Sterically Demanding Unsymmetrical Diaryl-λ3-iodanes for Electrophilic Pentafluorophenylation and an Approach to α-Pentafluorophenyl Carbonyl Compounds with an All-Carbon Stereocenter

A sterically demanding unsymmetrical pentafluorophenyl-triisopropylphenyl-λ³-iodane was developed as an effective reagent for the electrophilic pentafluorophenylation of various β-keto esters and a β-keto amide. 17 examples of α-pentafluorophenylated 1,3-dicarbonyl compounds 3 having a quaternary carbon center are provided. The resulting compounds were nicely transformed into chiral α-pentafluorophenyl ketones with an all-carbon stereogenic center in high yields and high enantioselectivities using asymmetric organocatalysis (up to 98 % ee) or asymmetric metal catalysis (up to 82 % ee).     

The first bisgermylene,its synthesis and addition to organic halides and dihalides

The first bisgermylene with an acyclic structure was synthesized for the first time by one-pot, two-step ligand substitution reactions from the 1,4-dioxane complex of germanium dichloride. The reactions of the bisgermylene with organic halides gave corresponding oxidative addition products, and with organic dihalides gave oligomeric polyadditon products.     

Polymer synthesis by means of germylene and stannylene

Divalent group 14 metal species, a germylene(la) and a stannylene(lb), behaved as a comonomer(reductant monomer) in the copolymerization with p-benzoquinone derivatives(oxidant monomer)(“oxidation-reduction copolymerization”) and as an initiator for anionic monomers. The copolymerization took place without initiator at a lower temperature to give an alternating copolymer. N-phenyl-p-quinoneimine also behaved as a reactive oxidant monomer toward la and lb. These species have been shown to induce the polymerization of anionically polymerizable monomers such as methyl methacrylate, methacrylonitrile, and 4-vinylpyridine. Based on the mechanistic examination of the polymerization, a new alternating copolymerization between la and 2-cyclohexene-l-one has been developed to produce a copolymer having a metal-enolate structure, which involves the oxidation-reduction process during the copolymerization.     

Detection of diminished response to cold pressor test in smokers: Assessment using phase-contrast cine magnetic resonance imaging of the coronary sinus

Purpose

The purposes of this study were to evaluate the reproducibility for measuring the cold pressor test (CPT)-induced myocardial blood flow (MBF) alteration using phase-contrast (PC) cine MRI, and to determine if this approach could detect altered MBF response to CPT in smokers.

Materials and methods

After obtaining informed consent, ten healthy male non-smokers (mean age: 28 ± 5 years) and ten age-matched male smokers (smoking duration ≥ 5 years, mean age: 28 ± 3 years) were examined in this institutional review board approved study. Breath-hold PC cine MR images of the coronary sinus were obtained with a 3 T MR imager with 32 channel coils at rest and during a CPT performed after immersing one foot in ice water. MBF was calculated as coronary sinus flow divided by the left ventricular (LV) mass which was given as a total LV myocardial volume measured on cine MRI multiplied by the specific gravity (1.05 g/mL).

Results

In non-smokers, MBF was 0.86 ± 0.25 mL/min/g at rest, with a significant increase to 1.20 ± 0.36 mL/min/g seen during CPT (percentage change of MBF (?MBF (%)); 39.2% ± 14.4%, p < 0.001). Inter-study reproducibility for ?MBF (%) measurements by different MR technologist was good, as indicated by the intraclass correlation coefficient of 0.93 and reproducibility coefficient of 10.5%. There was no significant difference between smokers and non-smokers for resting MBF (0.85 ± 0.32 mL/min/g, p = 0.91). However, ?MBF (%) in smokers was significantly reduced (-4.0 ± 32.2% vs. 39.2 ± 14.4%, p = 0.011).

Conclusion

PC cine MRI can be used to reproducibly quantify MBF response to CPT and to detect impaired flow response in smokers. This MR approach may be useful for monitoring the sequential change of coronary blood flow in various potentially pathologic conditions and for investigating its relationship with cardiovascular risk.     

Good ideals in Gorenstein local rings

Let be an -primary ideal in a Gorenstein local ring (, ) with , and assume that contains a parameter ideal in as a reduction. We say that is a good ideal in if is a Gorenstein ring with . The associated graded ring of is a Gorenstein ring with if and only if . Hence good ideals in our sense are good ones next to the parameter ideals in . A basic theory of good ideals is developed in this paper. We have that is a good ideal in if and only if and . First a criterion for finite-dimensional Gorenstein graded algebras over fields to have nonempty sets of good ideals will be given. Second in the case where we will give a correspondence theorem between the set and the set of certain overrings of . A characterization of good ideals in the case where will be given in terms of the goodness in their powers. Thanks to Kato's Riemann-Roch theorem, we are able to classify the good ideals in two-dimensional Gorenstein rational local rings. As a conclusion we will show that the structure of the set of good ideals in heavily depends on . The set may be empty if , while is necessarily infinite if and contains a field. To analyze this phenomenon we shall explore monomial good ideals in the polynomial ring in three variables over a field . Examples are given to illustrate the theorems.

     

Fuzzy logic in measurements

Our main interest in this paper is to translate from “natural language” into “system theoretical language”. This is of course important since a statement in system theory can be analyzed mathematically or computationally. We assume that, in order to obtain a good translation, “system theoretical language” should have great power of expression. Thus we first propose a new frame of system theory, which includes the concepts of “measurement” as well as “state equation”. And we show that a certain statement in usual conversation, i.e., fuzzy modus ponens with the word “very”, can be translated into a statement in the new frame of system theory. Though our result is merely one example of the translation from “natural language” into “system theoretical language”, we believe that our method is fairly general.     

Effect of particle size and shape on nonresonant random laser action of dye-doped polymer random media

We present an experimental study of the light emission from dye-doped polymer random media dispersed with TiO₂ particles of various sizes, shapes, and structures. Random lasing with nonresonant feedback, similar to that for spherically shaped particles that are used for conventional random lasers, is observed for almost all types of particles and aggregates. The efficiency of random lasing for each medium is analyzed using the relationship between the emission spectrum and the transport mean free path (TMFP), which is measured by enhanced backscattering experiments. Results show that the peak emission intensity depends strongly on the particle shape and structure, whereas the spectral linewidth is governed by the TMFP.     

Absolute stereochemistry of amphidinolides G and H

[structure: see text] Absolute stereochemistry of amphidinolides G (1) and H (2), potent cytotoxic 27- and 26-membered macrolides, respectively, isolated from a marine dinoflagellate Amphidinium sp., was determined by X-ray diffraction analysis, synthesis of a degradation product (3) of 2, and interconversion between 1 and 2.     

Heteroleptic and Homoleptic Iron(III) Complexes with a Tris(N-Heterocyclic Carbene) Borate Ligand: Synthesis,Characterization, and Catalytic Application

Heteroleptic and homoleptic iron(III) complexes supported by a tris(N-heterocyclic carbene) borate ligand have been prepared and crystallographically characterized. The strong electron-donating character of the tris(carbene) donor was revealed by UV-vis absorption spectroscopy and electrochemical measurements combined with quantum chemical calculations. The catalytic activity of each complex was evaluated in cyclohexane oxidation reaction using meta-chloroperoxybenzoic acid (=mCPBA) as an oxidant, and both complexes show high catalytic activity and selectivity with TON=∼350 and A/(K+L)=8–10. Mechanistic studies suggested that radical-chain processes are involved in the reaction due to mCPBA acting as a one-electron oxidant, concomitant with the pathway of metal-based reactive species. Moreover, it was found that the homoleptic and heteroleptic complexes differed significantly in the involvement of metal-based active species, with the homoleptic complex exhibiting more metal-based reactions.     

A new fluorescent probe for zinc(II): an 8-hydroxy-5-N,N-dimethylaminosulfonylquinoline-pendant 1,4,7,10-tetraazacyclododecane

A new fluorescent probe for Zn2+, namely, 8-hydroxy-5-N,N-dimethylaminosulfonylquinolin-2-ylmethyl-pendant cyclen (L8), was designed and synthesized (cyclen=1,4,7,10-tetraazacyclododecane). By potentiometric pH, 1H NMR, and UV spectroscopic titrations, the deprotonation constants pKa1-pKa6 of L(8)4 HCl were determined to be <2, <2, <2 (for amino groups of the cyclen and quinoline moieties), 7.19+/-0.05 (for 8-OH of the quinoline moiety), 10.10+/-0.05, and 11.49+/-0.05, respectively, at 25 degrees C with I=0.1 (NaNO3). The results of 1H NMR, potentiometric pH, and UV titrations, as well as single-crystal X-ray diffraction analysis, showed that L8 and Zn2+ form a 1:1 complex [Zn(H-1L8)], in which the 8-OH group of the quinoline ring of L8 is deprotonated and coordinates to Zn2+, in aqueous solution at neutral pH. On addition of one equivalent of Zn2+ and Cd2+, the fluorescence emission of L8 (5 microM) at 512 nm in aqueous solution at pH 7.4 [10 mM HEPES with I=0.1 (NaNO3)] and 25 degrees C increased by factors of 17 and 43, respectively. We found that the cyclen moiety has the unique property of quenching the fluorescence emission of the quinolinol moiety when not complexed with metal cations, but enhancing emission when complexed with Zn2+ or Cd2+. In addition, the Zn2+-L8 complex [Zn(H-1L8)] is much more thermodynamically and kinetically stable (Kd{Zn(H-1L8)}=[Zn2+]free[L8]free/[Zn(H-1L8)]=8 fM at pH 7.4) than the Zn2+ complexes of our previous Zn2+ fluorophores ([Zn(H-1L2)] and [Zn(L3)]). Furthermore, formation of [Zn(H-1L8)] is much faster than those of [Zn(H-1L2)] and [Zn(L3)]. The staining of early-stage apoptotic cells with L8 is also described.