Visible‐Light‐Induced Trifluoromethylation of Isonitrile‐Substituted Methylenecyclopropanes: Facile Access to 6‐(Trifluoromethyl)‐7,8‐Dihydrobenzo[k]phenanthridine Derivatives

A new visible‐light‐induced trifluoromethylation of isonitrile‐substituted methylenecyclopropanes is developed. A range of substituted 6‐(trifluoromethyl)‐7,8‐dihydrobenzo[k]phenanthridine derivatives are readily furnished by this newly developed tandem reaction with moderate to good yields. This reaction allows the direct formation of two six‐membered rings and three new C?C bonds, including the C?CF₃ bond, under visible light irradiation.     

A Selective RhI‐Catalyzed Substrate‐Controlled C−C Bond Activation of Benzyl Sulfonamide/Alcohol‐Tethered Alkylidenecyclopropanes

Benzyl sulfonamide/alcohol‐tethered alkylidenecyclopropanes undergo a rhodium‐catalyzed and substrate‐controlled selective C?C bond activation, producing three types of common organic structural units: benzo[c]azepine/oxepines, dihydronaphthalen‐1‐amines, and conjugated dienes. Epoxidation and aromatization of these products to construct two useful compounds have also been achieved.     

Zn or O? An Atomic Level Comparison on Antibacterial Activities of Zinc Oxides

For the first time, the influence of different types of atoms (Zn and O) on the antibacterial activities of nanosized ZnO was quantitatively evaluated with the aid of a 3D‐printing‐manufactured evaluation system. Two different outermost atomic layers were manufactured separately by using an ALD (atomic layer deposition) method. Interestingly, we found that each outermost atomic layer exhibited certain differences against gram‐positive or gram‐negative bacterial species. Zinc atoms as outermost layer (ZnO?Zn) showed a more pronounced antibacterial effect towards gram‐negative E. coli (Escherichia coli), whereas oxygen atoms (ZnO?O) showed a stronger antibacterial activity against gram‐positive S. aureus (Staphylococcus aureus). A possible antibacterial mechanism has been comprehensively discussed from different perspectives, including Zn²⁺ concentrations, oxygen vacancies, photocatalytic activities and the DNA structural characteristics of different bacterial species.     

Manage Pension Deficit with Heterogeneous Insurance

This paper considers a positive and increasing pension deficit of a certain pay-as-you-go (PAYG) pension system, and tries to make up for this deficit by using heterogeneous insurance. The positive pension deficit is formulated as a mathematical function in continuous time. The surplus of an appropriate heterogeneous insurance is described by diffusion approximation of a Cramér-Lundberg process. The system of extended Hamilton-Jacobi-Bellman equations under mean-variance criterion is established. The closed-form solution and optimal surplus-multiplier of heterogenous insurance are obtained. Some interpretations further explain the theoretical values of the results.

     

Gold‐Catalyzed Fluorination–Hydration: Synthesis of α‐Fluorobenzofuranones from 2‐Alkynylphenol Derivatives

The Au^I‐catalyzed fluorination–hydration of 2‐alkynylphenol derivatives in the presence of Selectfluor [1‐chloromethyl‐4‐fluoro‐1,4‐diazoniabicyclo‐[2.2.2]octane bis(tetrafluoroborate)] has been developed. This method provides straightforward access to α‐fluorobenzofuranones with the construction of C?O, C=O, and C?F bonds in a single step on the basis of an Au^I/Au^III redox catalytic cycle. Several control experiments, including the asymmetric variant of this reaction, were also conducted to gain insight into the reaction mechanism.     

Synthesis and Insecticidal Activities of Chlorothiazolyl Analogs of Nitromethylene Neonicotinoids with Tetrahydropyridine Fixed cis‐Configuration

The chlorothiazolyl moiety was an effective bioisoster of chloropyridyl in pesticide molecular design. Replacement of chloropyridyl in cis‐nitromethylene neonicotinoids with chlorothiazolyl generated the chlorothiazolyl counterpart of nitromethylene neonicotinoids with tetrahydropyridine fixed cis‐configuration. Bioassay against cowpea aphis (Aphis craccivora) indicated that the chlorothiazolyl analogs could maintain the high insecticidal activity.     

The roles of cysteines in the heme domain of human soluble guanylate cyclase

Soluble guanylate cyclase(sGC) is a critical heme-containing enzyme involved in NO signaling.The dimerization of sGC subunits is necessary for its bioactivity and its mechanism is a striking and an indistinct issue.The roles of heme domain cysteines of the sGC on the dimerization and heme binding were investigated herein.The site-directed mutations of three conserved cysteines(C78A,C122A and C174S) were studied systematically and the three mutants were characterized by gel filtration analysis,UV-vis spectroscopy and heme transfer examination.Cys78 was involved in heme binding but not referred to the dimerization,while Cys174 was demonstrated to be involved in the homodimerization.These results provide new insights into the cysteine-related dimerization regulation of sGC.     

Cold crystallization behavior of polyamide 6 in PS‐g‐PA6 graft copolymers

TEM micrographs show that the PA grafts of PS‐g‐PA6 graft copolymers, which are obtained directly by extracting homo‐PA6 out from the homo‐PA6/PS‐g‐PA6 blends, are in the form of wormlike structure. The wormlike PA6 domains can shrink into droplets after annealing at 250 °C for 15 min. The diameter of the droplet determined by TEM and SAXS is in the range of 50–60 nm. This article reports on a unique crystallization behavior of the PA6 grafts in PS‐g‐PA6 graft copolymers. In a DSC cooling scan, PA6 grafts do not crystallize from the melt with a cooling rate of 10 °C/min. However, there is a cold crystallization peak around 65 °C in the subsequent heating scan. This cold crystallization phenomenon, which has not yet been reported in the literature till now, follows well the homogeneous nucleation mechanism and is depressed at relatively slow cooling rates (2 °C/min) or even completely eliminated after annealing within a specific temperature range. It may be caused by the slow diffusion or transport rate of the less flexible PA6 grafts to the crystal fronts when crystallization takes place around its glass transition temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 65–73, 2010     

Synthesis of novel chiral oxazoline-Schiff base ligands for the catalytic asymmetric chlorination of β-keto esters

A series of novel monooxazoline-Schiff base ligands 1 has been successfully synthesized. The Cu(I)–1a complex showed excellent catalytic activities with up to 83% ee for the asymmetric α-chlorination of β-keto esters.