Open‐cage fullerenes as tailor‐made container for a single water molecule

Water is the most important liquid on earth. Clusters of water have been investigated extensively in an effort to understand the bulk property of water. But the behavior of single water molecule without H‐bond has been rarely studied. Open‐cage [60]fullerenes have been shown to trap a single water molecule selectively over molecules with comparable size and act as the smallest “water bottle”. Copyright © 2013 John Wiley & Sons, Ltd.     

A 119Sn Mössbauer Spectroscopic Investigation of Tin Complexes with Amidines

Several novel tin(IV) adducts of amidines, [SnClPh₃L], [SnCl₂Ph₂L] and [SnBr₄L] {L=N,N-diphenylacetamidine (Hdpac) or N,N-diphenylbenzamidine (Hdpba)}, were prepared and investigated by Mössbauer spectroscopy which was an important tool for the elucidation of bonding and structural features. The resulting Mössbauer data also led to the conclusion that the tin(IV) centre for the adduct [SnClPh₃L] is pentacoordinated in a trigonal bipyramidal arrangement and hexacoordinated for [SnCl₂Ph₂L] and [SnBr₄L] in a geometric patterns of an octahedral. The amidines act as monodentate ligands to the metal centre for the former and bidentate for the latter.     

A mathematical and computational review of Hartree–Fock SCF methods in quantum chemistry

We present a review of the fundamental topics of Hartree–Fock theory in quantum chemistry. From the molecular Hamiltonian, using and discussing the Born–Oppenheimer approximation, we arrive at the Hartree and Hartree–Fock equations for the electronic problem. Special emphasis is placed on the most relevant mathematical aspects of the theoretical derivation of the final equations, and on the results regarding the existence and uniqueness of their solutions. All Hartree–Fock versions with different spin restrictions are systematically extracted from the general case, thus providing a unifying framework. The discretization of the one-electron orbital space is then reviewed and the Roothaan–Hall formalism introduced. This leads to an exposition of the basic underlying concepts related to the construction and selection of Gaussian basis sets, focusing on algorithmic efficiency issues. Finally, we close the review with a section in which the most relevant modern developments (especially those related to the design of linear-scaling methods) are commented on and linked to the issues discussed. The paper is intentionally introductory and rather self-contained, and may be useful for non-experts intending to use quantum chemical methods in interdisciplinary applications. Moreover, much material that can be found scattered in the literature has been put together to facilitate comprehension and to serve as a handy reference.     

Nonlinear optical and structural properties of M@C N endohedrals (M = Li,Ca and Sc,N = 60 and 70)

We have investigated the static (ω = 0) and frequency-dependent nonlinear optical (NLO) properties of the M@C _N endohedrals (M = Li, Ca, Sc, N = 60 and 70) using the SSH (Su–Schrieffer–Heeger) approximation and sum-over-state (SOS) approach. Also, we study the effects of displacement and alkali, alkaline earth and lanthanide metal atoms and type of cage on the hyperpolarisabilities of the M@C _N endohedrals. The hyperpolarisability magnitudes and spectra are in agreement with experiment and the work of others using the SSH approximation. Our results indicate that the cage-type effect on the NLO spectra of M@C _N endohedrals is dramatic. Also, atom type has little effect on the highest peak value. These relationships between the atom and cage type and hyperpolarisability values may be beneficial to experimentalists when designing new NLO materials with large NLO responses.     

Electrochemically induced oxidative cyclization of 2,3‐dihydroxypyridine. Synthesis of a novel highly oxygenated heterocyclic compound

Electrochemical oxidation of 2,3‐dihydroxypyridine in aqueous phosphate buffer solution at a glassy carbon electrode has been studied using cyclic voltammetry and controlled potential coulometry. The results indicate that oxidation of 2,3‐dihydroxypyridine on glassy carbon electrode shows an irreversible feature in aqueous solution. This data indicates that the electrochemically generated pyridindione is unstable and via an oxidative conversion pathway converts to a novel highly oxygenated heterocyclic compound. By means of the obtained electrochemical data, an efficient, one‐pot method for the synthesis of this heterocyclic compound based on the oxidative cyclization of 2,3‐dihydroxypyridine under green conditions, and in a good yield and purity is described. Copyright © 2011 John Wiley & Sons, Ltd.     

One-step green route to narrowly dispersed copper nanocrystals

We report a total “green” chemical method in aqueous solution for synthesizing stable narrowly distributed copper nanoparticles with average diameter less than 5 nm in the presence of Polyvinylpyrrolidone (PVP) as a stabilizer and without any inert gas protection. In our synthesis route, ascorbic acid, natural vitamin C (VC), an excellent oxygen scavenger, acts as both reducing agent and antioxidant, to reduce the metallic ion precursor, and to effectively prevent the common oxidation process of the newborn pure copper nanoclusters.     

Determination of 25 elements in the complex oxide mineral zirconolite by analytical electron microscopy

In this paper we describe a technique for the determination of 25 elements in natural zirconolite using energy-dispersive analytical electron microscopy (AEM). The method presented here allows one to quantitatively investigate the chemistry of submicron-scale zones in complex oxide minerals. The effects of electron channeling, thickness variability and variations in detector resolution were minimized by using a controlled set of operating procedures and instrument parameters. To provide a high level of accurayy, k_ATI-factors were determined from standards for most of the 25 elements of interest, including all of the major elements. Each analytical spectrum is reduced to a set of raw peak counts (and errors) using a digital top-hat filter to suppress background followed by multiple least squares fitting of reference spectra. Counting times of 12–15 min per analysis were required to provide suitable counting statistics. Results are presented for zirconolite samples from the contact metamorphic aureole of the Bergell granodiorite intrusion, Switzerland-Italy. A comparison of 43 AEM analyses with 15 analyses obtained by wavelength-dispersive electron probe microanalysis (EPMA) shows that there is excellent agreement between the two data sets in the amounts of individual elements present, chemical trends and overall stoichiometry. An assessment of the combined data set shows that the major substitution mechanisms in the Bergell samples are coupled substitutions involving the M5,6- and M8-sites of the zirconolite structure: ^M8Ca²⁺ + ^M5,6Ti⁴⁺→^M8REE³⁺ + ^M5,6(Al,Fe)³⁺ and ^M8Ca²⁺ + ^M5,6Ti⁴⁺→^M8(Th,U)⁴⁺ + ^M5,6 (Mg,Fe)²⁺.     

激光诱导直接化学光刻

本文利用Ar~+激光倍频257.3nm进行扫描蚀刻Si、GaAs和Zn片,获得的最小光刻线宽为1.2μm,给出蚀刻深度与光强/扫描速度的关系曲线等参量,首次利用光刻技术估计卤素自由基的扩散系数、自由路程以及激光聚焦光斑大小,以及观察到阈值现象。     

Solid-supported reagents and catalysts for the preparation of large ring compounds

Parallel combinatorial synthesis in solution using immobilized reagents, catalysts, and scavengers has emerged as a powerful technique for the preparation of diverse libraries of compounds. This technique has only recently been applied to the synthesis of large-ring compounds. In this comprehensive review several strategies are presented and discussed, including Pd-catalyzed allylic alkylation, Stille-coupling, macrolactonization and macrolactamization using solid supported reagents and catalysts. In several cases site isolation has allowed operation of these macrocyclization reactions in concentrated solution (pseudo-dilution effect).