Halonium-Induced Polyene Cyclizations

International audienceThis review covers the methods that chemists have developed to access halogenated polycyclic structures from polyenes, by emulating Nature's enzymatic machineries. From pioneering studies to the most recent developments, the different strategies, whether based on the use of standard reagents or on the design of specific ones, will be presented. Finally, asymmetric reactions and applications for the total synthesis of natural products will be exposed

Iodine(III)-mediated halogenations of acyclic monoterpenoids

International audienceFive different halofunctionalizations of acyclic monoterpenoids were performed using a combination of a hypervalent iodine(III) reagent and a halide salt. In this manner, the dibromination, the bromo(trifluoro)acetoxylation, the bromohydroxylation, the iodo(trifluoro)acetoxylation or the ene-type chlorination of the distal trisubstituted double bond occurred with excellent selectivity and moderate to good yields. 110

Transition Metal Trichalcogenides as Novel Layered Nano Species

In search for new materials for nanoelectronics, many efforts have been put into development of chem-istry and physics of graphene, and, more recently, of other inorganic layered compounds having a bandgap (h-BN, MoS2 etc.). Here we introduce a new view on the family of transition metal trichalcogenides MQ3 (M=Ti, Zr, Nb, Ta; Q=S, Se), which were earlier considered as quasi-one-dimensional systems, and demon-strate that they also may be regarded as layered species suitable for exfoliation by a chemical method. Stable, concentrated colloidal dispersions of high-quality crystalline NbS3 and NbSe3 nanoribbons down to mono- and few-layer-thick are prepared by ultrasonic treatment of the bulk compound in several common organic solvents (DMF, NMP, CH3CN, iPrOH, H2O/EtOH). The dispersions and thin films prepared from them by vacuum filtration or spraying are characterized by a set of physical-chemical methods. Current-voltage characteristics of the NbS3 films show that charge carrier mobility is as high as 1200 – 2400 cm2V-1s-1, exceeding that of MoS2 and making NbQ3 promising potential candidates for field-effect transistors. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3522

Amphibian (Xenopus laevis) Interleukin-8 (CXCL8): A Perspective on the Evolutionary Divergence of Granulocyte Chemotaxis

The glutamic acid-leucine-arginine (ELR) motif is a hallmark feature shared by mammalian inflammatory CXC chemokines such the granulocyte chemo-attractant CXCL8 (interleukin-8, IL-8). By contrast, most teleost fish inflammatory chemokines lack this motif. Interestingly, the amphibian Xenopus laevis encodes multiple isoforms of CXCL8, one of which (CXCL8a) possesses an ELR motif, while another (CXCL8b) does not. These CXCL8 isoforms exhibit distinct expression patterns during frog development and following immune challenge of animals and primary myeloid cultures. To define potential functional differences between these X. laevis CXCL8 chemokines, we produced them in recombinant form (rCXCL8a and rCXCL8b) and performed dose-response chemotaxis assays. Our results indicate that compared to rCXCL8b, rCXCL8a is a significantly more potent chemo-attractant of in vivo-derived tadpole granulocytes and of in vitro-differentiated frog bone marrow granulocytes. The mammalian CXCL8 mediates its effects through two distinct chemokine receptors, CXCR1 and CXCR2 and our pharmacological inhibition of these receptors in frog granulocytes indicates that the X. laevis CXCL8a and CXCL8b both chemoattract tadpole and adult frog granulocytes by engaging CXCR1 and CXCR2. To delineate which frog cells are recruited by CXCL8a and CXCL8b in vivo, we injected tadpoles and adult frogs intraperitoneally with rCXCL8a or rCXCL8b and recovered the accumulated cells by lavage. Our transcriptional and cytological analyses of these tadpole and adult frog peritoneal exudates indicate that they are comprised predominantly of granulocytes. Interestingly, the granulocytes recruited into the tadpole, but not adult frog peritonea by rCXCL8b, express significantly greater levels of several pan immunosuppressive genes

Interaction of 1,3,2,4-benzodithiadiazines with aromatic phosphines and phosphites

Although an interaction between hydrocarbon and fluorocarbon 1,3,2,4-benzodithiadiazines (1 ) and P(C6H5)3 continuously produces chiral 1,2,3-benzodithiadiazol-2-yl iminophosporanes (2; in this work, 5,7-difluoro derivative 2a ) via 1:1 condensation, an interaction between 1 and other PR3 reagents gives different products. With R [DOUBLE BOND] OC6H5 and both hydrocarbon and fluorocarbon 1, only X=P(OC6H5)3 (X = S, O) were identified in the complex reaction mixtures by 13С and 31Р NMR and GC-MS. With R = C6F5, no interaction with the archetypal 1 was observed but catalytic addition of atmospheric water to the heterocycle afforded 2-amino-N-sulfinylbenzenesulfenamide (4 ). With electrophilic B(C6F5)3 instead of nucleophilic P(C6F5)3, only adduct H3N→B(C6F5)3 and a new polymorph of C6F5B(OH)2 were isolated and identified by X-ray diffraction (XRD). A molecular structure of 2a was confirmed by XRD, and the π-stacked orientation of one of phenyl groups and heterocyclic moiety was observed. This structure is in general agreement with that calculated at the RI-MP2 level of theory, as well as at three different levels of DFT theory with the PBE and B3LYP functionals. Mild thermolysis of 2a in a dilute decane solution gave persistent 5,7-difluoro-1,2,3-benzodithiazolyl (3a ) identified by EPR in combination with DFT calculations

Allylic Carbocyclic Inhibitors Covalently Bind Glycoside Hydrolases

Allylic cyclitols were investigated as covalent inhibitors of glycoside hydrolases by chemical, enzymatic, proteomic, and computational methods. This approach was inspired by the C$_{7}$ cyclitol natural product streptol glucoside, which features a potential carbohydrate leaving group in the 4-position (carbohydrate numbering). To test this hypothesis, carbocyclic inhibitors with leaving groups in the 4- and 6- positions were prepared. The results of enzyme kinetics analyses demonstrated that dinitrophenyl ethers covalently inhibit α-glucosidases of the GH13 family without reactivation. The labeled enzyme was studied by proteomics, and the active site residue Asp214 was identified as modified. Additionally, computational studies, including enzyme homology modeling and density functional theory (DFT) calculations, further delineate the electronic and structural requirements for activity. This study demonstrates that previously unexplored 4- and 6-positions can be exploited for successful inhibitor design

TGF-β1 Exerts Opposing Effects on Grass Carp Leukocytes: Implication in Teleost Immunity, Receptor Signaling and Potential Self-Regulatory Mechanisms

In fish immunity, the regulatory role of transforming growth factor-β1 (TGF-β1) has not been fully characterized. Here we examined the immunoregulatory effects of TGF-β1 in grass carp peripheral blood leukocytes (PBL) and head kidney leukocytes (HKL). It is interesting that TGF-β1 consistently stimulated the cell viability and the mRNA levels of pro-inflammatory cytokines (Tnfα and Ifnγ) and T/B cell markers [Cd4-like (Cd4l), Cd8α, Cd8β and Igμ] in PBL, which contrasted with its inhibitory tone in HKL. Further studies showed that grass carp TGF-β1 type I receptor, activin receptor-like kinase 5 (ALK5), was indispensable for the immunoregulatory effects of TGF-β1 in PBL and HKL. Notably, TGF-β1 persistently attenuated ALK5 expression, whereas immunoneutralization of endogenous grass carp TGF-β1 could increase ALK5 mRNA and protein levels. It is consistent with the observation that TGF-β1 decreased the number of ALK5+ leukocytes in PBL and HKL, revealing a negative regulation of TGF-β1 signaling at the receptor level. Moreover, transient treatment with TGF-β1 for 24 h was sufficient to induce similar cellular responses compared with the continuous treatment. This indicated a possible mechanism by which TGF-β1 triggered the down-regulation of ALK5 mRNA and protein, leading to the desensitization of grass carp leukocytes toward TGF-β1. Accordingly, our data revealed a dual role of TGF-β1 in teleost immunity in which it can serve as a positive or negative control device and provided additional mechanistic insights as to how TGF-β1 controls its signaling in vertebrate leukocytes

Highly Exfoliated Graphite Fluoride as a Precursor for Graphene Fluoride Dispersions and Films

We synthesized highly exfoliated graphite fluoride of approximate composition C2F by treating highly exfoliated graphite with ClF3. The formed material was found to be dispersible in solvents giving 1 to 5 layered fluorinated graphene. Dispersions successfully formed in polar organic solvents capable of establishing hydrogen bonds. The highest stability is achieved in branched alcohols such as tert-butanol. The dispersions may be further processed into thin films by vacuum filtration technique. Also, composite multilayered films of graphene fluoride and graphene may be prepared. (doi: 10.5562/cca1972

Highly Exfoliated Graphite Fluoride as a Precursor for Graphene Fluoride Dispersions and Films

We synthesized highly exfoliated graphite fluoride of approximate composition C2F by treating highly exfoliated graphite with ClF3. The formed material was found to be dispersible in solvents giving 1 to 5 layered fluorinated graphene. Dispersions successfully formed in polar organic solvents capable of establishing hydrogen bonds. The highest stability is achieved in branched alcohols such as tert-butanol. The dispersions may be further processed into thin films by vacuum filtration technique. Also, composite multilayered films of graphene fluoride and graphene may be prepared. (doi: 10.5562/cca1972