Aqueous complexation of thorium(IV), uranium(IV), neptunium(IV), plutonium(III/IV), and cerium(III/IV) with DTPA

Aqueous complexation of Th(IV), U(IV), Np(IV), Pu(III/IV), and Ce(III/IV) with DTPA was studied by potentiometry, absorption spectrophotometry, and cyclic voltammetry at 1 M ionic strength and 25 °C. The stability constants for the 1:1 complex of each trivalent and tetravalent metal were calculated. From the potentiometric data, we report stability constant values for Ce(III)DTPA, Ce(III)HDTPA, and Th(IV)DTPA of log β(101) = 20.01 ± 0.02, log β(111) = 22.0 ± 0.2, and log β(101) = 29.6 ± 1, respectively. From the absorption spectrophotometry data, we report stability constant values for U(IV)DTPA, Np(IV)DTPA, and Pu(IV)DTPA of log β(101) = 31.8 ± 0.1, 32.3 ± 0.1, and 33.67 ± 0.02, respectively. From the cyclic voltammetry data, we report stability constant values for Ce(IV) and Pu(III) of log β(101) = 34.04 ± 0.04 and 20.58 ± 0.04, respectively. The values obtained in this work are compared and discussed with respect to the ionic radius of each cationic metal.     

Rhodium complexes of a chelating ligand with imidazol-2-ylidene and pyridin-2-ylidene donors: the effect of C-metalation of nicotinamide groups on uptake of hydride ion

Rhodium complexes of the imidazolylidene (C-im) N-heterocyclic carbene (NHC) ligand, C-im-pyH(+), bearing a nicotinamide cation substituent (pyH(+)) have been targeted for ligand-centered uptake and delivery of hydride ion. This work reveals that rhodium(I) complexes such as [Rh(C-im-pyH(+))(COD)X][PF(6)] (1, a: X = Cl, b: X = I) undergo facile C-metalation of the nicotinamide ring to afford rhodium complexes of a novel chelate ligand, C,C'-im-py, with coordinated imidazolylidene (C(im)) and pyridylidene (C(py)) NHC-donors. Seven examples were characterized and include rhodium(III) monomers of the general formula [Rh(C,C'-im-py)L(x)I(2)](z+) (2: z = 1, L = H(2)O or solvent, x = 2; 3, 5, 7: z = 0, L = carboxylate, x = 1) and novel rhodium(II) dimers, the anti/syn-isomers of [Rh(2)(C,C'-im-py)(2)(μOAc)(2)I(2)] (4-anti/syn). The NMR data, backed by DFT calculations, is consistent with attribution of the C,C'-im-py ligand as a bis(carbene) donor. Single crystal X-ray diffraction studies are reported for 2, 3, 4-anti, 4-syn and 7. Consistently, within the each complex, the Rh-C(im) bond length is shorter than the Rh-C(py) bond length, which is the opposite trend to that expected based on simple electronic considerations. It is proposed that intramolecular steric interactions imposed by different rings in the rigid C,C'-im-py chelate ligand dictate the observed Rh-C(NHC) bond lengths. Attempts to add hydride to the C-metalated nicotinamide ring in 3 were unsuccessful. The redox behavior of 3 and 4 and, for comparison, an analogous bis(imidazolylidene)rhodium(III) monomer (8), were characterized by cyclic voltammetry, electron paramagnetic resonance (EPR), and UV-vis spectroelectrochemistry. In 3 and 4, the C-metalated nicotinamide ring is found to exhibit a one-electron reduction process at far lower potential (-2.34 V vs. Fc(+)/Fc in acetonitrile) than the two-electron nicotinamide cation-dihydronicotinamide couple found for the corresponding nonmetalated ring (-1.24 V). The C,C'-ligand is electrochemically silent over a large potential range (from -2.3 V to the anodic solvent limit), thus for both 3 and 4 the first reduction processes are metal-centered. For 4-anti, the cyclic voltammetry and UV-vis spectrochemical results are consistent with a diamagnetic [Rh(I)Rh(II)](2) tetrameric reduction product. Density functional theory (DFT) calculations were used to further probe the uptake of hydride ion by the nicotinamide ring, both before and after C-metalation. It is found that C-metalation significantly decreases the ability of the nicotinamide ring to take up hydride ion, which is attributed to the "carbene-like" character of a C-metalated pyridylidene ring.     

Four-electron oxygen reduction by brominated cobalt corrole

The carbon-supported cobalt(III) complex of β-pyrrole-brominated 5,10,15-tris(pentafluorophenyl)corrole [Co(tpfc)Br(8)/C] is introduced as a nonplatinum alternative for electrocatalytic oxygen reduction in aqueous solutions. Through systematic work, the basic kinetic parameters of this reaction were studied, using rotating ring disk electrode electrochemical methods in the pH range of 0-11. Pronounced catalytic activity was detected in acid solutions along with shifts of the Co(II)/Co(III) and O(2) redox couples to more positive values (onset of 0.56 V at pH 0). A series of independent measurements have been used to prove that the dominant mechanism for oxygen reduction by Co(tpfc)Br(8)/C catalysis is the direct four-electron pathway to water.     

Electronic polarization effects in the photodissociation of Cl2

Velocity mapped ion imaging and resonantly enhanced multiphoton ionization time-of-flight methods have been used to investigate the photodissociation dynamics of the diatomic molecule Cl(2) following excitation to the first UV absorption band. The experimental results presented here are compared with high level time dependent wavepacket calculations performed on a set of ab initio potential energy curves [D. B. Kokh, A. B. Alekseyev, and R. J. Buenker, J. Chem. Phys. 120, 11549 (2004)]. The theoretical calculations provide the first determination of all dynamical information regarding the dissociation of a system of this complexity, including angular momentum polarization. Both low rank K = 1, 2 and high rank K = 3 electronic polarization are predicted to be important for dissociation into both asymptotic product channels and, in general, good agreement is found between the recent theory and the measurements made here, which include the first experimental determination of high rank K = 3 orientation.     

The effect of inter-cluster interactions on the structure of colloidal clusters

Colloidal systems present exciting opportunities to study clusters. Unlike atomic clusters, which are frequently produced at extremely low density, colloidal clusters may interact with one another. Here we consider the effect of such interactions on the intra-cluster structure in simulations of colloidal cluster fluids. A sufficient increase in density leads to a higher population of clusters in the ground state. In other words, inter-cluster interactions perturb the intra-cluster behaviour, such that each cluster may no longer be considered as an isolated system. Conversely, for dilute, weakly interacting cluster fluids little dependence on colloid concentration is observed, and we thus argue that it is reasonable to treat each cluster as an isolated system.     

单原子配位结构及与载体相互作用的调控用于二氧化碳电催化还原

电催化二氧化碳还原(ECR) 制备高值化学品被认为是在碳中和背景下实现可再生能源存储及降低CO₂浓度的一种有效策略。为了实现此目标,催化剂的开发与设计是ECR研究的关键。单原子催化剂(SACs) 因其独特的电子结构、明确的配位环境和极高的原子利用率,近年来在ECR领域引起了广泛关注。通过调节SACs的中心金属元素种类和局部配位结构,可有效调节SACs对CO₂和其还原中间体的吸附强度和催化活性。本文总结了SACs在ECR领域所取得的最新研究进展,重点讨论了SACs的配位结构及其与载体之间的相互作用对催化活性的影响以及相关调控策略,最后,提出了SACs应用于ECR所面临的机遇与挑战。     

The effect of wavy leading edges on aerofoil–gust interaction noise

High-order accurate numerical simulations are performed to investigate the effects of wavy leading edges (WLEs) on aerofoil–gust interaction (AGI) noise. The present study is based on periodic velocity disturbances predominantly in streamwise and vertical directions that are mainly responsible for the surface pressure fluctuation of an aerofoil. In general, the present results show that WLEs lead to reduced AGI noise. It is found that the ratio of the wavy leading-edge peak-to-peak amplitude (LEA) to the longitudinal wavelength of the incident gust (_λg${\lambda }_g$) is the most important factor for the reduction of AGI noise. It is observed that there exists a tendency that the reduction of AGI noise increases with LEA/_λg$\mathrm{LEA}/{\lambda }_g$ and the noise reduction is significant for LEA/_λg≥0.3$\mathrm{LEA}/{\lambda }_g\ge 0.3$. The present results also suggest that any two different cases with the same LEA/_λg$\mathrm{LEA}/{\lambda }_g$ lead to a strong similarity in their profiles of noise reduction relative to the straight leading-edge case. The wavelength of wavy leading edges (LEW), however, shows minor influence on the reduction of AGI noise under the present gust profiles used. Nevertheless, the present results show that a meaningful improvement in noise reduction may be achieved when 1.0≤LEW/_λg≤1.5$1.0\le \mathrm{LEW}/{\lambda }_g\le 1.5$. In addition, it is found that the beneficial effects of WLEs are maintained for various flow incidence angles and aerofoil thicknesses. Also, the WLEs remain effective for gust profiles containing multiple frequency components. It is discovered in this paper that WLEs result in incoherent response time to the incident gust across the span, which results in a decreased level of surface pressure fluctuations, hence a reduced level of AGI noise.     

Molecular Structure of Heterocycles: 3. Semiempirical MO Calculations and Karplus-Type Dihedral Angle Dependence for the Coupling Constant Relationship of Some 4,5-Dihydro-5-Hydroxy- 5(3)-Halomethylisoxazoles

Molecular modeling by semiempirical MO calculations (AM1) was used to predict configurational and conformational preferences of a series of 4,5-dihydro-5- hydroxy-5(3)-halomethylisoxazoles. The relationship among dihedral angles calculated and the experimental ¹H NMR coupling constants, J³{Ha,b-H}, are established with Karplus-Type Equation.

     

Global supersymmetry on curved spaces in various dimensions

We propose methods towards a systematic determination of d  -dimensional curved spaces where Euclidean field theories with rigid supersymmetry can be defined. The analysis is carried out from a group theory as well as from a supergravity point of view. In particular, by using appropriate gauged supergravities in various dimensions we show that supersymmetry can be defined in conformally flat spaces, such as non-compact hyperboloids Hⁿ⁺¹${\mathbb{H}}^{n+1}$ and compact spheres Sⁿ${\mathbb{S}}^n$ or – by turning on appropriate Wilson lines corresponding to R-symmetry vector fields – on S¹×Sⁿ${\mathbb{S}}^1\times {\mathbb{S}}^n$, with n<6$n<6$. By group theory arguments we show that Euclidean field theories with rigid supersymmetry cannot be consistently defined on round spheres S^d${\mathbb{S}}^d$ if d>5$d>5$ (despite the existence of Killing spinors). We also show that distorted spheres and certain orbifolds are also allowed by the group theory classification.     

Co-registration of the distribution of wall shear stress and 140 complex plaques of the aorta

Previous studies provide evidence that atherosclerosis develops in vascular regions exposed to low wall shear stress (WSS) and high oscillatory shear index (OSI). 4D flow MRI was analyzed in 70 stroke patients with complex plaques (≥ 4 mm thickness, ulcerated or superimposed thrombi) and in 12 young healthy volunteers. The segmental distribution of peak systolic WSS_systole and OSI was quantified in analysis planes positioned directly at the location of 140 complex plaques found in the 70 patients. In addition, WSS_systole and OSI were evaluated in 8 standard analysis planes distributed along the aorta. Complex plaques were predominantly found at the inner curvature of the aortic arch and of the descending aorta. High OSI was co-located with the segments mostly affected by complex plaque while WSS_systole demonstrated a homogenous distribution. In standard analysis planes, patients demonstrated significantly (p < 0.01) altered distribution of wall parameters compared to volunteers (reduced WSS_systole in 91% of aortic wall segments, increased OSI in 48% of segments). OSI distribution was asymmetric with higher values at the inner curvature of the aorta. While WSS and OSI showed expected changes in patients compared to healthy controls, their distribution pattern at complex plaques indicated a more complex and heterogeneous relationship than previously anticipated.