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51.
The tentative identification of the reactive species in the condensation of Cp2 TiCl2 with salts of diacids to form titanium polysters is made. The reactive species are believed to be the same for both aqueous solution and interfacial systems, i.e., R -CO2 ? and Cp2 Ti2+ with reaction occurring in the aqueous phase. The condensation of Cp2 TiCl2 with disodium terephthalate in interfacial systems occurs via a pseudo-first-order reaction: Rate = K[Cp2 TiCl2] The rate-determining step (s) is believed to be diffusion of CP2 TiCl2 into the aqueous layer and/or hydrolysis of Cp2 TiCl2 相似文献
52.
Utilizing a hexadentate ligand platform, a trinuclear manganese complex of the type ((H)L)Mn(3)(thf)(3) was synthesized and characterized ([(H)L](6-) = [MeC(CH(2)N(C(6)H(4)-o-NH))(3)](6-)). The pale-orange, formally divalent trimanganese complex rapidly reacts with O-atom transfer reagents to afford the μ(6)-oxo complex ((H)L)(2)Mn(6)(μ(6)-O)(NCMe)(4), where two trinuclear subunits bind the central O-atom and the ((H)L) ligands cooperatively bind both trinuclear subunits. The trimanganese complex ((H)L)Mn(3)(thf)(3) rapidly consumes inorganic azide ([N(3)]NBu(4)) to afford a dianionic hexanuclear nitride complex [((H)L)(2)Mn(6)(μ(6)-N)](NBu(4))(2), which subsequently can be oxidized with elemental iodine to ((H)L)(2)Mn(6)(μ(6)-N)(NCMe)(4). EPR and alkylation of the interstitial light atom substituent were used to distinguish the nitride from the oxo complex. The oxo and oxidized nitride complexes give rise to well-defined Mn(II) and Mn(III) sites, determined by bond valence summation, while the dianionic nitride shows a more symmetric complex, giving rise to indistinguishable ion oxidation states based on crystal structure bond metrics. 相似文献
53.
OVERSTREET GEORGE A. JR; BREDLEY EDWIN L. JR 《IMA Journal of Management Mathematics》1996,7(4):291-311
Although credit-scoring models represent a widely used managerialaid for large financial intermediaries, the vast majority ofU.S. credit unionsrelatively small cooperatively ownedretail intermediaries, constrained by sample and funding limitationshaveyet to adopt such techniques. Lovie & Lovie (1986) havetheorized that the flat-maximum effect or curve of insensitivityassociated with linear scoring models could be advantageousin areas of applied prediction such as credit scoring. In thiscontext, we reported the relative predictive power of genericcredit-scoring models versus customized models in an earlierpaper (Overstreet et al. 1992). Unfortunately, these findingswere not readily adaptable to the credit-union industry dueto a dated sample with incomplete credit-bureau information.Consequently, from 1988 to 1991, we gathered a refined databasefrom which to further develop and field-test generic scoringmodels in the credit-union environment. The results reportedherein not only confirm, but amplify, the relative predictivepower of such models found earlier. Relative costs and benefitsof generic versus customized models are modelled for a representativecredit union. Future research directions are set forth in theconclusions. 相似文献
54.
D. L. Damcott J. M. Cookson R. D. Carter JR. J. R. Martin M. Atzmon G. S. Was 《辐射效应与固体损伤》2013,168(4):383-392
Abstract A technique is developed which addresses the problem of irradiation assisted stress corrosion cracking of stainless steels in light water reactors using high energy protons to induce grain boundary segregation. These results represent the first grain boundary segregation measurements in bulk produced by proton irradiation of stainless steel. The technique allows the study of grain boundary composition with negligible sample activation, short irradiation time, rapid sample turnaround and at minimal cost. Scanning Auger electron microscopy is used to obtain grain boundary composition measurements of irradiated and unirradiated samples of ultra high purity (UHP) type 304L stainless steel and UHP type 304L steels with the additions of phosphorus (UHP + P) and sulphur (UHP + S). Results show that irradiation of all three alloys causes significant Ni segregation to the grain boundary and Cr and Fe away from it. Irradiation of the UHP + P alloy also results in segregation of P at the grain boundary from 5.3 to 8.7 at %, over 80 times the bulk value. No radiation-induced grain boundary segregation of S was measured in the UHP + S alloy. Results also indicate that the presence of P or S may enhance radiation-induced segregation of major alloying elements at the boundary. Comparison of irradiated and unirradiated regions of the UHP + P alloy indicate that while a prior thermal treatment segregates P to the grain boundary to 5.3 at %, the major element concentrations at the grain boundary are completely different from those under irradiation. 相似文献
55.
Systematic electronic variations were introduced into the monoanionic dipyrrinato ligand scaffold via halogenation of the pyrrolic β-positions and/or via the use of fluorinated aryl substituents in the ligand bridgehead position in order to synthesize proligands of the type 1,9-dimesityl-β-R(4)-5-Ar-dipyrrin [R = H, Cl, Br, I; Ar = mesityl, 3,5-(F(3)C)(2)C(6)H(3), C(6)F(5) in ligand 5-position; β = 2,3,7,8 ligand substitution; abbreviated ((β,Ar)L)H]. The electronic perturbations were probed using standard electronic absorption and electrochemical techniques on the different ligand variations and their divalent iron complexes. The free-ligand variations cause modest shifts in the electronic absorption maxima (λ(max): 464-499 nm) and more pronounced shifts in the electrochemical redox potentials for one-electron proligand reductions (E(1/2): -1.25 to -1.99 V) and oxidations (E(1/2): +0.52 to +1.14 V vs [Cp(2)Fe](+/0)). Installation of iron into the dipyrrinato scaffolds was effected via deprotonation of the proligands followed by treatment with FeCl(2) and excess pyridine in tetrahydrofuran to afford complexes of the type ((β,Ar)L)FeCl(py) (py = pyridine). The electrochemical and spectroscopic behavior of these complexes varies significantly across the series: the redox potential of the fully reversible Fe(III/II) couple spans more than 400 mV (E(1/2): -0.34 to +0.50 V vs [Cp(2)Fe](+/0)); λ(max) spans more than 40 nm (506-548 nm); and the (57)Fe M?ssbauer quadrupole splitting (|ΔE(Q)|) spans nearly 2.0 mm/s while the isomer shift (δ) remains essentially constant (0.86-0.89 mm/s) across the series. These effects demonstrate how peripheral variation of the dipyrrinato ligand scaffold can allow systematic variation of the chemical and physical properties of iron dipyrrinato complexes. 相似文献
56.
O. EL AKRAMINE W. A. LESTER JR X. KROKIDIS C. A. TAFT T. C. GUIMARAES A. C. PAVAO 《Molecular physics》2013,111(1-2):277-285
The chemisorption of CO on a Cr (110) surface is investigated using the quantum Monte Carlo method in the diffusion Monte Carlo (DMC) variant and a model Cr2CO cluster. The present results are consistent with the earlier ab initio HF study with this model that showed the tilted/near-parallel orientation as energetically favoured over the perpendicular arrangement. The DMC energy difference between the two orientations is larger (1.9 eV) than that computed in the previous study. The distribution and reorganization of electrons during CO adsorption on the model surface are analysed using the topological electron localization function method that yields electron populations, charge transfer and clear insight on the chemical bonding that occurs with CO adsorption and dissociation on the model surface. 相似文献
57.
In this study, the aromatic-thiol π hydrogen bonding and phenylalanine-cysteine side chain interactions are characterized through both molecular orbital calculations on a C6H6-HSCH3 model complex and database analyses of 609 X-ray protein structures. The aromatic-thiol π hydrogen bonding interaction can achieve a stabilization energy of 2.60 kcal mol?1, and is stronger than the already documented aromatic-hydroxyl and aromatic-amino hydrogen bonds. However, the occurrence of the aromatic-thiol hydrogen bond is rather rare in proteins. This is because most of the thiol groups participate in the formation of either disulphide bonds or stronger S—H…O (or N) ‘normal’ hydrogen bonds in a protein environment. Interactions between the side chains of phenylalanine and cysteine residues are characterized as the phenyl(Phe)(HSCH2-)(Cys) interaction. The bonding energy for such interactions is approximately 3.71 kcal mol-1 and is achieved in a geometric arrangement with an optimal phenyl(Phe)-(HS-)(Cys) π-type hydrogen bonding interaction. The interaction is very sensitive to the orientation of the two lone electron pairs on the sulphur atom relative to the π electron cloud of the phenyl ring. Accordingly, the interaction configurations that can accomplish a significant bonding energy exist only within a narrow configurational space. The database analysis of 609 experimental X-ray protein structures demonstrates that only 268 of the 1620 cysteine residues involve such phenylalanine-cysteine side chain interactions. Most of these interactions occur in the form of π (aromatic)-lone pair(sulphur) attractions, and correspond to a bonding energy less than 1.5 kcal mol?1. A few were identified as the aromatic-thiol hydrogen bond with a bonding energy of 2.0–3.6 kcal mol?1. 相似文献
58.
59.
This paper presents a method of obtaining the complete asymptoticsolution of boundary value problems of the form
for x [0,1] where b(x) is strictly positive andfor small and positive. Physically, the problem arises in determiningthe steady-state concentration of a substance in a chemicalflow reactor. A "two-variable" expansion procedure is used. 相似文献
60.
Aitala EM Amato S Anjos JC Appel JA Ashery D Banerjee S Bediaga I Blaylock G Bracker SB Burchat PR Burnstein RA Carter T Carvalho HS Copty NK Costa I Cremaldi LM Darling C Denisenko K Fernandez A Gagnon P Gerzon S Gobel C Gounder K Halling AM Herrera G Hurvits G James C Kasper PA Kwan S Langs DC Leslie J Lundberg B MayTal-Beck S Meadows B de Mello Neto JR Milburn RH de Miranda JM Napier A Nguyen A d'Oliveira AB O'Shaughnessy K Peng KC Perera LP Purohit MV Quinn B Radeztsky S Rafatian A 《Physical review letters》1996,77(12):2384-2387