Long‐range corrected density functionals combined with local response dispersion: A promising method for weak interactions

Density functional theory, in general, is considered to underestimate the weak van der Waals type of intermolecular interactions. We optimized parameters of the local response dispersion (LRD) method applied to the long‐range corrected exchange‐correlation functionals (LC‐BOP12+LRD and LCgau‐BOP+LRD) on the interaction energy for the complexes in the recently compiled S66 database and found to be comparable with the high‐level wave function‐based methods reported in ?ezá? et al. (J. Chem. Theory Comput. 2011 , 7, 2427). Our calculations with the S66 intermolecular complexes at equilibrium geometries suggests that the LC‐BOP12+LRD and LCgau‐BOP+LRD are well‐balanced and lower cost alternatives to the methods reported in the database. Further, test on the S66X8 database (with eight nonequilibrium points) and the HBC6 and NBC10 database shows LC+LRD method with newly optimized parameters is a promising candidate for dealing such weak interactions. Finally, the new parameterized LC+LRD method was tested on X40 benchmark halogenated complexes.Copyright © 2013 Wiley Periodicals, Inc.     

Effect of Electron Beam Irradiation on the Kinetics of Non-isothermal Crystallization of Nylon 66

The non-isothermal crystallization kinetics was studied by differential scanning calorimetric analysis on nylon 66 and e-beam irradiated nylon 66 at different cooling rates. The Modified Avrami equation, the Ozawa equation and the Combined Avrami-Ozawa equation were applied to study the kinetics of non-isothermal crystallization of nylon 66. The crystallization behavior of pristine nylon 66 polymer was compared with that of e-beam irradiated nylon 66 and observed that the kinetics of non-isothermal crystallization of nylon66 was affected largely upon e-beam irradiation. E-beam irradiation not only decreased the crystallization temperature of nylon 66, but influenced the mechanism of nucleation and crystal growth and reduced the overall crystallization rate of nylon 66 also. The crystallization activation energy calculated by the Kissinger method for irradiated nylon 66 was lower than that of pristine nylon 66.     

UiO-66-NH2 and Zeolite-Templated Carbon Composites for the Degradation and Adsorption of Nerve Agents

Composites of metal-organic frameworks and carbon materials have been suggested to be effective materials for the decomposition of chemical warfare agents. In this study, we synthesized UiO-66-NH₂/zeolite-templated carbon (ZTC) composites for the adsorption and decomposition of the nerve agents sarin and soman. UiO-66-NH₂/ZTC composites with good dispersion were prepared via a solvothermal method. Characterization studies showed that the composites had higher specific surface areas than pristine UiO-66-NH₂, with broad pore size distributions centered at 1–2 nm. Owing to their porous nature, the UiO-66-NH₂/ZTC composites could adsorb more water at 80% relative humidity. Among the UiO-66-NH₂/ZTC composites, U_0.8Z_0.2 showed the best degradation performance. Characterization and gas adsorption studies revealed that beta-ZTC in U_0.8Z_0.2 provided additional adsorption and degradation sites for nerve agents. Among the investigated materials, including the pristine materials, U_0.8Z_0.2 also exhibited the best protection performance against the nerve agents. These results demonstrate that U_0.8Z_0.2 has the optimal composition for exploiting the degradation performance of pristine UiO-66-NH₂ and the adsorption performance of pristine beta-ZTC.     

Martensitic transformation and magnetic properties of ferromagnetic shape memory Fe66Pd30Rh4 alloys

This study mainly shows that in the Fe₆₆Pd₃₀Rh₄ (at%) alloys, the L1₀ phase plays an important role in magnetostriction due to the interplay of L1₀ martensitic twins with magnetic domains. The L1₀ martensitic twin structure exhibits a strong magnetocrystalline anisotropy energy constant (K_u=1.27-2.84×10⁶ (ergs/cm³)) along the tetragonal c axis direction. In addition, the L1₀ tetragonal martensitic twin structure shows both a perfect shape memory and a reversible shape memory effect; therefore, it is expected to be applicable in magneto-mechanical applications (such as microactuators or springs). However, in this study, we discover that solution treatment (ST) and aging heat treatments of Fe₆₆Pd₃₀Rh₄ ferromagnetic shape memory alloys influence the behavior of the martensitic transition, which is associated with the change in magnetic properties. The process of a thermoelastic L1₀+L1_m twin phase decomposition→non-thermoelastic L1₀+L1_m+α_bct structure in Fe₆₆Pd₃₀Rh₄ alloys during solution treatment and aging at 400-550 °C for various times is studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The relation of phase separation morphology to the magnetic property change is examined with a superconducting quantum interference device (SQUID) magnetometer, and magnetostriction measurement is performed with a strain gage method and magnetostrictive meter setup. The results indicate that the process of martensitic transformation during aging leads to an increase in coercivity and a decrease in magnetostriction, simultaneously.     

Highly Sensitive and Selective Detection of Pb(II) by NH2−SiO2/Ru(bpy)32+−UiO66 based Solid‐state ECL Sensor

In this study, a novel electrochemiluminescence (ECL) sensor for highly sensitive and selective detection of Pb(II) was developed based on Ru(bpy)₃²⁺ encapsulated UiO66 metal‐organic‐framework (Ru(bpy)₃²⁺?UiO66 MOF) and ?NH₂ group functionalized silica (NH₂?SiO₂). The NH₂?SiO₂ with large surface area provided an excellent platform for the ECL sensor. As numerous exposed carboxyl groups were present on UiO66 backbone, the Ru(bpy)₃²⁺?UiO66 could be steadily immobilized to NH₂?SiO₂ by forming amide bonds. Meanwhile, the introduced UiO66 MOF which used for the encapsulation of Ru(bpy)₃²⁺, significantly enhanced the ECL efficiency of the proposed sensor, as it possessed a large specific surface area and porosity for the loading of Ru(bpy)₃²⁺. Moreover, a high quenching effect on ECL intensity was obtained in the presence of Pb(II) in the electrolyte. Under the optimal conditions, the quenched ECL intensity showed a good linear relationship within Pb(II) concentration in the range from 1.0×10^?6 to 1.0×10² μM, with a detection limit of 1.0×10^?7 μM (S/N=3). The proposed sensor for Pb(II) detection was simple in operation, rapid in testing, stable in signal, and showed a good anti‐interference ability to some other metal ions. Besides, its application for detecting Pb(II) in a real sample was also investigated here. This work provides a potential platform for metal ions detection in environmental monitoring field.     

Unitary Spaces on Clifford Algebras

For the complex Clifford algebra (p, q) of dimension n = p + q we define a Hermitian scalar product. This scalar product depends on the signature (p, q) of Clifford algebra. So, we arrive at unitary spaces on Clifford algebras. With the aid of Hermitian idempotents we suggest a new construction of, so called, normal matrix representations of Clifford algebra elements. These representations take into account the structure of unitary space on Clifford algebra. The work of N.M. is supported in part by the Russian President’s grant NSh-6705.2006.1.     

Norms and Generating Functions in Clifford Algebras

Generating functions are commonly used in combinatorics to recover sequences from power series expansions. Convergence of formal power series in Clifford algebras of arbitrary signature is discussed. Given , powers of u are recovered by expanding (1 − tu)⁻¹ as a polynomial in t with Clifford-algebraic coefficients. It is clear that (1 − tu)(1 + tu + t ² u ² + ...) = 1, provided the sum (1 + tu + t ² u ² + ...) exists, in which case u ^m is the Cliffordalgebraic coefficient of t ^m in the series expansion of (1 − tu)⁻¹. In this paper, conditions on for the existence of (1 − tu)⁻¹ are given, and an explicit formulation of the generating function is obtained. Allowing A to be an m × m matrix with entries in , a “Clifford-Frobenius” norm of A is defined. Norm inequalities are then considered, and conditions for the existence of (I − tA)⁻¹ are determined. As an application, adjacency matrices for graphs are defined with vectors of as entries. For positive odd integer k > 3, k-cycles based at a fixed vertex of a graph are enumerated by considering the appropriate entry of A ^k . Moreover, k-cycles in finite graphs are enumerated and expected numbers of k-cycles in random graphs are obtained from the norm of the degree-2k part of tr(1 − tu)⁻¹. Unlike earlier work using commutative subalgebras of , this approach represents a “true” application of Clifford algebras to graph theory.      

Tailoring the Asymmetric Structure of NH2-UiO-66 Metal-Organic Frameworks for Light-promoted Selective and Efficient Gold Extraction and Separation

Designing adsorption materials with high adsorption capacities and selectivities is highly desirable for precious metal recovery. Desorption performance is also particularly crucial for subsequent precious metal recovery and adsorbent regeneration. Herein, a metal–organic framework (MOF) material (NH₂-UiO-66) with an asymmetric electronic structure of the central zirconium oxygen cluster has an exceptional gold extraction capacity of 2.04 g g⁻¹ under light irradiation. The selectivity of NH₂-UiO-66 for gold ions is up to 98.8 % in the presence of interfering ions. Interestingly, the gold ions adsorbed on the surface of NH₂-UiO-66 spontaneously reduce in situ, undergo nucleation and growth and finally achieve the phase separation of high-purity gold particles from NH₂-UiO-66. The desorption and separation efficiency of gold particles from the adsorbent surface reaches 89 %. Theoretical calculations indicate that -NH₂ functions as a dual donor of electrons and protons, and the asymmetric structure of NH₂-UiO-66 leads to energetically advantageous multinuclear gold capture and desorption. This adsorption material can greatly facilitate the recovery of gold from wastewater and can easily realize the recycling of the adsorbent.     

A new three‐dimensional zinc(II) coordination polymer involving 2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl]‐1H‐benzimidazole and benzene‐1,4‐dicarboxylate ligands

Metal–organic frameworks (MOFs) based on multidentate N‐heterocyclic ligands involving imidazole, triazole, tetrazole, benzimidazole, benzotriazole or pyridine present intriguing molecular topologies and have potential applications in ion exchange, magnetism, gas sorption and storage, catalysis, optics and biomedicine. The 2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl]‐1H‐benzimidazole (tmb) ligand has four potential N‐atom donors and can act in monodentate, chelating, bridging and tridentate coordination modes in the construction of complexes, and can also act as both a hydrogen‐bond donor and acceptor. In addition, the tmb ligand can adopt different coordination conformations, resulting in complexes with helical structures due to the presence of the flexible methylene spacer. A new three‐dimensional coordination polymer, poly[[bis(μ₂‐benzene‐1,4‐dicarboxylato)‐κ⁴O¹,O^1′:O⁴,O^4′;κ²O¹:O⁴‐bis{μ₂‐2‐[(1H‐1,2,4‐triazol‐1‐yl)methyl‐κN⁴]‐1H‐benzimidazole‐κN³}dizinc(II)] trihydrate], {[Zn(C₈H₄O₄)(C₁₀H₉N₅)]·1.5H₂O}_n, has been synthesized by the reaction of ZnCl₂ with tmb and benzene‐1,4‐dicarboxylic acid (H₂bdic) under solvothermal conditions. There are two crystallographically distinct bdic²⁻ ligands [bdic²⁻(A) and bdic²⁻(B)] in the structure which adopt different coordination modes. The Zn^II ions are bridged by tmb ligands, leading to one‐dimensional helical chains with different handedness, and adjacent helices are linked by bdic²⁻(A) ligands, forming a two‐dimensional network structure. The two‐dimensional layers are further connected by bdic²⁻(B) ligands, resulting in a three‐dimensional framework with the topological notation 6⁶. The IR spectra and thermogravimetric curves are consistent with the results of the X‐ray crystal structure analysis and the title polymer exhibits good fluorescence in the solid state at room temperature.