

NASA Astrophysics Data System (ADS)

Simões, Ana; Gavroglu, Kostas

By 1935 quantum chemistry was already delineated as a distinct sub-discipline due to the contributions of Fritz London, Walter Heitler, Friedrich Hund, Erich Hückel, Robert Mulliken, Linus Pauling, John van Vleck and John Slater. These people are credited with showing that the application of quantum mechanics to the solution of chemical problems was, indeed, possible, especially so after the introduction of a number of new concepts and the adoption of certain approximation methods. And though a number of chemists had started talking of the formation of theoretical or, even, mathematical chemistry, a fully developed mathematical framework of quantum chemistry was still wanting. The work of three persons in particular-of John E. Lennard-Jones, Douglas R. Hartree, and Charles Alfred Coulson-has been absolutely crucial in the development of such a framework. In this paper we shall discuss the work of these three researchers who started their careers in the Cambridge tradition of mathematical physics and who at some point of their careers all became professors of applied mathematics. We shall argue that their work consisted of decisive contributions to the development of such a mathematical framework for quantum chemistry.

Digital biology and chemistry.

PubMed

Witters, Daan; Sun, Bing; Begolo, Stefano; Rodriguez-Manzano, Jesus; Robles, Whitney; Ismagilov, Rustem F

2014-09-07

This account examines developments in "digital" biology and chemistry within the context of microfluidics, from a personal perspective. Using microfluidics as a frame of reference, we identify two areas of research within digital biology and chemistry that are of special interest: (i) the study of systems that switch between discrete states in response to changes in chemical concentration of signals, and (ii) the study of single biological entities such as molecules or cells. In particular, microfluidics accelerates analysis of switching systems (i.e., those that exhibit a sharp change in output over a narrow range of input) by enabling monitoring of multiple reactions in parallel over a range of concentrations of signals. Conversely, such switching systems can be used to create new kinds of microfluidic detection systems that provide "analog-to-digital" signal conversion and logic. Microfluidic compartmentalization technologies for studying and isolating single entities can be used to reconstruct and understand cellular processes, study interactions between single biological entities, and examine the intrinsic heterogeneity of populations of molecules, cells, or organisms. Furthermore, compartmentalization of single cells or molecules in "digital" microfluidic experiments can induce switching in a range of reaction systems to enable sensitive detection of cells or biomolecules, such as with digital ELISA or digital PCR. This "digitizing" offers advantages in terms of robustness, assay design, and simplicity because quantitative information can be obtained with qualitative measurements. While digital formats have been shown to improve the robustness of existing chemistries, we anticipate that in the future they will enable new chemistries to be used for quantitative measurements, and that digital biology and chemistry will continue to provide further opportunities for measuring biomolecules, understanding natural systems more deeply, and advancing molecular and

Bioorganic and bioinorganic chemistry.

PubMed

Constable, Edwin C; Housecroft, Catherine E; Creus, Marc; Gademann, Karl; Giese, Bernd; Ward, Thomas R; Woggon, Wolf D; Chougnet, Antoinette

2010-01-01

The interdisciplinary projects in bioinorganic and bioorganic chemistry of the Department of Chemistry, University of Basel led to the preparation of new systems that mimic biologically important processes and to the discovery of compounds from natural sources which are very promising with respect to medical applications. The advances in these areas are reported here.

Student continuation in high school chemistry

NASA Astrophysics Data System (ADS)

Bowen, James Iddon

2006-12-01

This investigation originally intended to uncover teacher behaviors that encourage students to persist in AP Chemistry in a typical urban Texas high school. As the investigation progressed, however, alternative reasons were sought for the persistence of some students when it became apparent that teacher behaviors might not be a factor in the decision to select AP Chemistry at the school under observation. In response to this, "Branding", a business theory which suggests certain attractive aspects of a product are promoted as a way to improve sales, is introduced as an alternative way of thinking about persistence in chemistry. "Branding" can explain why some students continue to select chemistry in the face of disappointing teaching. It is also argued here that "Branding" can encourage more students to take chemistry in the future.

Analysis of Network Clustering Algorithms and Cluster Quality Metrics at Scale

PubMed Central

Kobourov, Stephen; Gallant, Mike; Börner, Katy

2016-01-01

Overview Notions of community quality underlie the clustering of networks. While studies surrounding network clustering are increasingly common, a precise understanding of the realtionship between different cluster quality metrics is unknown. In this paper, we examine the relationship between stand-alone cluster quality metrics and information recovery metrics through a rigorous analysis of four widely-used network clustering algorithms—Louvain, Infomap, label propagation, and smart local moving. We consider the stand-alone quality metrics of modularity, conductance, and coverage, and we consider the information recovery metrics of adjusted Rand score, normalized mutual information, and a variant of normalized mutual information used in previous work. Our study includes both synthetic graphs and empirical data sets of sizes varying from 1,000 to 1,000,000 nodes. Cluster Quality Metrics We find significant differences among the results of the different cluster quality metrics. For example, clustering algorithms can return a value of 0.4 out of 1 on modularity but score 0 out of 1 on information recovery. We find conductance, though imperfect, to be the stand-alone quality metric that best indicates performance on the information recovery metrics. Additionally, our study shows that the variant of normalized mutual information used in previous work cannot be assumed to differ only slightly from traditional normalized mutual information. Network Clustering Algorithms Smart local moving is the overall best performing algorithm in our study, but discrepancies between cluster evaluation metrics prevent us from declaring it an absolutely superior algorithm. Interestingly, Louvain performed better than Infomap in nearly all the tests in our study, contradicting the results of previous work in which Infomap was superior to Louvain. We find that although label propagation performs poorly when clusters are less clearly defined, it scales efficiently and accurately to large

Changes in stream chemistry and biology in response to reduced levels of acid deposition during 1987-2003 in the Neversink River Basin, Catskill Mountains

USGS Publications Warehouse

Burns, Douglas A.; Riva-Murray, K.; Bode, R.W.; Passy, S.

2008-01-01

Atmospheric acid deposition has decreased in the northeastern United States since the 1970s, resulting in modest increases in pH, acid-neutralizing capacity (ANC), and decreases in inorganic monomeric aluminum (AlIM) concentrations since stream chemistry monitoring began in the 1980s in the acid-sensitive upper Neversink River basin in the Catskill Mountains of New York. Stream pH has increased by 0.01 units/year during 1987-2003 at three sites in the Neversink basin as determined by Seasonal Kendall trend analysis. In light of this observed decrease in stream acidity, we sampled 12 stream sites within the Neversink River watershed for water chemistry, macroinvertebrates, fish, and periphytic diatoms in 2003 to compare with a similar data set collected in 1987. Metrics and indices that reflect sensitivity to stream acidity were developed with these biological data to determine whether changes in stream biota over the intervening 16 years parallel those of stream chemistry. Statistical comparisons of data on stream chemistry and an acid biological assessment profile (Acid BAP) derived from invertebrate data showed no significant differences between the two years. For pH and ANC, however, values in 2003 were generally lower than those in 1987; this difference likely resulted from higher streamflow in summer 2003. Despite these likely flow-induced changes in summer 2003, an ordination and cluster analysis of macroinvertebrate taxa based on the Acid BAP indicated that the most acidic sites in the upstream half of the East Branch Neversink River form a statistically significant separate cluster consistent with less acidic stream conditions. This analysis is consistent with limited recovery of invertebrate species in the most acidic reaches of the river, but will require additional improvement in stream chemistry before a stronger conclusion can be drawn. Data on the fish and periphytic diatom communities in 2003 indicate that slimy sculpin had not extended their habitat

Globular cluster formation with multiple stellar populations from hierarchical star cluster complexes

NASA Astrophysics Data System (ADS)

Bekki, Kenji

2017-05-01

Most old globular clusters (GCs) in the Galaxy are observed to have internal chemical abundance spreads in light elements. We discuss a new GC formation scenario based on hierarchical star formation within fractal molecular clouds. In the new scenario, a cluster of bound and unbound star clusters ('star cluster complex', SCC) that have a power-law cluster mass function with a slope (β) of 2 is first formed from a massive gas clump developed in a dwarf galaxy. Such cluster complexes and β = 2 are observed and expected from hierarchical star formation. The most massive star cluster ('main cluster'), which is the progenitor of a GC, can accrete gas ejected from asymptotic giant branch (AGB) stars initially in the cluster and other low-mass clusters before the clusters are tidally stripped or destroyed to become field stars in the dwarf. The SCC is initially embedded in a giant gas hole created by numerous supernovae of the SCC so that cold gas outside the hole can be accreted on to the main cluster later. New stars formed from the accreted gas have chemical abundances that are different from those of the original SCC. Using hydrodynamical simulations of GC formation based on this scenario, we show that the main cluster with the initial mass as large as [2-5] × 105 M⊙ can accrete more than 105 M⊙ gas from AGB stars of the SCC. We suggest that merging of hierarchical SSCs can play key roles in stellar halo formation around GCs and self-enrichment processes in the early phase of GC formation.

Relative efficiency and sample size for cluster randomized trials with variable cluster sizes.

PubMed

You, Zhiying; Williams, O Dale; Aban, Inmaculada; Kabagambe, Edmond Kato; Tiwari, Hemant K; Cutter, Gary

2011-02-01

The statistical power of cluster randomized trials depends on two sample size components, the number of clusters per group and the numbers of individuals within clusters (cluster size). Variable cluster sizes are common and this variation alone may have significant impact on study power. Previous approaches have taken this into account by either adjusting total sample size using a designated design effect or adjusting the number of clusters according to an assessment of the relative efficiency of unequal versus equal cluster sizes. This article defines a relative efficiency of unequal versus equal cluster sizes using noncentrality parameters, investigates properties of this measure, and proposes an approach for adjusting the required sample size accordingly. We focus on comparing two groups with normally distributed outcomes using t-test, and use the noncentrality parameter to define the relative efficiency of unequal versus equal cluster sizes and show that statistical power depends only on this parameter for a given number of clusters. We calculate the sample size required for an unequal cluster sizes trial to have the same power as one with equal cluster sizes. Relative efficiency based on the noncentrality parameter is straightforward to calculate and easy to interpret. It connects the required mean cluster size directly to the required sample size with equal cluster sizes. Consequently, our approach first determines the sample size requirements with equal cluster sizes for a pre-specified study power and then calculates the required mean cluster size while keeping the number of clusters unchanged. Our approach allows adjustment in mean cluster size alone or simultaneous adjustment in mean cluster size and number of clusters, and is a flexible alternative to and a useful complement to existing methods. Comparison indicated that we have defined a relative efficiency that is greater than the relative efficiency in the literature under some conditions. Our measure

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