Synthesis and γ-radiolysis of 2′-deoxy-5-fluorouridine and 5-fluorouridine derivatives

Seventeen compounds having a variety of substituents at the 3- and 5′-positions of 2′-deoxy-5-fluorouridine (5-FUdR) and 5-fluorouridine (5-FUR) were synthesized, and their γ-radiolysis in aqueous solutions were studied. The compounds having thioureido (RNHCSNH, R  H, PhCH₂, acyl) and thiocarbonylamino (XCSNH, X  PhCH₂S, PhO) groups at the 3-position of 5-FUdR were efficiently cleaved to give 5-FUdR with high G values upon γ-irradiation of their aqueous solutions. The active species for these cleavage reactions were hydrated electron (e⁻ _aq), H^• and HO^•. However, the compounds having a dimethylsulfoxyimino group at 3-position of 5-FUdR and 5-FUR afforded 5-FUdR and 5-FUR only under the radiolysis conditions where e⁻ _aq becomes a principal active species. The compound having a 2-benzoylthiazoylthiocarbonylamino group at the 3-position of 5-FUdR showed the highest reactivity toward HO^.. The mechanisms of these γ-radiolysis reactions are discussed. The examination of anticellular activities of γ-irradiated compounds having a thiocarbonylamino group at the 3-position of 5-FUdR toward murine Sarcoma 180 cells revealed that these compounds may be utilized as a candidate for a radiation-induced drug (RID).     

Essential Oils Derived from Cistus Species Activate Mitochondria by Inducing SIRT1 Expression in Human Keratinocytes,Leading to Senescence Inhibition

Cistus L. is a genus of dicotyledonous perennial herbaceous plants. Cistus species have been commonly used in folk medicine in the Mediterranean region. In the present study, the biological activities of essential oils derived from Cistus species (Cistus laurifolius, C. monspeliensis, C. creticus, and C. salviifolius) were evaluated. Essential oils derived from C. laurifolius and C. monspeliensis were found to augment the expression of SIRT1, an anti-aging gene, in the normal culture of HaCaT cells. Furthermore, these essential oils increased the number and size of mitochondria and augmented their activity. These effects were thought to be caused by the up- and downregulated expression of MITOL and Drp1 in HaCaT cells, respectively, in response to the essential oil treatment. In addition, these essential oils were found to attenuate ultraviolet-B-induced mitochondrial damage and cellular senescence in HaCaT cells. These findings indicate that essential oils derived from C. laurifolius and C. monspeliensis may inhibit skin aging through mitochondrial regulation via SIRT1 activation.     

Carbonylative Stille coupling reactions of benzyl chlorides with allyltributylstannane catalyzed by palladium nanoparticles

The carbonylative Stille coupling reaction of benzyl chlorides with allyltributylstannane was successfully conducted by using palladium nanoparticles as the catalyst under phosphine ligand-free conditions. The corresponding α,β-unsaturated ketone products were obtained in good to excellent yields.     

Chemical modification of diamond powder using photolysis of perfluoroazooctane

Photolysis of perfluoroazooctane with diamond powders led to chemical modification of the surface with the introduction of perfluorooctyl ester and ether functional groups, the presence of which was confirmed by means of FT-IR, XPS and 19F NMR measurements.     

Investigation of the center intensity of first- and second-order Laguerre-Gaussian beams with linear and circular polarization

The vectorial Debye integral shows that tightly focused Laguerre-Gaussian (LG) beams have a residual intensity at the focal point for linear polarization, for a topological charge of m=1 and 2. We measured the shapes of linearly and circularly polarized LG beams and found that a central intensity appeared at m=1 and 2 for linear and right-handed circular polarization, however, it is completely canceled for left-handed circular polarization. In general, when the orbital angular momentum of the LG beam is parallel to the spin angular momentum of the photons, zero intensity is always achieved at the focus.     

Transversal infinitesimal automorphisms of harmonic foliations on complete manifolds

Summary In this paper we study infinitesimal automorphisms of finiteL ²-norm for harmonic Riemannian and Kähler foliations admitting a complete bundle-like metric. The results generalize facts established recently in the compact case.1980 Mathematics Subject Classification: Primary 57 R 30, Secondary 58 E 20.Work supported in part by a grant from the National Science Foundation.     

Measurement of the vector A y and tensor A yy , A xx , A xz analyzing powers for the dd → 3H p reaction at 200 MeV

The data on the vector A _y and tensor A _yy , A _xx , A _xz analyzing powers for the d → ³H p reaction have been obtained at the energy of the initial deuteron of 200MeV in the angular range of 0–95 degrees in the c.m.s. The calculations performed within one-nucleon exchange model with the use of the standard three-nucleon bound state wave functions fail to reproduce the data on the tensor analyzing powers.     

Catalytic Alkynylation of Polyfluoroarenes by Amide Base Generated In Situ

We herein demonstrate that the amide base generated in situ from CsF and N(TMS)₃ catalyzes the deprotonative coupling reactions of terminal alkynes with polyfluoroarenes, wherein mono- and dialkynylations occur efficiently for penta- and hexafluorobenzenes, respectively. Tetraalkynylated products could also be synthesized from dialkynylated compounds.     

Stimulation of Microvascular Networks on Sulfonated Polyrotaxane Surfaces with Immobilized Vascular Endothelial Growth Factor

Modulation of material properties and growth factor application are critical in constructing suitable cell culture environments to induce desired cellular functions. Sulfonated polyrotaxane (PRX) surfaces with immobilized vascular endothelial growth factors (VEGFs) are prepared to improve network formation in vascular endothelial cells. Sulfonated PRXs, whereby sulfonated α‐cyclodextrins (α‐CDs) are threaded onto a linear poly(ethylene glycol) chain capped with bulky groups at both terminals, are coated onto surfaces. The molecular mobility of sulfonated PRX surfaces is modulated by tuning the number of threading α‐CDs. VEGF is immobilized onto surfaces with varying mobility. Low mobility and VEGF‐immobilization reinforce cell proliferation, yes‐associated protein activity, and rhoA, pdgf, ang‐1, and pecam‐1 gene expression. Highly mobile surfaces and soluble VEGF weakly affect these cell responses. Network formation is strongly stimulated in vascular endothelial cells only on low‐mobility VEGF‐immobilized surfaces, suggesting that molecular mobility and VEGF immobilization synergistically control cell function.