Inverse electron demand Diels–Alder reaction as a novel method for functionalization of natural chlorins

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Kharasch reaction: Cu-catalyzed and non-Kharasch metal-free peroxidation of barbituric acids

It was discovered that the Kharasch peroxidation of barbituric acids proceeds both with a Cu-catalyst and without a metal catalyst. Despite the presence of possible thermal-initiated side oxidation pathways, α-tert-butylperoxybarbiturates were selectively prepared from substituted barbituric acids and tert-butyl hydroperoxide.     

Low-Flammable Parahydrogen-Polarized MRI Contrast Agents

Many MRI contrast agents formed with the parahydrogen-induced polarization (PHIP) technique exhibit biocompatible profiles. In the context of respiratory imaging with inhalable molecular contrast agents, the development of nonflammable contrast agents would nonetheless be highly beneficial for the biomedical translation of this sensitive, high-throughput and affordable hyperpolarization technique. To this end, we assess the hydrogenation kinetics, the polarization levels and the lifetimes of PHIP hyperpolarized products (acids, ethers and esters) at various degrees of fluorine substitution. The results highlight important trends as a function of molecular structure that are instrumental for the design of new, safe contrast agents for in vivo imaging applications of the PHIP technique, with an emphasis on the highly volatile group of ethers used as inhalable anesthetics.     

Cyclobutadiene cobalt complexes as catalysts for insertion of diazo compounds into X–H bonds

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Synthesis and microbiological properties of novel bis-quaternary ammonium compounds based on 4,4′-oxydiphenol spacer

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A review of normalization techniques in analytical atomic spectrometry with laser sampling: From single to multivariate correction

Despite many advantages of laser sampling in analytical atomic spectrometry, the signal intensity of these hyphenated methods suffers from the specific influences resulting from the laser ablation process of a sample. The problems that arise affect the accuracy and precision of analytical results. Different techniques of analytical signal normalization which improve figures-of-merit for atomic spectrometry with laser sampling are considered in this review. The characteristics and application of these approaches including the use of internal standards, single or several reference signals and multivariate correction of analytical signal are discussed.     

Orienting Effect of the Cage Addends: The Case of Nucleophilic Cyclopropanation of C2‐C70(CF3)8

C₂‐C₇₀(CF₃)₈ was found to be a very promising substrate in the Bingel and the Bingel–Hirsch reactions combining perfect regioselectivity with much higher reactivity compared to its analogs. The reactions with diethyl malonate yield a single isomer of the monoadduct C₇₀(CF₃)₈[C(CO₂Et)₂] and a single C₂‐symmetrical bisadduct C₇₀(CF₃)₈[C(CO₂Et)₂]₂. The Bingel–Hirsch variation is particularly interesting in that it additionally affords, in a similar regioselective manner, the unexpected alkylated derivatives C₇₀(CF₃)₈[CH(CO₂Et)₂]H and C₇₀(CF₃)₈[C(CO₂Et)₂][CH(CO₂Et)₂]H. The novel compounds have been isolated and structurally characterized by means of ¹H and ¹⁹F NMR spectroscopy as well as single‐crystal X‐ray diffraction. The mechanistic and regiochemical aspects of the reaction are explained with the aid of DFT calculations.     

Expansions in non-integer bases: Lower, middle and top orders

Let q∈(1,2); it is known that each x∈[0,1/(q−1)] has an expansion of the form with an∈{0,1}. It was shown in [P. Erd?s, I. Joó, V. Komornik, Characterization of the unique expansions and related problems, Bull. Soc. Math. France 118 (1990) 377-390] that if , then each x∈(0,1/(q−1)) has a continuum of such expansions; however, if , then there exist infinitely many x having a unique expansion [P. Glendinning, N. Sidorov, Unique representations of real numbers in non-integer bases, Math. Res. Lett. 8 (2001) 535-543]. In the present paper we begin the study of parameters q for which there exists x having a fixed finite number m>1 of expansions in base q. In particular, we show that if q<q₂=1.71…, then each x has either 1 or infinitely many expansions, i.e., there are no such q in . On the other hand, for each m>1 there exists γm>0 such that for any q∈(2−γm,2), there exists x which has exactly m expansions in base q.     

Instanton partition functions and M-theory

We discuss instanton partition functions in various spacetime dimensions. These partition functions capture some information about the spectrum of the supersymmetric gauge theories and their low-energy dynamics. Some of these theories can be defined microscopically only through string theory. Remarkably, they even know about the M-theory. Our conjectures include the identities between the generalization of the MacMahon formula and the character of M-theory, compactified down to 0 + 1 dimension. This article is based on the 5th Takagi Lectures that the author delivered at the University of Tokyo on October 4 and 5, 2008.