Two distinct [Cu-O-Cu](2+) sites with methane monooxygenase activity are identified in the zeolite Cu-MOR, emphasizing that this Cu-O-Cu active site geometry, having a ∠Cu-O-Cu ∼140°, is particularly formed and stabilized in zeolite topologies. Whereas in ZSM-5 a similar [Cu-O-Cu](2+) active site is located in the intersection of the two 10 membered rings, Cu-MOR provides two distinct local structures, situated in the 8 membered ring windows of the side pockets. Despite their structural similarity, as ascertained by electronic absorption and resonance Raman spectroscopy, the two Cu-O-Cu active sites in Cu-MOR clearly show different kinetic behaviors in selective methane oxidation. This difference in reactivity is too large to be ascribed to subtle differences in the ground states of the Cu-O-Cu sites, indicating the zeolite lattice tunes their reactivity through second-sphere effects. The MOR lattice is therefore functionally analogous to the active site pocket of a metalloenzyme, demonstrating that both the active site and its framework environment contribute to and direct reactivity in transition metal ion-zeolites.

Understanding the formation mechanism of the [Cu2O](2+) active site in Cu-ZSM-5 is important for the design of efficient catalysts to selectively convert methane to methanol and related value-added chemicals and for N2O decomposition. Spectroscopically validated DFT calculations are used here to evaluate the thermodynamic and kinetic requirements for formation of [Cu2O](2+) active sites from the reaction between binuclear Cu(I) sites and N2O in the 10-membered rings Cu-ZSM-5. Thermodynamically, the most stable Cu(I) center prefers bidentate coordination with a close to linear bite angle. This binuclear Cu(I) site reacts with N2O to generate the experimentally observed [Cu2O](2+) site. Kinetically, the reaction coordinate was evaluated for two representative binuclear Cu(I) sites. When the Cu-Cu distance is sufficiently short (<4.2 Å), N2O can bind in a "bridged" μ-1,1-O fashion and the oxo-transfer reaction is calculated to proceed with a low activation energy barrier (2 kcal/mol). This is in good agreement with the experimental Ea for N2O activation (2.5 ± 0.5 kcal/mol). However, when the Cu-Cu distance is long (>5.0 Å), N2O binds in a "terminal" η(1)-O fashion to a single Cu(I) site of the dimer and the resulting E(a) for N2O activation is significantly higher (16 kcal/mol). Therefore, bridging N2O between two Cu(I) centers is necessary for its efficient two-electron activation in [Cu2O](2+) active site formation. In nature, this N2O reduction reaction is catalyzed by a tetranuclear CuZ cluster that has a higher E(a). The lower E(a) for Cu-ZSM-5 is attributed to the larger thermodynamic driving force resulting from formation of strong Cu(II)-oxo bonds in the ZSM-5 framework.

Dinitrosyl iron complexes (DNICs) have been recognized as storage and transport agents of nitric oxide capable of selectively modifying crucial biological targets via its distinct redox forms (NO(+), NO(•) and NO(-)) to initiate the signaling transduction pathways associated with versatile physiological and pathological responses. For decades, the molecular geometry and spectroscopic identification of {Fe(NO)2}(9) DNICs ({Fe(NO)x}(n) where n is the sum of electrons in the Fe 3d orbitals and NO π* orbitals based on Enemark-Feltham notation) in biology were limited to tetrahedral (CN = 4) and EPR g-value ∼2.03, respectively, due to the inadequacy of structurally well-defined biomimetic DNICs as well as the corresponding spectroscopic library accessible in biological environments. The developed synthetic methodologies expand the scope of DNICs into nonclassical square pyramidal and trigonal bipyramidal (CN = 5) and octahedral (CN = 6) {Fe(NO)2}(9) DNICs, as well as two/three accessible redox couples for mononuclear {Fe(NO)2}(9/10) and dinuclear [{Fe(NO)2}(9/10)-{Fe(NO)2}(9/10)] DNICs with biologically relevant S/O/N ligation modes. The unprecedented molecular geometries and electronic states of structurally well-defined DNIC models provide the foundation to construct a spectroscopic library for uncovering the identity of DNICs in biological environments as well as to determine the electronic structures of the {Fe(NO)2} core in qualitative and quantitative fashions by a wide range of spectroscopic methods. On the basis of (15)N NMR, electron paramagnetic resonance (EPR), IR, cyclic voltammetry (CV), superconducting quantum interference device (SQUID) magnetometry, UV-vis, single-crystal X-ray crystallography, and Fe/S K-edge X-ray absorption and Fe Kβ X-ray emission spectroscopies, the molecular geometry, ligation modes, nuclearity, and electronic states of the mononuclear {Fe(NO)2}(9/10) and dinuclear [{Fe(NO)2}(9/10)-{Fe(NO)2}(9/10)] DNICs could be characterized and differentiated. In addition, Fe/S K-edge X-ray absorption spectroscopy of tetrahedral DNICs deduced the qualitative assignment of Fe/NO oxidation states of {Fe(NO)2}(9) DNICs as a resonance hybrid of {Fe(II)((•)NO)(NO(-))}(9) and {Fe(III)(NO(-))2}(9) electronic states; the quantitative NO oxidation states of [(PhS)3Fe(NO)](-), [(PhS)2Fe(NO)2](-), and [(PhO)2Fe(NO)2](-) were further achieved by newly developed valence to core Fe Kβ X-ray emission spectroscopy as -0.58 ± 0.18, -0.77 ± 0.18, and -0.95 ± 0.18, respectively. The in-depth elaborations of electronic structures provide credible guidance to elucidate (a) the essential roles of DNICs modeling the degradation and repair of [Fe-S] clusters under the presence of NO, (b) transformation of DNIC into S-nitrosothiol (RSNO)/N-nitrosamine (R2NNO) and NO(+)/NO(•)/NO(-), (c) nitrite/nitrate activation producing NO regulated by redox shuttling of {Fe(NO)2}(9) and {Fe(NO)2}(10) DNICs, and (d) DNICs as H2S storage and cellular permeation pathway of DNIC/Roussin's red ester (RRE) for subsequent protein S-nitros...

Copper-containing zeolites, such as mordenite (MOR), have recently gained increased attention as a consequence of their catalytic potential. While the preferred copper loadings in these catalytic studies are generally high, the literature lacks appropriate spectroscopic and structural information on such Cu-rich zeolite samples. Higher copper loadings increase the complexity of the copper identity and their location in the zeolite host, but they also provide the opportunity to create novel Cu sites, which are perhaps energetically less favorable, but possibly more reactive and more suitable for catalysis. In order to address the different role of each Cu site in catalysis, we here report a combined electron paramagnetic resonance (EPR), UV/Vis-NIR and temperature-programmed reduction (TPR) study on highly copper-loaded MOR. Highly resolved diffuse reflectance (DR) spectra of the CuMOR samples were obtained due to the increased copper loading, allowing the differentiation of two isolated mononuclear Cu(2+) sites and the unambiguous correlation with extensively reported features in the EPR spectrum. Ligand field theory is applied together with earlier suggested theoretical calculations to determine their coordination chemistry and location within the zeolite matrix, and the theoretical analysis further allowed us to define factors governing their redox behavior. In addition to monomeric species, an EPR-silent, possibly dimeric, copper site is present in accordance with its charge transfer absorption feature at 22200 cm(-1), and quantified with TPR. Its full description and true location in MOR is currently being investigated.

Purpose -The objective of this study is to discuss the critical success factors involved in implementing a knowledge management system (KMS), in order to enhance a firm's competitiveness, while keeping costs to a minimum. Design/methodology/approach -Based on field studies and a literature review, this study outlined 32 variables in the implementation of a KMS. The research targets were on members of the Taiwan Pharmaceutical Marketing and Management Association (TPMMA). Out of the 355 questionnaires sent, 98 valid questionnaires were returned, resulting in a valid return rate of 27.6 percent. Findings -After completing the statistical analysis, seven factors were determined to be critical: a benchmarking strategy and knowledge structure; the organizational culture; information technology; employee involvement and training; the leadership and the commitment of senior management; a learning environment and resource control; and evaluation of professional training and teamwork. Research limitations/implications -This paper chooses members of TPMMA as research targets; thus, to apply this study to other than pharmaceutical industries requires further research. Practical implications -Strategy and organizational culture are important in the adoption of a KMS. This study has determined that the pharmaceutical industry has paid special attention to benchmarking strategy. Adopting a KMS can be easy with a core department to maintain proper function of the system. However, companies should utilize the intangible assets available through a KMS to attain full participation from the employees to ensure the success of implementing an effective KMS. Originality/value -This paper identifies critical factors in adopting a KMS for the pharmaceutical industry. That can offer pragmatic indication for those companies intent on introducing a KMS.

Dinitrosyl iron complex [(-SC(7)H(4)SN)(2)Fe(NO)(2)](-) (1) was prepared by reaction of [S(5)Fe(NO)(2)](-) and bis(2-benzothiozolyl) disulfide. In synthesis of the analogous dinitrosyl iron compounds (DNICs), the stronger electron-donating thiolates [RS](-) (R = C(6)H(4)-o-NHCOCH(3), C(4)H(3)S, C(6)H(4)NH(2), Ph), compared to [-SC(7)H(4)SN](-) of complex 1, trigger thiolate-ligand substitution to yield [(-SC(6)H(4)-o-NHCOCH(3))(2)Fe(NO)(2)](-) (2), [(-SC(4)H(3)S)(2)Fe(NO)(2)](-) (3), and [(SPh)(2)Fe(NO)(2)](-) (4), respectively. At 298 K, complexes 2 and 3 exhibit a well-resolved five-line EPR signal at g = 2.038 and 2.027, respectively, the characteristic g value of DNICs. The magnetic susceptibility fit indicates that the resonance hybrid of {Fe(+)((*)NO)(2)}(9) and {Fe(-)((+)NO)(2)}(9) in 2 is dynamic by temperature. The IR nu(NO) stretching frequencies (ranging from (1766, 1716) to (1737, 1693) cm(-)(1) (THF)) of complexes 1-4 signal the entire window of possible electronic configurations for such stable and isolable {Fe(NO)(2)}(9) [(RS)(2)Fe(NO)(2)](-). The NO-releasing ability of {Fe(NO)(2)}(9) [(RS)(2)Fe(NO)(2)](-) is finely tuned by the coordinated thiolate ligands. The less electron-donating thiolate ligands coordinated to {Fe(NO)(2)}(9) motif act as better NO-donor DNICs in the presence of NO-trapping agent [Fe(S,S-C(6)H(4))(2)](2)(2-). Interconversion between {Fe(NO)(2)}(9) [(RS)(2)Fe(NO)(2)](-) and {Fe(NO)(2)}(10) [(Ph(3)P)(2)Fe(NO)(2)] was verified in the reaction of (a) [(RS)(2)Fe(NO)(2)](-), 10 equiv of PPh(3) and sodium-biphenyl, and (b) 2 equiv of thiol, [RS](-), and [(Ph(3)P)(2)Fe(NO)(2)], respectively. The biomimetic reaction cycle, transformation between {Fe(NO)(2)}(9) [(RS)(2)Fe(NO)(2)](-) and {Fe(NO)(2)}(9) [(R'S)(2)Fe(NO)(2)](-), reversible interconversion of {Fe(NO)(2)}(9) and {Fe(NO)(2)}(10) DNICs, and degradation/reassembly of [2Fe-2S] clusters may decipher and predict the biological cycle of interconversion of {Fe(NO)(2)}(9) DNICs, {Fe(NO)(2)}(10) DNICs, and the [Fe-S] clusters in proteins.

The synthesis, characterization, and transformation of the anionic {Fe(NO)(2)}(9) dinitrosyl iron complexes (DNICs) [(NO)(2)Fe(ONO)(2)](-) (1), [(NO)(2)Fe(OPh)(2)](-) (2), [(NO)(2)Fe(OPh)(C(3)H(3)N(2))](-) (3) (C(3)H(3)N(2) = imidazolate), [(NO)(2)Fe(OPh)(-SC(4)H(3)S)](-) (4), [(NO)(2)Fe(p-OPhF)(2)](-) (5), and [(NO)(2)Fe(SPh)(ONO)](-) (6) were investigated. The binding affinity of ligands ([SPh](-), [-SC(4)H(3)S](-), [C(3)H(3)N(2)](-), [OPh](-), and [NO(2)](-)) toward the {Fe(NO)(2)}(9) motif follows the ligand-displacement series [SPh](-) approximately [-SC(4)H(3)S](-) > [C(3)H(3)N(2)](-) > [OPh](-) > [NO(2)](-). The findings, the pre-edge energy derived from the 1s --> 3d transition in a distorted T(d) environment of the Fe center falling within the range of 7113.4-7113.8 eV for the anionic {Fe(NO)(2)}(9) DNICs, implicate that the iron metal center of DNICs is tailored to minimize the electronic changes accompanying changes in coordinated ligands. Our results bridging the ligand-substitution reaction study and X-ray absorption spectroscopy study of the electronic richness of the {Fe(NO)(2)}(9) core may point the way to understanding the reasons for nature's choice of combinations of cysteine, histidine, and tyrosine in protein-bound DNICs and rationalize that most DNICs characterized/proposed nowadays are bound to the proteins almost through the thiolate groups of cysteinate/glutathione side chains in biological systems.

Bubbling O into a THF solution of Co(BDPP) (1) at -90 °C generates an O adduct, Co(BDPP)(O) (3). The resonance Raman and EPR investigations reveal that 3 contains a low spin cobalt(III) ion bound to a superoxo ligand. Significantly, at -90 °C, 3 can react with 2,2,6,6-tetramethyl-1-hydroxypiperidine (TEMPOH) to form a structurally characterized cobalt(III)-hydroperoxo complex, Co(BDPP)(OOH) (4) and TEMPO. Our findings show that cobalt(III)-superoxo species are capable of performing hydrogen atom abstraction processes. Such a stepwise O-activating process helps to rationalize cobalt-catalyzed aerobic oxidations and sheds light on the possible mechanism of action for Co-bleomycin.