New basis sets for the evaluation of interaction‐induced electric properties in hydrogen‐bonded complexes

Interaction‐induced static electric properties, that is, dipole moment, polarizability, and first hyperpolarizability, of the CO? (HF)_n and N₂? (HF)_n, n = 1–9 hydrogen‐bonded complexes are evaluated within the finite field approach using the Hartree–Fock, density functional theory, Møller–Plesset second‐order perturbation theory, and coupled cluster methods, and the LPol‐n (n = ds, dl, fs, fl) basis sets. To compare the performance of the different methods with respect to the increase of the complex size, we consider as model systems linear chains of the complexes. We analyze the results in terms of the many‐body and cooperative effects. © 2012 Wiley Periodicals, Inc.     

Naphthalene and benzene levels in microenvironments associated with potential exposure: new and old apartments with moth repellents,and cabins of passenger cars

A lesser degree of information is available with respect to microenvironments associated with potential exposure to naphthalene, in comparison with other volatile organic compounds. The current study investigated the levels of benzene as well as naphthalene, both in the indoor and outdoor air of apartments and in the cabins of passenger cars. Two groups of 20 apartment buildings (20 new and 20 old) were chosen on the basis of the selection criteria (apartment location and size). In addition, 10 actual commuters were recruited for this study. The equal number of drivers was recruited for the study for comparison of two types of fuels for vehicles (five drivers of gasoline-fuelled and five drivers of diesel-fuelled passenger cars). Indoor naphthalene concentrations were similar between old and new apartments, while the benzene concentrations in new apartments were significantly higher than those of old apartments. The naphthalene concentrations in bedrooms, where wardrobes with moth repellent (MRs) were placed, were significantly higher than those for living rooms where no MRs were present. In turn, these indoor concentrations were significantly higher than outdoor levels. It is noteworthy that the mean and median values of naphthalene measured in the bedrooms exceeded the USEPA RfC (inhalation reference concentration) of 3?µg?m^?3, and the living room values were close to the RfC, while the residential benzene levels exceeded the European benzene limit of 5?µg?m^?3. In contrast, the maximum outdoor levels were well below that of the RfC. The use of passenger cars appeared to be a significant daily activity for both naphthalene and benzene exposure. The naphthalene-to-benzene ratios varied with the type of microenvironments. Both the indoor naphthalene and benzene concentrations in the present study were much higher than those of other studies.     

有机杂化锑基主族异金属硫属化物的研究进展

本文综述了有机杂化锑基主族异金属硫属化物的研究进展,对它们的结构和异金属次级结构基元进行了描述、归类和总结;探讨了有机组分分别作为结构导向剂和配体两种角色所起到的不同作用;介绍了这类化合物在离子交换、光催化性能方面的研究;展望了该体系的发展趋势。     

有机杂化锑基主族异金属硫属化物的研究进展

本文综述了有机杂化锑基主族异金属硫属化物的研究进展, 对它们的结构和异金属次级结构基元进行了描述、归类和总结;探讨了有机组分分别作为结构导向剂和配体两种角色所起到的不同作用;介绍了这类化合物在离子交换、光催化性能方面的研究;展望了该体系的发展趋势。     

Resonant equations with the Neumann p-Laplacian plus an indefinite potential

We consider a nonlinear Neumann problem driven by the p  -Laplacian plus an indefinite potential and a Carathéodory reaction which at ±∞ is resonant with respect to any nonprincipal variational eigenvalue of the differential operator. Using critical point theory and Morse theory (critical groups), we show that the problem has at least three nontrivial smooth solutions, two of which have constant sign. In the process we prove some results of independent interest concerning the unique continuation property of eigenfunctions and the critical groups at infinity of a C¹$C^1$-functionals.     

The Deuterated “Magic Methyl” Group: A Guide to Site-Selective Trideuteromethyl Incorporation and Labeling by Using CD3 Reagents

In the field of medicinal chemistry, the precise installation of a trideuteromethyl group is gaining ever-increasing attention. Site-selective incorporation of the deuterated “magic methyl” group can provide profound pharmacological benefits and can be considered an important tool for drug optimization and development. This review provides a structured overview, according to trideuteromethylation reagent, of currently established methods for site-selective trideuteromethylation of carbon atoms. In addition to CD₃, the selective introduction of CD₂H and CDH₂ groups is also considered. For all methods, the corresponding mechanism and scope are discussed whenever reported. As such, this review can be a starting point for synthetic chemists to further advance trideuteromethylation methodologies. At the same time, this review aims to be a guide for medicinal chemists, offering them the available C−CD₃ formation strategies for the preparation of new or modified drugs.     

Reachable set bounding for nonlinear perturbed time-delay systems: The smallest bound

In this letter, we propose a new approach to obtain the smallest box which bounds all reachable sets of a class of nonlinear time-delay systems with bounded disturbances. A numerical example is studied to illustrate the obtained result.     

Construction of mixed carboxylate and pyrogallate building units for luminescent metal-organic frameworks

A metal-organic framework,Ce-FDM-50,was constructed by employing gallic acid featuring both carboxylate and pyrogallate as the coordinating sites and Ce(Ⅲ).The co-assembly of the carboxylates and pyrogallates with two metal ions have achieved a new type of paddle wheel secondary building unit.These building units were further joined by organic struts to obtain frameworks in sql topology.This synthetic approach could be expanded to five different lanthanide metals(Nd,Eu,Gd,Tb,Yb)for the construction of a series of isoreticular MOFs based on FDM-50,and even MTV-MOFs in which mixed lanthanide metals with specific ratios were distributed.In addition,featuring the lanthanide metals as the inorganic nodes in the network,Tb-FDM-50 showed distinct luminescence properties that could be furtherly tuned for variable applications.     

Base Metal Catalyzed Isocyanide Insertions

Isocyanides are diverse C₁ building blocks considering their potential to react with nucleophiles, electrophiles, and radicals. Therefore, perhaps not surprisingly, isocyanides are highly valuable as inputs for multicomponent reactions (MCRs) and other one‐pot cascade processes. In the field of organometallic chemistry, isocyanides typically serve as ligands for transition metals. The coordination of isocyanides to metal centers alters the electronic distribution of the isocyano moiety, and reaction pathways can therefore be accessed that are not possible in the absence of the metal. The tunable reactivity of the isocyanide functional group by transition metals has evolved into numerous useful applications. Especially palladium‐catalyzed isocyanide insertion processes have emerged as powerful reactions in the past decade. However, reports on the use of earth‐abundant and cheap base metals in these types of transformations are scarce and have received far less attention. In this Minireview, we focus on these emerging base metal catalyzed reactions and highlight their potential in synthetic organic chemistry. Although mechanistic studies are still scarce, we discuss distinct proposed catalytic cycles and categorize the literature according to 1) the (hetero)atom bound to and 2) the type of bonding with the transition metal in which the (formal) insertion occurs.     

Acyl Fluorides in Late‐Transition‐Metal Catalysis

In this Review, we summarize the current state of the art in late‐transition‐metal‐catalyzed reactions of acyl fluorides, covering both their synthesis and further transformations. In organic reactions, the relationship between stability and reactivity of the starting substrates is usually characterized by a trade‐off. Yet, acyl fluorides display a very good balance between these properties, which is mostly due to their moderate electrophilicity. Thus, acyl fluorides (RCOF) can be used as versatile building blocks in transition‐metal‐catalyzed reactions, for example, as an “RCO” source in acyl coupling reactions, as an “R” source in decarbonylative coupling reactions, and as an “F” source in fluorination reactions. Starting from the cleavage of the acyl C?F bond in acyl fluorides, various transformations are accessible, including C?C, C?H, C?B, and C?F bond‐forming reactions that are catalyzed by transition‐metal catalysts that contain the Group 9–11 metals Co, Rh, Ir, Ni, Pd, or Cu.