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  Partner: UNT College of Arts and Sciences
 Decade: 2000-2009
 Year: 2004
Rediscovery of the Elements: The Second Discovery of Vanadium

Rediscovery of the Elements: The Second Discovery of Vanadium

Date: Autumn 2004
Creator: Marshall, James L., 1940- & Marshall, Virginia R.
Description: Article describing how vanadium was "rediscovered" in Sweden and found to be identical to del Rio's sample. Includes tourist information regarding areas relevant to this portion of vanadium's history.
Contributing Partner: UNT College of Arts and Sciences
Rediscovery of the Elements: The Undiscovery of Vanadium

Rediscovery of the Elements: The Undiscovery of Vanadium

Date: Summer 2004
Creator: Marshall, James L., 1940- & Marshall, Virginia R.
Description: Article describing the how the original vanadium sample was misanalysed and identified as chromium. Includes tourist information regarding Paris, France.
Contributing Partner: UNT College of Arts and Sciences
LIN, a Medicago truncatula Gene Required for Nodule Differentiation and Persistence of Rhizobial Infections

LIN, a Medicago truncatula Gene Required for Nodule Differentiation and Persistence of Rhizobial Infections

Date: November 2004
Creator: Kuppusamy, Kavitha T.; Endre, Gabriella; Prabhu, Radhika; Penmetsa, R. Varma; Veereshlingam, Harita; Cook, Douglas R. et al
Description: This article discusses LIN, a Medicago truncatula gene. Abstract: Ethyl methanesulfonate mutagenesis of the model legume Medicago truncatula has previously identified several genes required for early steps in nodulation. Here, the authors describe a new mutant that is defective in intermediate steps of nodule differentiation. The lin (lumpy infections) mutant is characterized by a 4-fold reduction in the number of infections, all of which arrest in the root epidermis, and by nodule primordia that initiate normally but fail to mature. Genetic analyses indicate that the symbiotic phenotype is conferred by a single gene that maps to the lower arm of linkage group 1. Transcriptional markers for early Nod factor responses (RIP1 and ENOD40) are induced in lin, as is another early nodulin, ENOD20, a gene expressed during the differentiation of nodule primordia. By contrast, other markers correlated with primordium differentiation (CCS52A), infection progression (MtN6), or nodule morphogenesis (ENOD2 and ENOD8) show reduced or no induction in homozygous lin individuals. Taken together, these results suggest that LIN functions in maintenance of rhizobial infections and differentiation of nodules from nodule primordia.
Contributing Partner: UNT College of Arts and Sciences
Non-Poisson Dichotomous Noise: Higher-Order Correlation Functions and Aging

Non-Poisson Dichotomous Noise: Higher-Order Correlation Functions and Aging

Date: October 26, 2004
Creator: Allegrini, Paolo; Grigolini, Paolo; Palatella, Luigi & West, Bruce J.
Description: In this article, the authors study a two-state symmetric noise, with a given waiting time distribution ψ(τ), and focus their attention on the connection between the four-time and two-time correlation functions. The transition of ψ(τ) from the exponential to the nonexponential condition yields the breakdown of the usual factorization condition of high-order correlation functions, as well as the birth of aging effects. The authors discuss the subtle connections between these two properties and establish the condition that the Liouville-like approach has to satisfy in order to produce a correct description of the resulting diffusion process.
Contributing Partner: UNT College of Arts and Sciences
Reactions of TpRu(CO) (NCMe) (Me) (Tp = Hydridotris(pyrazolyl)borate) with Heteroaromatic Substrates: Stoichiometric and Catalytic C-H Activation

Reactions of TpRu(CO) (NCMe) (Me) (Tp = Hydridotris(pyrazolyl)borate) with Heteroaromatic Substrates: Stoichiometric and Catalytic C-H Activation

Date: October 15, 2004
Creator: Pittard, Karl A.; Lee, John P.; Cundari, Thomas R., 1964-; Gunnoe, T. Brent & Petersen, Jeffrey L.
Description: This article discusses reactions of TpRu(CO)(NCMe)(Me) (Tp = Hydridotris(pyrazolyl)borate) with heteroaromatic substrates. The Ru(II) complex TpRu(CO)(NCMe)(Me) (Tp = hydridotris(pyrazolyl)borate) initiates carbon-hydrogen bond activation at the 2-position of furan and thiophene to produce methane and TpRu(CO)(NCMe)(aryl) (aryl = 2-furyl or 2-thienyl). Solid-state structures have been determined for TpRu(CO)(NCMe)(2-thienyl) and [TpRu(CO)(μ-C,S-thienyl)]2. The complex TpRu(CO)(NCMe)(2-furyl) serves as a catalyst for the formation of 2-ethylfuran from ethylene and furan. DFT calculations of the C-H activation of furan by {(Tab)Ru-(CO)(Me)} (Tab = tris(azo)borate) indicate that the C-H activation sequence does not proceed through a Ru(IV) oxidative addition intermediate.
Contributing Partner: UNT College of Arts and Sciences
Using GIS technology to identify areas of tuberculosis transmission and incidence

Using GIS technology to identify areas of tuberculosis transmission and incidence

Date: October 13, 2004
Creator: Moonan, Patrick K.; Bayona, Manuel; Quitugua, Teresa N.; Oppong, Joseph R.; Dunbar, Denise; Jost, Kenneth C. et al
Description: This article discusses using GIS technology to identify areas of tuberculosis transmission and incidence. Background: Currently in the U.S. it is recommended that tuberculosis screening and treatment programs be targeted at high-risk populations. While a strategy of targeted testing and treatment of persons most likely to develop tuberculosis is attractive, it is uncertain how best to accomplish this goal. In this study the authors seek to identify geographical areas where on-going tuberculosis transmission is occurring by linking Geographic Information Systems (GIS) technology with molecular surveillance. Methods: This cross-sectional analysis was performed on data collected on persons newly diagnosed with culture positive tuberculosis at the Tarrant County Health Department (TCHD) between January 1, 1993 and December 31, 2000. Clinical isolates were molecularly characterized using IS6 110-based RFLP analysis and spoligotyping methods to identify patients infected with the same strain. Residential addresses at the time of diagnosis of tuberculosis were geocoded and mapped according to strain characterization. Generalized estimating equations (GEE) analysis models were used to identify risk factors involved in clustering. Results: Evaluation of the spatial distribution of cases within zip-code boundaries identified distinct areas of geographical distribution of same strain disease. The authors identified these geographical areas as having increased ...
Contributing Partner: UNT College of Arts and Sciences
Reversible Beta-Hydrogen Elimination of Three-Coordinate Iron(II) Alkyl Complexes: Mechanistic and Thermodynamic Studies

Reversible Beta-Hydrogen Elimination of Three-Coordinate Iron(II) Alkyl Complexes: Mechanistic and Thermodynamic Studies

Date: October 1, 2004
Creator: Vela, Javier; Vaddadi, Sridhar; Cundari, Thomas R., 1964-; Smith, Jeremy M.; Gregory, Elizabeth A.; Lachicotte, Rene J. et al
Description: This article discusses reversible beta-hydrogen elimination of three-coordinate iron(II) alkyl complexes. High-spin organometallic complexes have not received extensive mechanistic study, despite their potential importance as unsaturated intermediates in catalytic transformations. The authors have found that, with a suitably bulky bidentate ligand, three-coordinate, high-spin alkyl complexes of iron(II) are stable. They undergo isomerization and exchange reactions of the alkyl group through β-hydride elimination and reinsertion, and the β-hydride elimination step is rate-limiting. The alkyl complexes transfer a β-hydrogen atom to C=C, C=N, and C=O double bonds and undergo deprotonation by Brønsted acids. The reversible β-hydride elimination reactions can be used to explore relative M-C bond energies. Competition experiments and density functional calculations demonstrate an enthalpic preference for alkyl isomers with iron bound to the terminal carbon of the alkyl fragment. This preference arises from steric and electronic effects. The steric preference could be overcome with a phenyl substituent, which steers iron to the benzylic position. A Hammett correlation and density functional calculations suggest that the substituent effect is attributable to resonance stabilization of partial negative charge on the alkyl ligand.
Contributing Partner: UNT College of Arts and Sciences
Aging and Rejuvenation with Fractional Derivatives

Aging and Rejuvenation with Fractional Derivatives

Date: September 10, 2004
Creator: Aquino, Gerardo; Bologna, Mauro; Grigolini, Paolo & West, Bruce J.
Description: This article discusses aging rejuvenation with fractional derivatives. Abstract: We discuss a dynamic procedure that makes a fractional derivatives emerge in the time asymptotic limit of non-Poisson processes. We find that two-state fluctuations, with an inverse power-law distribution of waiting times, finite first moment, and divergent second moment, namely, with the power index μ in the interval 2<μ<3, yield a generalized master equation equivalent to the sum of an ordinary Markov contribution and a fractional derivative term. We show that the order of the fractional derivative depends on the age of the process under study. If the system is infinitely old, the order of the fractional derivative, o, is given by o=3-μ. A brand new system is characterized by the degree o=μ-2. If the system is prepared at time -tₐ<0 and the observation begins at time t=0, we derive the following scenario. For times 0<t«tₐ the system is satisfactorily described by the fractional derivative with o=3-μ. Upon time increase the system undergoes a rejuvenation process that in the time limit t⪢tₐ yields o=μ-2. The intermediate time regime is probably incompatible with a picture based on fractional derivatives, or, at least, with a mono-order fractional derivative.
Contributing Partner: UNT College of Arts and Sciences
Experimental and Computational Studies of Ruthenium(II)-Catalyzed Addition of Arene C-H Bonds to Olefins

Experimental and Computational Studies of Ruthenium(II)-Catalyzed Addition of Arene C-H Bonds to Olefins

Date: September 10, 2004
Creator: Lail, Marty; Bell, Christen M.; Conner, David; Cundari, Thomas R., 1964-; Gunnoe, T. Brent & Petersen, Jeffrey L.
Description: This article discusses experimental and computational studies of Ruthenium(II)-Catalyzed addition of arene C-H bonds to olefins. Abstract: Hydroarylation reactions of olefins are catalyzed by the octahedral Ru(II) complex TpRu-(CO)(NCMe)(Ph) (1) (Tp = hydridotris(pyrazolyl)borate). Experimental studies and density functional theory calculations support a reaction pathway that involves initial acetonitrile/olefin ligand exchange and subsequent olefin insertion into the ruthenium-phenyl bond. Metal-mediated C-H activation of arene to form a Ru-aryl bond with release of alkyl arene completes the proposed catalytic cycle. The cyclopentadienyl complex CpRu(PPh3)2(Ph) produces ethylbenzene and styrene from a benzene/ethylene solution at 90 ˚C; however, the transformation is not catalytic. A benzene solution of (PCP)Ru(CO)(Ph) (PCP = 2,6-)CH2Pt-Bu2)2C6H3) and ethylene at 90 ˚C produces styrene in 12% yield without observation of ethylbenzene. Computational studies (DFT) suggest that the C-H activation step does not proceed through the formation of a Ru(IV) oxidative addition intermediate but rather occurs by a concerted pathway.
Contributing Partner: UNT College of Arts and Sciences
Graft Transmission of a Floral Stimulant Derived from CONSTANS

Graft Transmission of a Floral Stimulant Derived from CONSTANS

Date: August 2004
Creator: Ayre, Brian G. & Turgeon, Robert
Description: This article discusses graft transmission of a floral stimulant derived from CONSTANS. Abstract: Photoperiod in plants is perceived by leaves and in many species influences the transition to reproductive growth through long-distance signaling. CONSTANS (CO) is implicated as a mediator between photoperiod perception and the transition to flowering in Arabidopsis. To test the role of CO in long-distance signaling, CO was expressed from a promoter specific to the companion cells of the smallest veins of mature leaves. This expression in tissues at the inception of the phloem translocation stream was sufficient to accelerate flowering at the apical meristem under noninductive (short-day) conditions. Grafts that conjoined the vegetative stems of plants with different flower-timing phenotypes demonstrated that minor-vein expression of CO is able to substitute for photoperiod in generating a mobile flowering signal. The authors' results suggest that a CO-derived signal(s), or possibly CO itself, fits the definition of the hypothetical flowering stimulant, florigen.
Contributing Partner: UNT College of Arts and Sciences
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