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.

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.

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).

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.

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.

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.

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.

Enzyme immobilization on silane-modified surface through short linkers: fate of interfacial phases and impact on catalytic activity.

We investigated the mechanism of enzyme immobilization on silanized surfaces through coupling agents (cross-linkers) in order to understand the role of these molecules on interfacial processes and their effect on catalytic activity. To this end, we used a model multimeric enzyme (G6PDH) and several cross-linking molecules with different chemical properties, including the nature of the end-group (-NCO, -NCS, -CHO), the connecting chain (aliphatic vs aromatic), and geometrical constraints (meta vs para-disubstituted aromatics). There did not seem to be radical differences in the mechanism of enzyme adsorption according to the linker used as judged from QCM-D, except that in the case of DIC (1,4-phenylene diisocyanate) the adsorption occurred more rapidly. In contrast, the nature of the cross-linker exerted a strong influence on the amount of enzyme immobilized as estimated from XPS, and more unexpectedly on the stability of the underlying silane layer. DIC, PDC (1,4-phenylene diisothiocyanate), or GA (glutaraldehyde) allowed successful enzyme immobilization. When the geometry of the linker was changed from 1,4-phenylene diisothiocyanate to 1,3-phenylene diisothiocyanate (MDC), the silane layer was subjected to degradation, upon enzyme adsorption, and the amount of immobilized molecules was significantly lowered. TE (terephtalaldehyde) and direct enzyme deposition without cross-linker were similar to MDC. The organization of immobilized enzymes also depended on the immobilization procedure, as different degrees of aggregation were observed by AFM. A correlation between the size of the aggregates and the catalytic properties of the enzyme was established, suggesting that aggregation may enhance the thermostability of the multimeric enzyme, probably through a compaction of the 3D structure.

Characterization of two-dimensional chiral self-assemblies L- and D-methionine on Au(111).

A combination of XPS, in situ RAIRS, LEED, and STM experiments together with ab initio DFT calculations were used to elucidate the self-assembly properties at the atomic level, and enabled the interpretation of the expression of surface chirality upon adsorption of both enantiomers of methionine on a clean Au(111) surface under UHV conditions. The combination of experimental results, in particular, LEED and STM data with quantum chemical calculations is shown to be a successful setup strategy for addressing this challenge. It was found that the methionine molecular self-assembly consists of the first molecule lying parallel to the gold surface and the second interacting with the first methionine through a 2D H-bond network. The interaction with the gold surface is weak. The stability of the assembly is mainly due to the presence of intermolecular H bonds, resulting in the formation of ziplike dimer rows on the Au(111) surface. The methionine molecules interact with each other via their amino acid functional groups. The assembly shows an asymmetric pattern due to a slightly different orientation of the methionine molecules with respect to the surface. Simulations of the STM image of methionine assemblies were consistent with the experimental STM image. The present study shows another example of Au(111) stabilizing a self-assembled biological layer, which is not chemically perturbed by the surface.

Selective hydrogenation of butadiene over TiO2 supported copper, gold and gold-copper catalysts prepared by deposition-precipitation.

Oxide supported copper and gold catalysts are active for the selective hydrogenation of polyunsaturated hydrocarbons but their low activity compared to palladium catalysts and the deactivation of copper catalysts limit their use. There are only a very limited number of studies concerned with the use of bimetallic Au-Cu catalysts for selective hydrogenation reactions and the aim of this work was to prepare TiO2-supported monometallic Au and Cu and bimetallic AuCu (Cu/Au atomic ratio of 1 and 3) catalysts and to evaluate their catalytic performance in the selective hydrogenation of butadiene. Small gold, copper and gold-copper nanoparticles (average particle size < 2 nm) were obtained on TiO2 using the preparation method of deposition-precipitation with urea followed by reduction under H2 at 300 °C. Very small clusters were observed for Cu/TiO2 (∼1 nm) which might result from O2 induced copper redispersion, as also supported by the XPS analyses. The alloying of copper with gold was found to inhibit its redispersion and also limits its reoxidation, as attested by XPS. The bimetallic character of the AuCu nanoparticles was confirmed by XPS and EDX-HAADF. Cu/TiO2 was initially more active than Au/TiO2 in the selective hydrogenation of butadiene at 75 °C but it deactivated rapidly during the first hours of reaction whereas the gold catalyst was very stable up to 20 hours of reaction. The bimetallic AuCu/TiO2 catalysts displayed an activation period during the first hours of the reaction, which was very pronounced for the sample containing a higher Cu/Au atomic ratio. This initial gain in activity was tentatively assigned to copper segregation at the surface of the bimetallic nanoparticles, induced by the reactants. When the AuCu/TiO2 catalysts were pre-exposed to air at 75 °C before butadiene hydrogenation, surface copper segregation occurred, leading to higher initial activity and the suppression of the activation period. Under the same conditions, Cu/TiO2 totally lost its activity, probably due to irreversible copper oxidation.

Interaction of ZnII porphyrin with TiO2 nanoparticles: from mechanism to synthesis of hybrid nanomaterials.

The mechanism of interaction of Zn porphyrin (ZnPP) with TiO2 surfaces is investigated with a view to optimizing the synthesis of hybrid nanomaterials. The strategy consists of studying the adsorption of ZnPP on TiO2 flat surfaces by taking advantage of complementary surface characterization techniques. Combining a detailed X-ray photoelectron spectroscopic analysis with AFM imaging allows ZnPP-surface and ZnPP intermolecular interactions to be discriminated. Probing the adsorption of ZnPP on TiO2 nanoparticles (NPs) reveals the dominant role of ZnPP-mediated interactions, which are associated with the formation of ZnPP multilayers and/or with the state of aggregation of NPs. These preliminary investigations provide a guideline to synthesizing a novel ZnPP-TiO2 hybrid nanomaterial in a one-step protocol. In this material, ZnPP molecules are presumably involved in the TiO2 lattice rather than on the NP surface. Furthermore, ZnPP molecules preserve their electronic properties within the TiO2 NPs, and this makes the ZnPP-TiO2 hybrid nanomaterial an excellent candidate for nanomedicine and related applications, such as localization of nanoparticles in cells and tissues or in photodynamic therapy.

Elaboration, activity and stability of silica-based nitroaromatic sensors.

Functionalized silica-based thin films, modified with hydrophobic groups, were synthesized and used as sensors for nitroaromatic compound (NAC) specific detection. Their performance and behavior, in terms of stability, ageing and regeneration, have been fully characterized by combining chemical characterization techniques and electron microscopy. NAC was efficiently and specifically detected using these silica-based sensors, but showed a great degradation in the presence of humidity. Moreover, the sensor sensitivity seriously decreases with storage time. Methyl- and phenyl-functionalization helped to overcome this humidity sensitivity. Surface characterization enabled us to establish a direct correlation between the appearance, and increasing amount, of adsorbed carbonyl-containing species, and sensor efficiency. This contamination, appearing after only one month, was particularly important when sensors were stored in plastic containers. Rinsing with cyclohexane enables us to recover part of the sensor performance but does not yield a complete regeneration of the sensors. This work led us to the definition of optimized elaboration and storage conditions for nitroaromatic sensors.

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.

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.

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.

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.

Structure of clean and hydrated α-Al2O3 (1102) surfaces: implication on surface charge.

Periodic DFT calculations coupled to a first-principle thermodynamic approach have allowed us to establish a surface phase diagram for the different terminations of the α-Al(2)O(3) (1102) surface in various temperature and water pressure conditions. Theoretical results are compared with previous experimental data from the literature. Under a wide range of temperature and water pressure (including ambient conditions) the most stable surface (denoted C2_1H(2)O in this work) is terminated with singly coordinated hydroxyls on four-fold coordinated aluminium (Al(4C)-µ(1)-OH) while most existing surface models are only considering six-fold coordinated surface Al atoms as in the bulk structure of alumina. The presence of more acidic Al(4C)-µ(1)-OH sites helps explain the low Point of Zero Charge (PZC) (between 5 and 6) determined from the onset of Mo oxoanions adsorption on (1102) single crystal wafers. It is also postulated that another termination (corresponding to the hydration of the non-polar, stoichiometric surface, stable in dehydrated conditions) may be observed in aqueous solution depending on the surface preparation conditions.

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.

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.

Synthesis and grafting of a BTP derivative onto a quartz crystal microbalance for lanthanide detection.

The ability of bis-triazinylpyridine (BTP) molecules to complex lanthanides is well-known in solution and can be judiciously utilized to elaborate solid sensing surfaces. This was done by synthesizing a new BTP derivative and covalently anchoring it onto gold surfaces. The BTP grafting, its chemical modification and the resultant lanthanide complexation were evaluated by combining X-ray Photoelectron Spectroscopy (XPS) and Polarization Modulation-Infrared Reflection Absorption Spectroscopy (PM-IRRAS). The detection of neodynium and europium cations was measured by a Quartz Crystal Microbalance (QCM). Interestingly, when immobilized on gold, BTP appeared to show very distinct sensitivities towards Eu(3+) and Nd(3+). Moreover, these sensitivities could be controlled by varying the pH and/or the nitrate concentration in solution. This novel strategy, consisting of the immobilization of BTP sensing molecules, is thus very promising for sensitive and specific lanthanide detection.