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51.
A single or a limited number of UVR exposures is recognized to suppress cell-mediated immunity in human subjects. The complex pathway leading from the absorption of photons by chromophores in the skin to the generation of T regulatory cells has been, at least partially, elucidated. However, the effect of repeated UV exposures on immune responses and associated mediators is not well studied, particularly to assess whether they lead, first, to the development of photoprotection so that these immune changes are reduced or no longer occur, and, secondly, to the development of photoprotection against the normal downregulation of immunity induced by a high UV dose. For almost all the parameters evaluated in this review--epidermal DNA damage/erythema, urocanic acid, Langerhans and dendritic cells, natural killer cells, macrophages, mast cells, contact and delayed hypersensitivity responses--none, aside from epidermal DNA damage/erythema and macrophage phagocytic activity, show convincing evidence of photoadaptation or, where appropriate, photoprotection. It is concluded that repeatedly irradiating individuals with UVR is likely to continue to result in downregulation of immunity. 相似文献
52.
Pauline W. Ondachi 《Tetrahedron letters》2008,49(3):569-572
Enantiopure (S)-6-alkoxynicotine derivatives have been synthesized in two steps from (S)-nicotine via (S)-6-iodonicotine. Deprotonation and substitution at the C-5 position of the pyridine ring of (S)-6-methoxynicotine were achieved using mesityllithium as the base at 0 °C. Conditions for the C-4 lithiation/substitution of (S)-6-isopropoxynicotine and (S)-5-chloro-6-methoxynicotine were also developed. 相似文献
53.
Boglio C Hasenknopf B Lenoble G Rémy P Gouzerh P Thorimbert S Lacôte E Malacria M Thouvenot R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(5):1532-1540
Lanthanide complexes of the chiral Dawson phosphotungstate [alpha(1)-P(2)W(17)O(61)](10-) were used to study the formation of diastereomers with optically pure organic ligands. The present work started with the full assignment of the (183)W NMR spectra of [alpha(1)-Yb(H(2)O)(4)P(2)W(17)O(61)](7-) at different temperatures and concentrations, which allowed the structure of the dimerized form in aqueous solution to be established. Different enantiopure amino acids and phosphonic acids were screened as ligands. Both types allowed chiral differentiation by multinuclear NMR spectroscopy under fast-exchange conditions. Functional groups with a good affinity for the oxo framework of the polyoxometalate were identified, and maps of the interactions between L-serine and N-phosphonomethyl-L-proline with [alpha(1)-Yb(H(2)O)(4)P(2)W(17)O(61)](7-) were established. This demonstrates the power of (183)W NMR spectroscopy to elucidate the molecular recognition of inorganic molecules by organic compounds. N-Phosphonomethyl-L-proline appears to be a convenient ligand to promote separation of the diastereomers and ultimately resolution of the enantiomers of [alpha(1)-Yb(H(2)O)(4)P(2)W(17)O(61)](7-). 相似文献
54.
Pauline Fournier Iwan Cornelius Mattia Donzelli Herwig Requardt Christian Nemoz Marco Petasecca Elke Bräuer-Krisch Anatoly Rosenfeld Michael Lerch 《Journal of synchrotron radiation》2016,23(5):1180-1190
Microbeam radiation therapy (MRT) is a novel irradiation technique for brain tumours treatment currently under development at the European Synchrotron Radiation Facility in Grenoble, France. The technique is based on the spatial fractionation of a highly brilliant synchrotron X‐ray beam into an array of microbeams using a multi‐slit collimator (MSC). After promising pre‐clinical results, veterinary trials have recently commenced requiring the need for dedicated quality assurance (QA) procedures. The quality of MRT treatment demands reproducible and precise spatial fractionation of the incoming synchrotron beam. The intensity profile of the microbeams must also be quickly and quantitatively characterized prior to each treatment for comparison with that used for input to the dose‐planning calculations. The Centre for Medical Radiation Physics (University of Wollongong, Australia) has developed an X‐ray treatment monitoring system (X‐Tream) which incorporates a high‐spatial‐resolution silicon strip detector (SSD) specifically designed for MRT. In‐air measurements of the horizontal profile of the intrinsic microbeam X‐ray field in order to determine the relative intensity of each microbeam are presented, and the alignment of the MSC is also assessed. The results show that the SSD is able to resolve individual microbeams which therefore provides invaluable QA of the horizontal field size and microbeam number and shape. They also demonstrate that the SSD used in the X‐Tream system is very sensitive to any small misalignment of the MSC. In order to allow as rapid QA as possible, a fast alignment procedure of the SSD based on X‐ray imaging with a low‐intensity low‐energy beam has been developed and is presented in this publication. 相似文献
55.
Nitrosylation of Nitric‐Oxide‐Sensing Regulatory Proteins Containing [4Fe‐4S] Clusters Gives Rise to Multiple Iron–Nitrosyl Complexes
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Pauline N. Serrano Dr. Hongxin Wang Dr. Jason C. Crack Christopher Prior Prof. Matthew I. Hutchings Prof. Andrew J. Thomson Dr. Saeed Kamali Dr. Yoshitaka Yoda Dr. Jiyong Zhao Dr. Michael Y. Hu Dr. Ercan E. Alp Dr. Vasily S. Oganesyan Prof. Nick E. Le Brun Prof. Stephen P. Cramer 《Angewandte Chemie (International ed. in English)》2016,55(47):14575-14579
The reaction of protein‐bound iron–sulfur (Fe‐S) clusters with nitric oxide (NO) plays key roles in NO‐mediated toxicity and signaling. Elucidation of the mechanism of the reaction of NO with DNA regulatory proteins that contain Fe‐S clusters has been hampered by a lack of information about the nature of the iron‐nitrosyl products formed. Herein, we report nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT) calculations that identify NO reaction products in WhiD and NsrR, regulatory proteins that use a [4Fe‐4S] cluster to sense NO. This work reveals that nitrosylation yields multiple products structurally related to Roussin's Red Ester (RRE, [Fe2(NO)4(Cys)2]) and Roussin's Black Salt (RBS, [Fe4(NO)7S3]. In the latter case, the absence of 32S/34S shifts in the Fe?S region of the NRVS spectra suggest that a new species, Roussin's Black Ester (RBE), may be formed, in which one or more of the sulfide ligands is replaced by Cys thiolates. 相似文献
56.
Richard JA Jean L Romieu A Massonneau M Noack-Fraissignes P Renard PY 《Organic letters》2007,9(23):4853-4855
A strategy involving the use of a self-immolative linker has been investigated for the chemiluminescent sensing of proteases. The reactive linker enabled the release of a 1,2-dioxetane light precursor. As a proof of principle, caspase-3, a key peptidase involved in apoptosis has been targeted. An in vitro assay has been carried out and proved the decomposition of the linker and the selectivity for caspase-3. 相似文献
57.
The first total synthesis of a secodolastane, (-)-indicol, has been accomplished. The key reaction is a rhodium(II)-mediated carbene cyclization-cycloaddition cascade, by which the core bicyclo[5.4.0]undecane skeleton was assembled. In this one-pot reaction, a domino series of transformations resulting in the construction of three sigma bonds and three stereocenters was realized in good yield. 相似文献
58.
Direct activation of unprotected thioimidoyl furanosides yielded in only one step and few minutes a panel of rare uridine 5'-diphospho-furanoses. Diastereoselectivity of the reaction was tightly connected with reaction time, temperature, and nature of the furanosyl donor. This approach was totally selective since no ring expansion from the initial five-membered ring to the more stable pyranose form was observed. 相似文献
59.
Coolen-Schrijner Pauline Pollett Phil 《Methodology and Computing in Applied Probability》1999,1(1):81-96
We consider a discrete-time Markov chain on the non-negative integers with drift to infinity and study the limiting behavior of the state probabilities conditioned on not having left state 0 for the last time. Using a transformation, we obtain a dual Markov chain with an absorbing state such that absorption occurs with probability 1. We prove that the state probabilities of the original chain conditioned on not having left state 0 for the last time are equal to the state probabilities of its dual conditioned on non-absorption. This allows us to establish the simultaneous existence, and then equivalence, of their limiting conditional distributions. Although a limiting conditional distribution for the dual chain is always a quasi-stationary distribution in the usual sense, a similar statement is not possible for the original chain. 相似文献
60.
Miarintsoa Michaele Ranarijaona Ny Aina Harivony Rambala Rakotomena Mbolatiana Tovo Andrianjafy Fenia Diane Ramiharimanana Lydia Clarisse Herinirina Niry Hasinandrianina Ramarosandratana Benoit Briou Pauline Fajardie Patrick Mavingui Estelle Mtay Voahangy Vestalys Ramanandraibe Marc Lemaire 《Molecules (Basel, Switzerland)》2021,26(24)
This article describes a part of the results obtained from the cooperation between the University of Lyon1 (France) and the University of Antananarivo (Madagascar). It shows (among others) that useful research can be carried out in developing countries of the tropics if their social, technical, and economic conditions are taken into account. The concepts and methods associated with so-called “green chemistry” are particularly appropriated for this purpose. To illustrate this approach, two examples are shown. The first deals with industrial ecology and concerns waste transformation from the production of cashew nut into an amphiphilic product, oxyacetic derivatives. This product was obtained with a high yield and in a single step reaction. It exhibited an important surfactant property similar to those of the main fossil-based ones but with a much lower ecological impact. The second talks about chemical ecology as an alternative to insecticides and used to control dangerous mosquito populations. New substituted chromones were synthesized and showed biological activities toward Aedes albopictus mosquito species. Strong repellent properties were recorded for some alkoxylated products if others had a significant attractant effect (Kairomone) depending on their stereochemistry and the length of the alkyl chain. 相似文献