Tandem diazonium salt electroreduction and click chemistry as a novel, efficient route for grafting macromolecules to gold surface

Bis-alkynylated oligoethyleneglycol (OEG) and a monopropargyl-functionalized perfluorinated ethylene glycol (FEG) were clicked to azide-functionalized gold surface (Au–N₃) at room temperature via the well known 1,3 cycloaddition click chemical reaction. The Au–N₃ substrate was obtained by nucleophilic attack of NaN₃ on gold substrates modified by the electrochemical reduction of the , ⁺N₂–C₆H₄–CH₂Br diazonium salt. This electrochemical process yields aryl layer-modified gold of the type Au–C₆H₄–CH₂Br (hereafter Au–Br). The untreated and modified gold plates were examined by XPS, PMIRRAS and contact angle measurements. XPS brought evidence for electrografting aryl layers by the detection of Br3d; azide functionalization by the increase of the N/Br atomic ratio; and click reaction of OEG with Au–N₃ by the increase of O/N ratio. In addition, the perfluorinated plate (Au-FEG) exhibited F1s and characteristic C1s peaks from -(CF₂)₇- chain and terminal CF₃. Infra red spectroscopy (PMIRRAS) evidenced (i) grafting N₃ to Au–Br; (ii) characteristic stretching bands, from ethylene glycol units, C–O–C (1100–1300 cm⁻¹); CF₂ (1000–1100 cm⁻¹) and CF₃ (1100–1350 cm⁻¹) from FEG grafts; and (iii) suppression of alkynyl bands from OEG and FEG after surface click chemistry. More importantly, PMIRRAS results support an important bridging of the bispropargyl oligoethylene glycol at the gold surface. Water drop contact angles were found to be 48.7° and 83.0° for Au-OEG and Au-FEG, respectively, therefore highlighting the control over the hydrophilic/hydrophobic character of the clicked substrate.This work shows that clicking macromolecules to grafted, diazonium salt-derived aryl layers is a novel, simple and valuable approach for designing robust, functional surface organic coatings.     

Functionalisation of mesoporous silica nanoparticles with 3-isocynatopropyltrichlorosilane

The functionalisation of Mesoporous Silica Nanoparticles (MSN) with the isocyanate group was carried out. The excellent reactivity of 3-isocynanatopropyltrichlorosilane allowed its grafting on the surface of MSN in mild conditions. Further reaction with different nucleophiles bearing primary amino groups led to the formation of a urea linkage and thus the covalent grafting of the nucleophiles to the MSN surface.     

Ultraviolet Radiation in the Rhône River Lenses of Low Salinity and in Marine Waters of the Northwestern Mediterranean Sea: Attenuation and Effects on Bacterial Activities and Net Community Production

The high content in nutrients of freshwater outflows induces highly productive and buoyant plumes spreading over marine waters (MW). As a consequence, the growth of organisms developing in these low‐salinity waters (LSW) might be potentially affected by UV‐R (280–400 nm). This study investigated the penetration of UV‐R and its impact on net community production (NCP) and bacterial protein (B_PROTS) and DNA (B_DNAS) synthesis in mesotrophic‐LSW formed from the Rhône River and in oligotrophic MW of the Northwestern Mediterranean Sea (Gulf of Lions) in May 2006. High concentrations of chlorophyll a (up to 8 μg L^?1) measured in the LSW (<37.8 psu, 0–10 m) were the main factor influencing the diffuse attenuation coefficients (K_d) of both UV‐R and photosynthetically active radiation (PAR). The mean ratio of the K_d measured between the LSW and the MW increased with wavelength from 2.4 at 305 nm to 2.9 at 380 nm and 3.1 for PAR indicating more similarity in the UV region. NCP was severely inhibited by UV‐R at the surface of the LSW, whereas no effect was measured in the surrounding MW. In contrast, B_PROTS and B_DNAS were affected deeper by UV‐R in the MW (up to 8 m depth) compared to the LSW where inhibition was only observed at the surface. Differences in response of bacteria in LSW and MW are largely explained by differences in UV‐R transparency; however, transplant experiments indicate that bacterial assemblages from the MW were also more sensitive to UV‐R than those present in the LSW. We also observed that higher activity of bacteria after nutrient additions increased their sensitivity to UV‐R during the day, but favored their recovery during the night incubation period for both LSW and MW. Results suggest that riverine and nutrient inputs may alter the effects of UV‐R on microbial activity by attenuating the UV‐R penetration and by modifying the physiology of bacteria.     

Diaqua(oxydiacetato‐κ3O,O′,O′′)(pyridine‐3‐carboxamide‐κN1)copper(II)

In the mononuclear title compound, [Cu(C₄H₄O₅)(C₆H₆N₂O)(H₂O)₂], the Cu^II centre is bound to a chelating oxydiacetate ligand, a monodentate pyridine‐3‐carboxamide unit and two water molecules, defining an octahedral coordination where the first two ligands form the equatorial plane and the last two occupy the apical sites. The planar oxydiacetate ligand is slightly disordered at its central ether O atom. The availability of efficient donors and acceptors for hydrogen bonding results in a complex interaction scheme where each monomer links to six similar units to define a well connected three‐dimensional structure. A comparison is made with related structures in the literature, and the reasons for their differences are discussed.     

Ultrathin-layer sodium dodecyl sulfate disc electrophoresis of proteins in the range from 10 to 220 kDa in homogeneous,low-concentrated polyacrylamide gels

This study describes an ultrathin-layer sodium dodecyl sulfate (SDS) disc electrophoresis in polyacrylamide gels of a thickness of only 150 microm. By use of 2-amino-2-methyl-1,3-propanediol/glycine instead of traditional Tris/HCl buffer in the resolving phase of the gel, proteins with a wide range of molecular sizes (10 kDa to over 220 kDa) are separated in unusually low-concentrated gels (4%T, 3.3%C). 2-Amino-2-methyl-1,3-propanediol in the resolving part of the gel contributes to stabilization of the pH value at 8.8, while glycine improves destacking as well as separation of small proteins from the bulk of stacked SDS. This method combines both the advantages of conventional slab-gel electrophoresis and capillary gel electrophoresis. It is easy to apply and well suited for all further miniaturization attempts.     

Single crystal EPR study of the dinuclear Cu(II) complex [Cu(tda)(phen)](2)·H(2)tda (tda = thiodiacetate, phen = phenanthroline): influence of weak interdimeric magnetic interactions

We report powder and single crystal EPR measurements of [Cu(tda)(phen)](2)·H(2)tda (tda = thiodiacetate, phen = phenanthroline) at 9.7 GHz. This compound consists of centrosymmetric copper(II) ion dimers, weakly ferromagnetically exchange-coupled (J = +3.2 cm(-1)), in which the dimeric units are linked by hydrophobic chemical paths involving the phen molecules. EPR revealed that the triplet spectra are collapsed by interdimeric exchange interactions mediated by that chemical path. Analysis and simulation of the single crystal EPR spectra were performed using Anderson's exchange narrowing model, together with statistical arguments. This approach allowed us to interpret the spectra modulated by the interdimeric interactions in situations of weak, intermediate, and strong exchange. We evaluated an interdimeric exchange constant J' = 0.0070(3) cm(-1), indicating that hydrophobic paths can transmit weak exchange interactions between centers at relatively long distances of the order of ～10 ?.     

Aqua(oxydiacetato‐κ3O,O′,O′′)(pyridine‐3‐carboxamide‐κN1)copper(II) sesquihydrate

In the monomeric title compound, [Cu(C₄H₄O₅)(C₆H₆N₂O)(H₂O)]·1.5H₂O, the Cu^II cation is bound in a square‐pyramidal coordination to a tridentate oxydiacetate (ODA) ligand, a monodentate pyridine‐3‐carboxamide (p3ca) ligand and one aqua ligand, where the two organic ligands form the basal plane and the water O atom occupies the unique apical site. The ODA ligand presents a slight out‐of‐plane puckering in its central ether O atom, while the p3ca ligand is essentially planar. The availability of efficient donors and acceptors for hydrogen bonding results in the formation of strongly linked hydrogen‐bonded bilayers parallel to (101), with an interplanar distance of 3.18 (1) Å and a stacking separation between the bilayers of 3.10 (1) Å, both of them governed by extended π–π interactions. The disordered nature of the solvent water molecules around inversion centres is discussed. The monoaqua compound is compared with the octahedral diaqua analogue, [Cu(C₄H₄O₅)(C₆H₆N₂O)(H₂O)₂], reported recently [Perec & Baggio (2009). Acta Cryst. C 65 , m296–m298].     

Octupolar Derivatives Functionalized with Superacceptor Peripheral Groups: Synthesis and Evaluation of the Electron‐Withdrawing Ability of Potent Unusual Groups

Novel tripodal derivatives with a triphenylamine core and that bear “superacidifiers” (i.e., fluorinated sulfoximinyl blocks) or novel sulfiliminyl moieties as peripheral groups were synthesized. These new chromophores show strong absorption in the near‐UV region and emission in the visible region. The fluorinated sulfoximinyl moieties were found to behave as potent auxochromic and electron‐withdrawing (EW) groups, thus leading to redshifted absorption and emission. These moieties promote a core‐to‐periphery intramolecular charge transfer (ctp‐ICT) transition, the energy of which was found to be correlated to their EW strength. In this study, we provide evidence of a linear correlation between the Hammett constant (σ_p) values and the electronic gap between the ground and first excited state of the three‐branched derivatives. This in turn was used to derive σ_p values of fluorinated sulfoximinyl moieties. These EWGs show unprecedentedly high σ_p values, up to 1.45 relative to 0.8 for NO₂. Also, by using this method, the sulfiliminyl moiety was shown to exhibit similar EW strength as NO₂, while promoting improved transparency and solubility. Finally, the superior EW strength of the fluorinated sulfoximine peripheral moieties was shown to induce significant enhancement of the two‐photon absorption responses in the red near‐IR region of the three‐branched derivatives relative to similar octupoles that bear more usual strong EW groups. These characteristics (improved nonlinear responses or transparency) open new routes for the design of nonlinear optical (NLO) chromophores for optical limiting or electro‐optical modulation. Such building blocks could also be of interest for optoelectronic applications, including the development of solar cells.     

Synthesis of Aminopyridines and Aminopyridones by Cobalt‐Catalyzed [2+2+2] Cycloadditions Involving Yne‐Ynamides: Scope,Limitations, and Mechanistic Insights

An in‐depth study of the cobalt‐catalyzed [2+2+2] cycloaddition between yne‐ynamides and nitriles to afford aminopyridines has been carried out. About 30 nitriles exhibiting a broad range of steric demand and electronic properties have been evaluated, some of which open new perspectives in metal‐catalyzed arene formation. In particular, the use of [CpCo(CO)(dmfu)] (dmfu=dimethyl fumarate) as a precatalyst made possible the incorporation of electron‐deficient nitriles into the pyridine core. Modification of the substitution pattern at the yne‐ynamide allows the regioselectivity to be switched toward 3‐ or 4‐aminopyridines. Application of this synthetic methodology to the construction of the aminopyridone framework using a yne‐ynamide and an isocyanate was also briefly examined. DFT computations suggest that 3‐aminopyridines are formed by formal [4+2] cycloaddition between the nitrile and the intermediate cobaltacyclopentadiene, whereas 4‐aminopyridines arise from an insertion pathway.     

Benzo[1,2‐d:4,5‐d′]bisimidazoles as a Convenient Platform Towards Dyes that are Capable of Excited‐State Intramolecular Proton Transfer and of Two‐Photon Absorption

New, strongly fluorescent benzo[1,2‐d:4,5‐d′]bisimidazoles have been prepared by the reaction of Bandrowski′s base with various aldehydes. Their structures were carefully designed to achieve efficient excited‐state intramolecular proton transfer and good two‐photon‐absorption (2PA) cross‐sections. Functional dyes that possessed both high fluorescence quantum yields and large Stokes shifts were prepared. A π‐expanded D‐A‐D derivative that possessed Φ_fl=50 % and σ₂=230 GM in the spectroscopic area of interest for biological imaging is an excellent candidate as a fluorescent probe. Thanks to the presence of two reactive amino groups, such compounds can be easily transformed into probes for bioconjugation. All of these benzo[1,2‐d:4,5‐d′]bisimidazoles were also strongly fluorescent in the solid state.