Copper Nanoparticles Supported on ZIF-8: Comparison of Cu(II) Reduction Processes and Application as Benzyl Alcohol Oxidation Catalysts.

We report the synthesis of a stable heterogeneous catalyst based on copper metal nanoparticles with oxidized surface supported on ZIF-8 for the oxidation of benzyl alcohol under mild temperature and using air as a sustainable oxygen source as well as for the implementation of the tandem "one-pot" catalytic system allowing the sustainable synthesis of benzylidene malononitrile. The influence of the reduction process applied to form the nanoparticle upon the catalyst texture and its performances was extensively examined. After ZIF-8 impregnation with a copper chloride precursor, the reduction of cupric ions into Cu0 nanoparticles was carried out according to two procedures: (i) by soaking the solid into a solution of NaBH4 and (ii) by submitting it to a flow of gaseous H2 at 340 °C. The in-depth physicochemical characterization and comparison of the resulting two types of Cu/ZIF-8 materials reveal significant differences: the reduction with NaBH4 led to the formation of 16 nm sized Cu0 nanoparticles (NP) mainly localized on the external surface of the ZIF-8 crystals together with ZnO nanocrystallites, while the reduction under H2 flow resulted in Cu0 nanoparticles with a mean size of 22 nm embedded within the bulk of ZIF-8 crystals. More, when NaBH4 was used to reduce cupric ions, ZnO particles were highlighted by high-resolution microcospy imaging. Formation of ZnO impurities was confirmed by the photoluminescence analysis of ZIF-8 after NaBH4 treatment. In contrast, ZnO was not detected on ZIF-8 treated with H2. Both types of Cu0 NPs supported on ZIF-8 were found to be active as catalysts toward the aerobic oxidation of benzyl alcohol under moderate temperature (T < 80 °C) and using air as a sustainable O2 source. Benzaldehyde yield of 66% and selectivity superior to 90% were obtained with the Cu/ZIF-8 catalyst prepared under H2 flow after 24 h under these conditions. The same material could be recycled 5 times without loss of activity, unlike the catalysts synthesized with NaBH4, as a result of the leaching of the surface copper NPs over the consecutive catalytic cycles. Finally, the most stable catalyst was successfully implemented in a tandem "one-pot" catalytic system associating benzyl alcohol oxidation and Knoevenagel condensation to synthesize benzylidene malononitrile.

Biomineralization in Barnacle Base Plate in Association with Adhesive Cement Protein.

Barnacles strongly attach to various underwater substrates by depositing and curing a proteinaceous cement that forms a permanent adhesive layer. The protein MrCP20 present within the calcareous base plate of the acorn barnacle Megabalanus rosa (M. rosa) was investigated for its role in regulating biomineralization and growth of the barnacle base plate, as well as the influence of the mineral on the protein structure and corresponding functional role. Calcium carbonate (CaCO3) growth on gold surfaces modified by 11-mercaptoundecanoic acid (MUA/Au) with or without the protein was followed using quartz crystal microbalance with dissipation monitoring (QCM-D), and the grown crystal polymorph was identified by Raman spectroscopy. It is found that MrCP20 either in solution or on the surface affects the kinetics of nucleation and growth of crystals and stabilizes the metastable vaterite polymorph of CaCO3. A comparative study of mass uptake calculated by applying the Sauerbrey equation to the QCM-D data and quantitative X-ray photoelectron spectroscopy determined that the final surface density of the crystals as well as the crystallization kinetics are influenced by MrCP20. In addition, polarization modulation infrared reflection-absorption spectroscopy of MrCP20 established that, during crystal growth, the content of ß-sheet structures in MrCP20 increases, in line with the formation of amyloid-like fibrils. The results provide insights into the molecular mechanisms by which MrCP20 regulates the biomineralization of the barnacle base plate, while favoring fibril formation, which is advantageous for other functional roles such as adhesion and cohesion.

All-quantum dot based Förster resonant energy transfer: key parameters for high-efficiency biosensing.

While colloidal quantum dots (QDs) are commonly used as fluorescent donors within biosensors based on Förster resonant energy transfer (FRET), they are hesitantly employed as acceptors. On the sole basis of Förster theory and the well-known behaviour of organic dyes, it is often argued that the QD absorption band over the UV-visible range is too wide. Discarding these preconceptions inherited from classical fluorophores, we experimentally examine the FRET process occurring between donor and acceptor CdTe QDs and provide a mathematical description of it. We evidence that the specific features of QDs unexpectedly lead to the enhancement of acceptors' emission (up to +400%), and are thus suitable for the design of highly efficient all-QD based FRET sensors. Our model enables us to identify the critical parameters maximizing the contrast between positive and negative biosensing readouts: the concentrations of donors and acceptors, their spectral overlap, the densities of their excitonic states, their dissipative coupling with the medium and the statistics of QD-QD chemical pairing emerge as subtle and determinant parameters. We relate them quantitatively to the measured QD-QD FRET efficiency and discuss how they must be optimized for biosensing applications.

Silica-coated gold nanorods biofunctionalization for localized surface plasmon resonance (LSPR) biosensing.

We introduce here the engineering of nanobiosensors designed from gold nanorods coated with an ultrathin layer of silica (AuNR@SiO2) and biofunctionalized with antibodies for the Localized Surface Plasmon Resonance (LSPR) biosensing of proteins. Despite the outstanding properties of AuNRs, their use for LSPR biosensing is limited due to the presence of the surfactant cetyltrimethylammonium bromide (CTAB) - mandatory for their synthesis - which forms a strongly-bounded and positively-charged bilayer at their surface and significantly complicates their bio-functionalization. When coated with a thin layer of silica, these nanomaterials exhibit an improved sensitivity to refractive index change which augurs for better analytical performances. Here, we undertook an in-depth investigation of the biofunctionalization of AuNR@SiO2via three different routes to design and test a label-free LSPR biosensor operating in solution. In the first route, we took advantage of the negatively charged external silica shell to immobilize anti-rabbit IgG antibody by electrostatic physisorption. In the second and third routes, the silica surface was reacted with thiol or aldehyde terminated silanes, subsequently utilized to covalently attach anti-rabbit IgG antibody to the surface. The resulting nanoprobes were characterized by a wide range of physical methods (TEM, XPS, DLS, ELS and UV-Visible spectroscopy) then tested for the biosensing of rabbit-IgG. The three nanobiosensors maintain an excellent colloidal stability after analyte recognition and exhibit extremely high analytical performances in terms of specificity and dynamic range, with an LoD down to 12 ng/mL.

Design and Analytical Performances of a Diclofenac Biosensor for Water Resources Monitoring.

Because the broadly consumed pain killer diclofenac (DCF) is a recognized pollutant, monitoring of its concentration is routinely performed in surface waters. As a valuable alternative to chromatographic and immunochemical assays, we developed a piezoelectric immunosensor to quantify DCF, first in buffer (PBS) and then in river water samples. A sensing layer comprising DCF was built up on the surface of silica-coated quartz sensors using a robust coupling chemistry. Binding of a highly affine monoclonal anti-DCF antibody was monitored in real time by quartz crystal microbalance with dissipation (QCM-D) measurements from which were determined a dissociation constant KD of 0.24 nM and an acoustic antibody surface coverage of 1120 ng/cm2 at saturation. On the other hand, an optical antibody surface coverage of 260 ng/cm2 was determined by combined nanoplasmonic sensing measurement, giving a hydration percentage of 75% for the antibody monolayer. DCF assay was further set up following a competitive format for which binding of antibody to the sensing layer is inhibited by DCF in solution. The piezoelectric sensor response expressed as frequency shift ΔF was inversely related to the concentration of DCF with a dynamic range of 15-46 nM and a limit of detection (LoD) of 9.5 nM (2.8 µg/L) in PBS. This piezoelectric immunosensor was eventually applied to the assay of DCF in surface water samples taken at three different locations in the Seine and Marne rivers. The calculated concentration of DCF in these samples was in good agreement with official data published by the French center of water analysis eaufrance.

A selective and stable Fe/TiO2 catalyst for selective hydrogenation of butadiene in alkene-rich stream.

The replacement of precious metals by more abundant and therefore much less expensive metals remains a very important challenge in catalysis. A Fe/TiO2 catalyst prepared by deposition-precipitation with urea showed very high selectivity to alkenes (>99%), even at high conversion (>90%), in selective hydrogenation of butadiene in an excess of propene. Its activity is very stable at 175 °C whereas the catalyst deactivates at 50 °C, although it is also initially very active. The presence of metallic iron seems to be necessary to ensure these excellent performances.

Nanostructured and Spiky Gold Shell Growth on Magnetic Particles for SERS Applications.

Multifunctional micro- and nanoparticles have potential uses in advanced detection methods, such as the combined separation and detection of biomolecules. Combining multiple tasks is possible but requires the specific tailoring of these particles during synthesis or further functionalization. Here, we synthesized nanostructured gold shells on magnetic particle cores and demonstrated the use of them in surface-enhanced Raman scattering (SERS). To grow the gold shells, gold seeds were bound to silica-coated iron oxide aggregate particles. We explored different functional groups on the surface to achieve different interactions with gold seeds. Then, we used an aqueous cetyltrimethylammonium bromide (CTAB)-based strategy to grow the seeds into spikes. We investigated the influence of the surface chemistry on seed attachment and on further growth of spikes. We also explored different experimental conditions to achieve either spiky or bumpy plasmonic structures on the particles. We demonstrated that the particles showed SERS enhancement of a model Raman probe molecule, 2-mercaptopyrimidine, on the order of 104. We also investigated the impact of gold shell morphology-spiky or bumpy-on SERS enhancements and on particle stability over time. We found that spiky shells lead to greater enhancements, however their high aspect ratio structures are less stable and morphological changes occur more quickly than observed with bumpy shells.

Electrospray ionization: an efficient approach to deposit polymetallic molecular switches onto gold surfaces.

Electrospray ionization (EI) deposition is proven efficient in obtaining monolayers of a polymetallic charge transfer complex on gold surfaces. The molecule's integrity is monitored by using PM-IRRAS and XPS. This approach broadens the perspective of molecular magnetic switch deposition, which is currently dominated by the thermal evaporation of monometallic spin crossover (SCO) complexes.

Halide Ligands To Release Strain in Cadmium Chalcogenide Nanoplatelets and Achieve High Brightness.

Zinc blende II-VI semiconductor nanoplatelets (NPLs) are defined at the atomic scale along the thickness of the nanoparticle and are initially capped with carboxylates on the top and bottom [001] facets. These ligands are exchanged on CdSe NPLs with halides that act as X-L-type ligands. These CdSe NPLs are costabilized by amines to provide colloidal stability in nonpolar solvents. The hydrogen from the amine can participate in a hydrogen bond with the lone pair electrons of surface halides. After ligand exchange, the optical features are red-shifted. Thus, ligand tuning is another way, in addition to confinement, to tune the optical features of NPLs. The improved surface passivation leads to an increase in the fluorescence quantum efficiency of up to 70% in the case of bromide. However, for chloride and iodide, the surface coverage is incomplete, and thus, the fluorescence quantum efficiency is lower. This ligand exchange is associated with a decrease in stress that leads to unfolding of the NPLs, which is particularly noticeable for iodide-capped NPLs.

Stable Carboxylate-Terminated Gold Surfaces Produced by Spontaneous Grafting of an Alkyltin Compound.

Self-assembled monolayers formed by chemisorption of thiolated molecules on gold surfaces are widely applied for biosensing. Moreover, and due to the low stability of thiol-gold chemistry, contributions to the functionalisation of gold substrates with linkers that provide a more stable platform for the immobilisation of electroactive or biological molecules are highly appreciated. Herein, it is demonstrated that a carboxylated organotin compound can be successfully grafted onto gold substrates to form a highly stable organic layer with reactivity for subsequent binding to an aminated molecule. A battery of techniques were used to characterise the surface chemistry. The grafted layer was used to anchor aminoferrocene and subjected to both thermostability tests and long-term stability studies over a period of one year, demonstrating thermostability up to 90 °C and storage stability for at least 12 months at 4 °C protected from light. The stable surface tethering of molecules on gold substrates can be exploited in a plethora of applications, including molecular techniques, such as solid-phase amplification and solid-phase melting curve analysis, that require elevated temperature stability, as well as biosensors, which require long-term storage stability.

Crystalline Molybdenum Oxide Thin-Films for Application as Interfacial Layers in Optoelectronic Devices.

The ability to control the interfacial properties in metal-oxide thin films through surface defect engineering is vital to fine-tune their optoelectronic properties and thus their integration in novel optoelectronic devices. This is exemplified in photovoltaic devices based on organic, inorganic or hybrid technologies, where precise control of the charge transport properties through the interfacial layer is highly important for improving device performance. In this work, we study the effects of in situ annealing in nearly stoichiometric MoOx (x ∼ 3.0) thin-films deposited by reactive sputtering. We report on a work function increase of almost 2 eV after inducing in situ crystallization of the films at 500 °C, resulting in the formation of a single crystalline α-MoO3 overlaid by substoichiometric and highly disordered nanoaggregates. The surface nanoaggregates possess various electronic properties, such as a work function ranging from 5.5 eV up to 6.2 eV, as determined from low-energy electron microscopy studies. The crystalline underlayer possesses a work function greater than 6.3 eV, up to 6.9 eV, characteristic of a very clean and nearly defect-free MoO3. By combining electronic spectroscopies together with structural characterizations, this work addresses a novel method for tuning, and correlating, the optoelectronic properties and microstructure of device-relevant MoOx layers.

Tuning the Surface Chirality of Adsorbed Gly-Pro Dipeptide/Cu(110) by Changing Its Chemical Form via Electrospray Deposition.

By changing the ultrahigh vacuum (UHV) deposition method, classical sublimation versus electrospray ionization, one can tune the chemistry of a chiral dipeptide molecule (Gly-Pro, GP), when adsorbed on a Cu(110) surface, from anionic to zwitterionic. This chemical shift will influence the adsorption mode of the dipeptide, either in a three-point fashion in the case of anionic GP molecules with a strong interaction among the copper surface, both O atoms of the carboxylate moiety, and the nitrogen atoms, or in the case of zwitterions GP, the adsorption mode relies on the sole interaction of one carboxylate oxygen atom. These different anchoring modes strongly modify the expression of surface 2D chirality and the supramolecular assemblies with two very distinct unit cells.

Control of calcium accessibility over hydroxyapatite by post-precipitation steps: influence on the catalytic reactivity toward alcohols.

Hydroxyapatites are increasingly used as heterogeneous catalysts since they present atypical behaviours for many acid base reactions. The aim of this study was to discuss the possible involvement of Ca2+ Lewis and/or PO-H Brønsted acid sites belonging to the hydroxyapatite system in the conversion of 2-methylbut-3-yn-1-ol, a model molecule that is known to account for the acid base properties, and of ethanol into n-butanol. A series of hydroxyapatite samples with similar bulk properties was prepared from a lone precipitation batch, but by varying the conditions of the washing and drying steps. Although the surface depth probed by XPS exhibited similar average composition, ISS analysis revealed a gradient of calcium concentration in the first surface layers. In fact, the different conditions of drying and washing resulted in a modulation of the relative amount of Ca2+ and PO-H accessible on the top surface, as revealed by the adsorption of the CO molecule monitored by FTIR. The conversion in the two alcohol molecules is linearly dependent on the nature of the acid base pairs involved: when accessible on the top surfaces, due to their stronger acidity, the Ca2+ Lewis acid sites are preferentially involved, but they are less efficient than PO-H, as illustrated by the linear decrease of the conversion levels with the increasing relative amount of accessible Ca2+ cations. It is thus concluded that PO-H sites enhance the performances of the catalysts for the two reactions, and that washing and drying conditions allowing us to decrease the calcium accessibility at the benefit of PO-H should be favoured.

One-pot synthesis of a gold nanoparticle-Vmh2 hydrophobin nanobiocomplex for glucose monitoring.

HydrophobinVmh2 is a small amphiphilic protein, which self-assembles on different surfaces and naturally interacts with glucose. Here, we report on the synthesis of a nanobiocomplex made of polyethylene glycol, Vmh2 and gold nanoparticles by a one-step process and on its ability to recognise glucose in an aqueous solution at 0.3-0.6-1.2 mg ml(-1) concentrations. Even though the Vmh2 proteins are intrinsically bonded to the gold core, effective glucose interaction monitoring was demonstrated by using dynamic light scattering, ultraviolet-visible, polarization-modulated infrared reflection-absorption and x-ray photoelectron spectroscopies. Experimental results highlighted an affinity constant of 7.3 ± 0.3 mg ml(-1) between the nanobiosystem and the sugar, and a detection sensitivity of 0.13 ± 0.06 a.u./mg ml(-1).

Co-grafting of antiadhesive and antimicrobial agents onto UV-micropatterned copper surfaces.

Adhesion of proteins and bacteria was reduced by a factor close to one order of magnitude, and adhered bacteria were dramatically damaged on copper surfaces by grafting a PEG-modified PMMA-based (polymethyl methacrylate) copolymer together with an antimicrobial peptide. To obtain PEG and a peptide grafted together on the surface, a UV sensitive copolymer (containing PMMA, PEG and a UV sensitive reagent) was primary synthesized and deposited. After selective UV irradiation of this copolymer layer, an antimicrobial peptide, Magainin I, was grafted onto freed-polymer coated-copper surface via a spacer molecule (a mercapto carboxylic acid). The functionalization was characterized at each step by Polarization Modulation Reflection Absorption Infrared Spectroscopy (PM-RAIRS). The antiadhesive properties of the copolymer layer and antibacterial activity of the anchored Magainin I, were individually tested toward adsorption of bovine serum albumin (BSA) proteins, and against Gram positive bacteria, Listeria ivanovii, respectively. The results revealed that adhesion of both proteins and bacteria has been considerably reduced; moreover, the peptide still displays some antimicrobial activity after grafting. This work gives new ideas and perspectives to elaborate complex surface coatings where several agents are needed like for anti-biofilm or sensing applications.

The amphiphilic hydrophobin Vmh2 plays a key role in one step synthesis of hybrid protein-gold nanoparticles.

We report a simple and original method to synthesize gold nanoparticles in which a fungal protein, the hydrophobin Vmh2 from Pleurotus ostreatus and dicarboxylic acid-terminated polyethylene-glycol (PEG) has been used as additional components in a one step process, leading to hybrid protein-metal nanoparticles (NPs). The nanoparticles have been characterized by ultra-violet/visible, infrared and X-ray photoelectron spectroscopies, dynamic light scattering and also by electron microscopy imaging. The results of these analytical techniques highlight nanometric sized, stable, hybrid complexes of about 12 nm, with outer surface rich in functional chemical groups. Interaction with protein and antibodies has also been exploited.

An experimental and theoretical approach to investigate the effect of chain length on aminothiol adsorption and assembly on gold.

Despite the numerous studies on the self-assembled monolayers (SAMs) of alkylthiols on gold, the mechanisms involved, especially the nature and influence of the thiol-gold interface are still under debate. In this work the adsorption of aminothiols on Au(111) surfaces has been studied by using surface IR and X-ray photoelectron spectroscopy (XPS) as well as by density functional theory (DFT) modeling. Two aminothiols were used, cysteamine (CEA) and mercaptoundecylamine (MUAM), which contain two and eleven carbon atoms, respectively. By combining experimental and theoretical methods, it was possible to draw a molecular picture of the thiol-gold interface. The long-chain aminothiol produced better ordered SAMs, but, interestingly, the XPS data showed different sulfur binding environments depending on the alkyl chain length; an additional peak at low binding energy was observed upon CEA adsorption, which indicates the presence of sulfur in a different environment. DFT modeling showed that the positions of the sulfur atoms in the SAMs on gold with similar unit cells [(2√3×2√3)R30°] depended on the length of the alkyl chain. Short-chain alkylthiol SAMs were adsorbed more strongly than long-chain thiol SAMs and were shown to induce surface reconstruction by extracting atoms from the surface, possibly forming adatom/vacancy combinations that lead to the additional XPS peak. In the case of short alkylthiols, the thiol-gold interface governs the layer, CEA adsorbs strongly, and the mechanism is closer to single-molecule adsorption than self-assembly, whereas for long chains, interactions between alkyl chains drive the system to self-assembly, leading to a higher level of SAM organization and restricting the influence of the sulfur-gold interface.

Surface Chirality of Gly-Pro Dipeptide Adsorbed on a Cu(110) Surface.

The adsorption of chiral Gly-Pro dipeptide on Cu(110) has been characterized by combining in situ polarization modulation infrared reflection absorption spectroscopy (PM-RAIRS) and X-ray photoelectron spectroscopy (XPS). The chemical state of the dipeptide, and its anchoring points and adsorption geometry, were determined at various coverage values. Gly-Pro molecules are present on Cu(110) in their anionic form (NH2 /COO(-)) and adsorb under a 3-point binding via both oxygen atoms of the carboxylate group and via the nitrogen atom of the amine group. Low-energy electron diffraction (LEED) and scanning tunneling microscopy (STM) have shown the presence of an extended 2D chiral array, sustained via intermolecular H-bonds interactions. Furthermore, due to the particular shape of the molecule, only one homochiral domain is formed, creating thus a truly chiral surface.

Potent antimicrobial peptides against Legionella pneumophila and its environmental host, Acanthamoeba castellanii.

Legionella pneumophila, the major causative agent of Legionnaires' disease, is most often found in the environment in close association with free-living amoebae, leading to persistence, spread, biocide resistance, and elevated virulence of the bacterium. In the present study, we evaluated the anti-Legionella and anti-Acanthamoeba activities of three alpha-helical antimicrobial peptides (AMPs), namely, NK-2, Ci-MAM-A24, and Ci-PAP-A22, already known for the extraordinary efficacy against other microbes. Our data represent the first demonstration of the activity of a particular AMP against both the human facultative intracellular pathogen L. pneumophila and its pathogenic host, Acanthamoeba castellanii. Interestingly, the most effective peptide, Ci-MAM-A24, was also found to reduce the Legionella cell number within amoebae. Accordingly, this peptide was immobilized on gold surfaces to assess its antimicrobial activity. Surfaces were characterized, and activity studies revealed that the potent bactericidal activity of the peptide was conserved after its immobilization. In the frame of elaborating anti-Legionella surfaces, Ci-MAM-A24 represents, by its direct and indirect activity against Legionella, a potent peptide template for biological control of the bacterium in plumbings.

Layer-by-layer generation of PEG-based regenerable immunosensing surfaces for small-sized analytes.

Small molecules (haptens) like pharmaceuticals or peptides can serve as targets for antibody binding in competitive immunoassay-based flow-through assays. In this work, a strategy for preparing polyethylene glycol (PEG) coatings for subsequent hapten immobilization on glass-type silica surfaces is presented and characterized in detail. Two substrates bearing terminal silanol groups were utilized, a glass slide and a silicon wafer. First, surfaces were thoroughly cleaned and pretreated to generate additional silanol groups. Then, a silane layer with terminal epoxy groups was created using 3-glycidyloxypropyltrimethoxysilane (GOPTS). Epoxy groups were used to bind a layer of diamino-poly(ethylene glycol) (DAPEG) with terminal amino groups. Finally, the low molecular weight compound diclofenac was bound to the surface to be used as model ligand for competitive biosensing of haptens. The elementary steps were characterized using atomic force microscopy (AFM), water contact angle measurement, grazing-angle attenuated total reflection (GA-ATR) FT-IR spectroscopy, and X-ray photoelectron spectroscopy (XPS). The data collected using these techniques have confirmed the successive grafting of the molecular species, evidencing, that homogeneous monolayers were created on the silica surfaces and validated the proposed mechanism of functionalization. The resulting surfaces were used to investigate polyclonal anti-diclofenac antibodies recognition and reversibility using quartz crystal microbalance with dissipation (QCM-D) measurements or an automated flow-through immunoassay with chemiluminescence (CL) read-out. For both techniques, recognition and reversibility of the antibody binding were observed. The stability of sensors over time was also assessed and no decrease in CL response was observed upon 14 days in aqueous solution. The herein presented strategy for surface functionalization can be used in the future as reproducible and reusable universal platform for hapten biosensors.