ADDITION OF SULPHENYL CHLORIDES TO ACETYLENES. STRUCTURE OF THE INTERMEDIATE

Abstract

Sulphenyl chlorides react in sulphur dioxide with acetylenes to give thiirenium chlorides 1 which lead to the final adducts 2.     

Exploring the Phase-Selective,Green, Hydrothermal Synthesis of Upconverting Doped Sodium Yttrium Fluoride: Effects of Temperature,Time, and Precursors

The aim of this work was i) to develop a hydrothermal, low-temperature synthesis protocol affording the upconverting hexagonal phase NaYF₄ with suitable dopants while adhering to the “green chemistry” standards and ii) to explore the effect that different parameters have on the products. In optimizing the synthesis protocol, short reaction times and low temperatures (below 150 °C) were considered. Yb³⁺ and Er³⁺ ions were chosen as dopants for the NaYF₄ material. Within the context of the second goal, parameters including nature of the precursors, treatment temperature, and treatment time were investigated to afford a pure hexagonal crystalline phase, both in the doped and undoped materials. To fully explore the synthesis results, the prepared materials were characterized from a structural (XRD), compositional (XPS, ICP-MS), and morphological (SEM) point of view. The upconverting properties of the compounds were confirmed by photoluminescence measurements.     

X-ray structures and anionotropic rearrangements of Di-tert-butyl-substituted thiiranium and thiirenium ions. A structure-reactivity relationship

The X-ray structures of c-2,t-3-di-tert-butyl-r-1-methylthiiranium 8 BF(4)(-), t-2,t-3-di-tert-butyl-r-1-methylthiiranium ion 10 BF(4)(-), and 2,3-di-tert-butyl-1-methylthiirenium 11 BF(4)(-) have been determined. The DeltaG()(298) values for the rearrangements from the cis and the trans tert-butyl groups of 8 SbCl(6)(-) to thietanium ion (two intramolecular S(N)2 displacements) and for the rearrangement of 11 SbCl(6)(-) to thietium ion (an intramolecular S(N)2-Vin displacement) are linearly correlated with the strengths of the C-S breaking bonds, suggesting that the two mechanisms are, in the absence of steric hindrance, uniquely governed by the nucleofugality of the sulfonium leaving group.     

Profinite Groups with Multiplicative Probabilistic Zeta Function

To a finitely generated profinite group G, a formal Dirichletseries P_G(s)=_na_n/n^s is associated, where a_n = _|G:H|=n µ_G(H).It is proved that G is prosoluble if and only if the sequence{a_n}_nN is multiplicative, that is, a_rs = a_ra_s for any pairof coprime positive integers r and s. This extends the analogousresult on the probabilistic zeta function of finite groups.     

Asymptotic Results for Transitive Permutation Groups

In this paper we give answers to some open questions concerninggeneration and enumeration of finite transitive permutationgroups. In [1], Bryant, Kovács and Robinson proved thatthere is a number c^' such that each soluble transitive permutationgroup of degree n2 can be generated by elements, and later A. Lucchini [5] extended thisresult (with a different constant c') to finite permutationgroups containing a soluble transitive subgroup. We are nowable to prove this theorem in full generality, and this solvesthe question of bounding the number of generators of a finitetransitive permutation group in terms of its degree. The resultobtained is the following. 1991 Mathematics Subject Classification20B05, 20D60.     

Dark and Photochemical Interactions of Dimethyltetrahydrobenzoangelicin with DNA

A study of dark interaction and photoreaction between 4,6-dimethyltetrahydrobenzoangelicin (THBA) and DNA is described. 4,6-Dimethyltetrahydrobenzoangelicin is a furocoumarin derivative in which 4'and 5'carbons are linked by a four-methylene bridge. In spite of the bulky aliphatic ring, THBA forms a complex with DNA in the dark and, on UVA irradiation, reacts with pyrimidine bases of DNA yielding monoadducts only involving its furan side double bond. Two main photoproducts form: they derive from a C₄-cycloaddition to thymine and cytosine, respectively, and account for 56% and 39% of the total photoreaction yield. Both show cis-syn configuration. Two other isomers, one with thymine and one with cytosine, formed with so much lower yield ( ca 3 and 1%, respectively) that their structure could not be assigned. Furthermore, in spite of its angular structure, THBA induces a small number of crosslinks in DNA.     

An upper bound on the Chebotarev invariant of a finite group

A subset {g ₁,..., g _d } of a finite group G invariably generates \(\left\{ {g_1^{{x_1}}, \ldots ,g_d^{{x_d}}} \right\}\) generates G for every choice of x _i ∈ G. The Chebotarev invariant C(G) of G is the expected value of the random variable n that is minimal subject to the requirement that n randomly chosen elements of G invariably generate G. The first author recently showed that \(C\left( G \right) \leqslant \beta \sqrt {\left| G \right|} \) for some absolute constant β. In this paper we show that, when G is soluble, then β is at most 5/3. We also show that this is best possible. Furthermore, we show that, in general, for each ε > 0 there exists a constant c _ε such that \(C\left( G \right) \leqslant \left( {1 + \in } \right)\sqrt {\left| G \right|} + {c_ \in }\).     

Timing performance of ZnO:Ga nanopowder composite scintillators

The implementation of nanocrystal‐based composite scintillators as a new generation of ultrafast particle detectors is explored using ZnO:Ga nanopowder. Samples are characterized with a spectral‐time resolved photon counting system and pulsed X‐rays, followed by coincidence time resolution (CTR) measurements under 511 keV gamma excitation. Results are comparable to CTR values obtained using bulk inorganic scintillators. Bringing the ZnO:Ga nanocrystal's timing performance to radiation detectors could pave the research path towards sub‐20 ps time resolution as shown in this contribution. However, an efficiency boost when placing nanopowders in a transparent host constitutes the main challenge in order to benefit from sub‐nanosecond recombination times. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)