Coherent d-wave superconducting gap in underdoped La2-xSrxCuO4 by angle-resolved photoemission spectroscopy

We present angle-resolved photoemission spectroscopy data on moderately underdoped La1.855Sr0.145CuO4 at temperatures below and above the superconducting transition temperature. Unlike previous studies of this material, we observe sharp spectral peaks along the entire underlying Fermi surface in the superconducting state. These peaks trace out an energy gap that follows a simple d-wave form, with a maximum superconducting gap of 14 meV. Our results are consistent with a single gap picture for the cuprates. Furthermore our data on the even more underdoped sample La1.895Sr0.105CuO4 also show sharp spectral peaks, even at the antinode, with a maximum superconducting gap of 26 meV.     

Synthesis of Conformationally Restricted Carbocyclic Nucleosides: The Role of the O(4′)-Atom in the Key Hydration Step of Adenosine Deaminase

Conformationally restricted carbocyclic nucleosides with either a northern(N)-type conformation, i.e., N-type 2′-deoxy-methanocarba-adenosine 8 ((N)MCdAdo), or a southern(S)-type conformation, i.e. S-type 2′-deoxy-methanocarba-adenosine 9 , ((S)MCdAdo), were used as substrates for adenosine deaminase (ADA) to assess the enzyme's preference for a fixed conformation relative to the flexible conformation represented by the carbocyclic nucleoside aristeromycin ( 10 ). Further comparison between the rates of deamination of these compounds with those of the two natural substrates adenosine (Ado; 1 ) and 2′-deoxyadenosine (dAdo; 2 ), as well as with that of the conformationally locked nucleoside LNA-Ado ( 11 ), which, like the natural substrates, has a furanose O(4′) atom, helped differentiate between the roles of the O(4′) anomeric effect and sugar conformation in controlling the rates of deamination by ADA. Differences in rates of deamination as large as 10000 can be attributed to the combined effect of the O(4′) atom and the enzyme's preference for an N-type conformation. The hypothesis proposed is that ADA's preference for N-type substrates is not arbitrary; it is rather the direct consequence of the conformationally dependent O(4′) anomeric effect, which is more efficient in N-type conformers in promoting the formation of a covalent hydrate at the active site of the enzyme. The formation of a covalent hydrate at the active site of ADA precedes deamination. A new and efficient synthesis of the important carbobicyclic template 14a , a useful intermediate for the synthesis of (N)MCdAdo ( 8 ) and other conformationally restricted nucleosides, is also reported.     

Synthesis and Fungicidal Activity of Hydrated Geranylated Phenols against Botrytis cinerea

Botrytis cinerea is a ubiquitous fungus that affects hundreds of plants, resulting in economic losses to the horticulture and fruit industry. The search for new antifungal agents is a matter of current interest. Thus, in this work a series of geranylated phenols in which the side alkyl chain has been hydrated have been synthesized, and their activity against B. cinerea has been evaluated. The coupling of phenol and geraniol has been accomplished under microwave irradiation obtaining the highest reaction yields in the shortest reaction times. Hydration of the side chain was carried out in dioxane with p-toluenesulfonic acid polymer-bound as the catalyst. All synthesized compounds were tested against B. cinerea using the growth inhibition assay and EC₅₀ values were determined. The results show that activity depends on the number and nature of functional groups in the phenol ring and hydration degree of the geranyl chain. The most active compound is 1,4-dihydroquinone with one hydroxyl group attached at the end of the alkyl chain. Results from a molecular docking study suggest that hydroxyl groups in the phenol ring and alkyl chain are important in the binding of compounds to the active site, and that the experimental antifungal activity correlates with the number of H-bond that can be formed in the binding site.     

Metal substrate catalysis in the confined space for platinum drug delivery

Catalysis-based approaches for the activation of anticancer agents hold considerable promise. These principally rely on the use of metal catalysts capable of deprotecting inactive precursors of organic drugs or transforming key biomolecules available in the cellular environment. Nevertheless, the efficiency of most of the schemes described so far is rather low, limiting the benefits of catalytic amplification as strategy for controlling the therapeutic effects of anticancer compounds. In the work presented here, we show that flavin reactivity within a hydrogel matrix provides a viable solution for the efficient catalytic activation and delivery of cisplatin, a worldwide clinically-approved inorganic chemotherapy agent. This is achieved by ionically adsorbing a flavin catalyst and a Pt(iv) prodrug as substrate into porous amino-functionalized agarose beads. The hydrogel chassis supplies high local concentrations of electron donating groups/molecules in the surrounding of the catalyst, ultimately boosting substrate conversion rates (TOF >200 min⁻¹) and enabling controlled liberation of the drug by light or chemical stimuli. Overall, this approach can afford platforms for the efficient delivery of platinum drugs as demonstrated herein by using a transdermal diffusion model simulating the human skin.

Loading of a flavin catalyst and Pt prodrug onto a hydrogel affords biomaterials for the catalytic generation and delivery of cisplatin upon light irradiation or addition of electron donors. Confinement boosts the turnover frequency of the flavin.     

Novel diacetylene-containing polymers for second order NLO applications: effect of main chains and structure property relationships

In order to obtain polymers having high second order nonlinear optical (NLO) response, various novel polymers that contain polar dye molecules in side chains and diacetylenic groups in the main chains were synthesized, and their second order NLO properties were studied. Some of these polymers consisting of para-benzoate and para-cinnamate main chains, showed extremely high NLO coefficients, d₃₃ of 200 - 350 pm/V, and the corresponding meta polymers showed much inferior NLO coefficients. The polymers having aliphatic main chains had very little NLO response probably because of their low glass transition temperatures and flexibility of main chains. The high SHG responses of these polymers are attributed to their facile orientation of both chromophores and main chains. In the case of para-polymers, the main chain orientation of alkoxybenzoate and cinnamate along the chromophore is thought to be a reason for their high NLO coefficients.     

C−S Cross-Coupling of Aryldiazonium Salts with Thiols Mediated by Gold

In this work, the coupling of aryldiazonium salts with thiols mediated by the readily accessible gold complex Me₂SAuCl is described. In the reported protocol, the addition of 2,2′-bipyridine as a ligand leads to higher yields than phosphines. The reaction proceeds at room temperature under soft mildconditions and has a broad scope in both the aryldiazonium salt and the thiol. Notably, the coupling works with aryldiazonium salts containing two additional substituents.     

Lichen colonization of an active volcanic environment: a Raman spectroscopic study of extremophile biomolecular protective strategies

The Raman spectra of some sixteen lichen specimens from eight genera growing on basaltic lava and wood substrates on new lava fields on the Kilauea volcano, Kona, Hawaii, have been analysed in therms of the pigments and biomolecules produced in this extreme environment. Chlorophyll and a carotenoid, probably lutein or astaxanthin, are ubiquitous, but otherwise, a range of protective pigments have been identified, including atranorin, usnic acid, gyrophoric acid, parietin and pulvinic acid dilactone. In addition, some species were observed to produce calcium oxalate monohydrate and dihydrate. Clearly, several strategies for survival were being adopted by the lichens to combat radiation insolation, desiccation and high temperatures; in one case, of the same lichen species colonizing wood and lava in the same location, a different survival strategy could be detected related to their substrate, but further long‐term ecological experiments would be indicated to derive more detailed information on this aspect. Copyright © 2009 John Wiley & Sons, Ltd.