Digital printing of a novel electrode for stable flexible organic solar cells with a power conversion efficiency of 8.5.

Poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) mixed with single-wall nanotubes (SWNTs) (10:1) and doped with (0.1 M) perchloric acid (HClO4) in a solution-processed film, working as an excellent thin transparent conducting film (TCF) in organic solar cells, was investigated. This new electrode structure can be an outstanding substitute for conventional indium tin oxide (ITO) for applications in flexible solar cells due to the potential of attaining high transparency with enhanced conductivity, good flexibility, and good durability via a low-cost process over a large area. In addition, solution-processed vanadium oxide (VOx) doped with a small amount of PEDOT-PSS(PH1000) can be applied as a hole transport layer (HTL) for achieving high efficiency and stability. From these viewpoints, we investigate the benefit of using printed SWNTs-PEDOT-PSS doped with HClO4 as a transparent conducting electrode in a flexible organic solar cell. Additionally, we applied a VOx-PEDOT-PSS thin film as a hole transporting layer and a blend of PTB7 (polythieno[3,4-b] thiophene/benzodithiophene): PC71BM (phenyl-C71-butyric acid methyl ester) as an active layer in devices. Zinc oxide (ZnO) nanoparticles were applied as an electron transport layer and Ag was used as the top electrode. The proposed solar cell structure showed an enhancement in short-circuit current, power conversion efficiency, and stability relative to a conventional cell based on ITO. This result suggests a great carrier injection throughout the interfacial layer, high conductivity and transparency, as well as firm adherence for the new electrode.

Inductive Coupling and Flow for Increased NMR Sensitivity.

A device is proposed to enhance the NMR sensitivity of slowly relaxing nuclei, taking advantage of a controlled solution flow within a microfluidic circuit and microsized NMR detection. Unlike our previous work ( Carret et al. Anal. Chem. 2017 , 89 ( 5 ), 2995 - 3000 ), this setup can be easily installed on any commercial NMR probehead as it uses induction between the commercial antenna and the microcoil. Such a system leads to a significant gain in sensitivity per time unit for slowly relaxing nuclei while preserving the capabilities of the host probehead.

GraftFast Surface Engineering to Improve MOF Nanoparticles Furtiveness.

Controlling the outer surface of nanometric metal-organic frameworks (nanoMOFs) and further understanding the in vivo effect of the coated material are crucial for the convenient biomedical applications of MOFs. However, in most studies, the surface modification protocol is often associated with significant toxicity and/or lack of selectivity. As an alternative, how the highly selective and general grafting GraftFast method leads, through a green and simple process, to the successful attachment of multifunctional biopolymers (polyethylene glycol (PEG) and hyaluronic acid) on the external surface of nanoMOFs is reported. In particular, effectively PEGylated iron trimesate MIL-100(Fe) nanoparticles (NPs) exhibit suitable grafting stability and superior chemical and colloidal stability in different biofluids, while conserving full porosity and allowing the adsorption of bioactive molecules (cosmetic and antitumor agents). Furthermore, the nature of the MOF-PEG interaction is deeply investigated using high-resolution soft X-ray spectroscopy. Finally, a cell penetration study using the radio-labeled antitumor agent gemcitabine monophosphate (3 H-GMP)-loaded MIL-100(Fe)@PEG NPs shows reduced macrophage phagocytosis, confirming a significant in vitro PEG furtiveness.

Measuring Dirac Cones in a Subwavelength Metamaterial.

The exciting discovery of bidimensional systems in condensed matter physics has triggered the search of their photonic analogues. In this Letter, we describe a general scheme to reproduce some of the systems ruled by a tight-binding Hamiltonian in a locally resonant metamaterial; by specifically controlling the structure and the composition it is possible to engineer the band structure at will. We numerically and experimentally demonstrate this assertion in the microwave domain by reproducing the band structure of graphene, the most famous example of those 2D systems, and by accurately extracting the Dirac cones. This is direct evidence that opting for a crystalline description of those subwavelength scaled systems, as opposed to the usual description in terms of effective parameters, makes them a really convenient tabletop platform to investigate the tantalizing challenges that solid-state physics offer.

Slow waves in locally resonant metamaterials line defect waveguides.

Many efforts have been devoted to wave slowing, as it is essential, for instance, in analog signal computing and is one prerequisite for increased wave/matter interactions. Despite the interest of many communities, researches have mostly been conducted in optics, where wavelength-scaled structured composite media are promising candidates for compact slow light components. Yet their structural scale prevents them from being transposed to lower frequencies. Here, we propose to overcome this limitation using the deep sub-wavelength scale of locally resonant metamaterials. We experimentally show, in the microwave regime, that introducing coupled resonant defects in such metamaterials creates sub-wavelength waveguides in which wave propagation exhibit reduced group velocities. We qualitatively explain the mechanism underlying this slow wave propagation and demonstrate how it can be used to tune the velocity, achieving group indices as high as 227. We conclude by highlighting the three beneficial consequences of our line defect slow wave waveguides: (1) the sub-wavelength scale making it a compact platform for low frequencies (2) the large group indices that together with the extreme field confinement enables efficient wave/matter interactions and (3) the fact that, contrarily to other approaches, slow wave propagation does not occur at the expense of drastic bandwidth reductions.

Crystalline metamaterials for topological properties at subwavelength scales.

The exciting discovery of topological condensed matter systems has lately triggered a search for their photonic analogues, motivated by the possibility of robust backscattering-immune light transport. However, topological photonic phases have so far only been observed in photonic crystals and waveguide arrays, which are inherently physically wavelength scaled, hindering their application in compact subwavelength systems. In this letter, we tackle this problem by patterning the deep subwavelength resonant elements of metamaterials onto specific lattices, and create crystalline metamaterials that can develop complex nonlocal properties due to multiple scattering, despite their very subwavelength spatial scale that usually implies to disregard their structure. These spatially dispersive systems can support subwavelength topological phases, as we demonstrate at microwaves by direct field mapping. Our approach gives a straightforward tabletop platform for the study of photonic topological phases, and allows to envision applications benefiting the compactness of metamaterials and the amazing potential of topological insulators.

Enhancing NMR of Nonrelaxing Species Using a Controlled Flow Motion and a Miniaturized Circuit.

In this article we show that circulation of the sample in a closed-loop circuit combined to microsized detection can lead to a significant signal NMR enhancement. We present an optimized NMR device based on a mini bubble-pump associated with fluidics and microdetection that can be installed on a commercial NMR spectrometer. In addition to a significant signal enhancement for slowly relaxing nuclei, we show that it enables more precise and frequent monitoring of chemical reactions. An additional modification leads to a stopped-flow system very efficient for instance for 2D NMR experiments with long mixing times.

Supramolecular Peptide/Surface Assembly for Monitoring Proteinase Activity and Cancer Diagnosis.

Matrix metalloproteinases (MMP) are a family of proteolytic enzymes, the expression of which in a key step of tumor progression has recently been better defined. The overexpression of one or more MMPs is thus common among malignant tumors. It may characterize tumor progression and help predict its response to chemotherapy. Consequently, the development of a device for measuring MMP activities is an important challenge for diagnosis and prognosis. In this study, we describe an innovative supramolecular peptide/surface assembly for screening MMP activities. This sensor was used to discriminate various MMP activities and to distinguish between invasive and noninvasive cancerous cell suspensions. Our results confirm the proof-of-concept of a powerful tool for the determination of the tumor aggressiveness and a technical building block for future development of MMP lab-on-chip devices.

Photolinker-free photoimmobilization of antibodies onto cellulose for the preparation of immunoassay membranes.

Paper-based detection devices such as lateral flow immunoassays (LFIAs) are inexpensive, rapid, user-friendly and therefore highly promising for providing resource-limited settings with point-of-care diagnostics. Recently, this biosensing field has trended towards three-dimensional microfluidic devices and multiplexed assay platforms. However, many multiplexed paper-based biosensors implement methods incompatible with the conventional LFIA carrier material: nitrocellulose. It thus tends to be replaced by cellulose. This major material change implies to undertake a covalent immobilization of biomolecules onto cellulose which preserves their biological activity. In this perspective, the immobilization process elaborated in this study is entirely biocompatible. While antibody immobilization onto cellulose usually requires chemical modifications of either the biomolecule and/or the membrane, the light-based procedure presented here was performed without any chemical photolinker. Native biomolecules have been successfully immobilized onto paper sheets which therefore enable to perform LFIAs. More generally, the process expounded herein is fast, simple, cost-saving, environmentally-friendly and would be helpful to immobilize chemical-sensitive biomolecules onto cellulose sheets.

Interaction of fluorescently labeled triethyleneglycol and peptide derivatives with ß-cyclodextrin.

A triethyleneglycol (TEG) chain, a linear peptide, and a cyclic peptide labeled with 7-methoxycoumarin-3-carboxylic acid (MC) and 7-diethylaminocoumarin-3-carboxylic acid (DAC) were used to thoroughly study Förster resonance energy transfer (FRET) in inclusion complexes. (1) H NMR evidence was given for the formation of a 1:1 inclusion complex between ß-cyclodextrin (ß-CD) and the fluorophore moieties of model compounds. The binding constant was 20 times higher for DAC than for MC derivatives. Molecular modeling provided additional information. The UV/Vis absorption and fluorescence properties were studied and the energy transfer process was quantified. Fluorescence quenching was particularly strong for the peptide derivatives. The presence of ß-CDs reduced the FRET efficiency slightly. Dye-labeled peptide derivatives can thus be used to form inclusion complexes with ß-CDs and retain most of their FRET properties. This paves the way for their subsequent use in analytical devices that are designed to measure the activity of matrix metalloproteinases.

Cellulose: from biocompatible to bioactive material.

Since the papyri, cellulose has played a significant role in human culture, especially as paper. Nowadays, this ancient product has found new scientific applications in the expanding sector of paper-based technology. Among paper-based devices, paper-based biosensors raise a special interest. The high selectivity of biomolecules for target analytes makes these sensors efficient. Moreover, simple paper-based detection devices do not require hardware or specific technical skill. They are inexpensive, rapid, user-friendly and therefore highly promising for providing resource-limited settings with point-of-care diagnostics. The immobilization of biomolecules onto cellulose is a key step in the development of these sensing devices. Following an overview of cellulose structural features and physicochemical properties, this article reviews current techniques for the immobilization of biomolecules on paper membranes. These procedures are categorized into physical, biological and chemical approaches. There is no universal method for biomolecule immobilization. Thus, for a given paper-based biochip, each strategy can be considered.

Piezoelectric tuning fork probe for atomic force microscopy imaging and specific recognition force spectroscopy of an enzyme and its ligand.

Piezoelectric quartz tuning fork has drawn the attention of many researchers for the development of new atomic force microscopy (AFM) self-sensing probes. However, only few works have been done for soft biological materials imaging in air or aqueous conditions. The aim of this work was to demonstrate the efficiency of the AFM tuning fork probe to perform high-resolution imaging of proteins and to study the specific interaction between a ligand and its receptor in aqueous media. Thus, a new kind of self-sensing AFM sensor was introduced to realize imaging and biochemical specific recognition spectroscopy of glucose oxidase enzyme using a new chemical functionalization procedure of the metallic tips based on the electrochemical reduction of diazonium salt. This scanning probe as well as the functionalization strategy proved to be efficient respectively for the topography and force spectroscopy of soft biological materials in buffer conditions.

Versatile and nondestructive photochemical process for biomolecule immobilization.

Covalent immobilization of unmodified biological materials as proteins has been performed through a one-step and soft method. This process is based on a polyazidophenylene layer derived from the electroreduction of the parent salt 4-azidobenzenediazonium tetrafluoborate on gold substrates. The wavelength used (365 nm) for the photochemical grafting of a large variety of molecules as biomolecules is a key point to this nondestructive immobilization method. This simple process is also versatile and could be used for covalently binding a wide range of molecules such as polyethylene glycol moieties, for example. To validate this approach for biochip or microarray fabrication, a surface plasmon resonance imaging (SPRi) platform for immobilization of various antibody families was created by grafting G-protein through this process. This SPRi antibodies platform was tested with several consecutive cycles of antigen injections/regeneration steps without loss of activity.

A one-step and biocompatible cellulose functionalization for covalent antibody immobilization on immunoassay membranes.

Among bioactive papers, many multiplexed assays implement methods incompatible with the conventional lateral flow immunoassay (LFIA) carrier material, nitrocellulose. Consequently, its replacement by cellulose has to be considered. This technological breakthrough requires a surface chemistry which ensures both the biomolecules covalent grafting to cellulose and the conservation of their biological activity. To comply with these requirements, the process elaborated in this study implements compounds and methods compatible with biological material. While cellulose chemical modification is usually operated under harsh conditions in organic solvents, the diazonium-based functionalization procedure presented here was performed onto cellulose sheets in water and at room temperature. Paper sheets have been successfully modified and bear different chemical functions which enable grafting of biomolecules by common bioconjugate techniques and to perform LFIAs. More generally, the chemical ways developed in this study are suitable for many biomolecules and would be helpful for any sensitive molecule immobilization onto cellulose sheets.

Design, characterization, and evaluation of peptide arrays allowing the direct monitoring of MMP activities.

Characterization of matrix metalloprotease (MMP) activities is of increasing interest for cancer prognosis or treatment follow-up. Indeed, MMP-1, -2 and -9 are widely involved in the growth of many tumors and progression steps such as angiogenesis, invasion, and metastasis. Fluorogenic peptide MMP substrates were previously synthesized with the aim of detecting MMP activities. One of their drawbacks is their limited solubility in biological media. Grafting them onto a solid support represented a novel way to yield efficient analysis devices whilst at the same time decreasing the quantities of peptides used. Novel peptide arrays were designed in order to detect MMP activities in biological fluids. Silicon plates were used as the solid support for the design of these novel tools. These were functionalized by organic self-assembled monolayers (SAMs) on which fluorogenic peptides were covalently coupled. SAM and peptide grafting on silicon plates were confirmed by epifluorescence, ellipsometry, and FT-IR analysis. Enzymatic assays were monitored by fluorescence spectrometry and showed that immobilized linear peptides were recognized and cleaved by MMPs.

3D amino-induced electroless plating: a powerful toolset for localized metallization on polymer substrates.

The "3D amino-induced electroless plating" (3D-AIEP) process is an easy and cost-effective way to produce metallic patterns onto flexible polymer substrates with a micrometric resolution and based on the direct printing of the mask with a commercial printer. Its effectiveness is based on the covalent grafting onto substrates of a 3D polymer layer which presents the ability to entrap Pd species. Therefore, this activated Pd-loaded and 3D polymer layer acts both as a seed layer for electroless metal growth and as an interdigital layer for enhanced mechanical properties of the metallic patterns. Consequently, flexible and transparent poly(ethylene terephtalate) (PET) sheets were selectively metalized with nickel or copper patterns. The electrical properties of the obtained metallic patterns were also studied.

"Click" conjugation of peptide on the surface of polymeric nanoparticles for targeting tumor angiogenesis.

PURPOSE: Angiogenesis plays a critical role in tumor growth. This phenomena is regulated by numerous mediators such as vascular endothelial growth factor (VEGF). CBO-P11, a cyclo-peptide, has proven to specifically bind to receptors of VEGF and may be used as targeting ligand for tumor angiogenesis. We herein report the design of novel nanoparticles conjugated to CBO-P11 in order to specifically target tumor site. METHODS: The conjugation of CBO-P11 on the surface of poly(vinylidene fluoride) (PVDF) nanoparticles was investigated using the copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition known as "click" reaction. CBO-P11 was modified with a near-infrared cyanine dye bearing an alkyne function, allowing both "click" coupling on azido-modified nanoparticles and fluorescence labelling. Each step of this nanodevice construction was judiciously performed in aqueous solution and successfully characterized. The cytotoxicity of nanoparticles was evaluated in human brain endothelial cell line and their affinity for VEGF receptors was determined via fluorescence-based uptake assays on porcine aortic endothelial cell line. RESULTS: Nanoparticles were found to be spherical, dense, monodisperse and stable. No cytotoxicity was observed after four days of incubation demonstrating the biocompatibility of nanoparticles. Fluorescence highlighted the specific interaction of these functionalized nanoparticles for VEGF receptors, suggesting that the targeting peptide bioactivity was retained. CONCLUSIONS: These results demonstrate the potential of these functionalized nanoparticles for targeting tumor angiogenesis and their possible use as multifunctional platform for cancer treatment if coupled with therapeutic agents.

Microscopic study of a ligand induced electroless plating process onto polymers.

The ligand induced electroless plating (LIEP) process was recently developed and thoroughly demonstrated with one of the most used polymers for plating processes: acrylonitrile-butadiene-styrene (ABS). This generic process is based, thanks to the use of diazonium salts as precursors, on the covalent grafting of a thin layer of poly(acrylic acid) (PAA) acting as ligand for metallic salts onto pristine polymer surfaces. This strategy takes advantage of the PAA ion exchange properties. Indeed, carboxylate groups contained in PAA allow one to complex copper ions which are eventually reduced and used as catalysts of the metallic deposition. Essentially based on ABS, ABS-PC (ABS-polycarbonate) and PA (polyamide) substrates, the present paper focuses on the role of the polymer substrate and the relationships between the macroscopic properties and microscopic characterizations such as infrared (IR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The adhesion strength of the metallic layer deposited via that LIEP process with the bulk polymer substrates was successfully compared with the adhesion of similar copper films deposited by the usual process based on chromic acid etching and palladium-based seed layer, by measuring the T-peel adhesion strength, and by carrying out the common industrial scotch tape test. Lastly, the electrical properties of the deposited layer were studied thanks to a four-point probe and scanning tunneling microscopy (STM) measurements.

Novel cyclopeptides for the design of MMP directed delivery devices: a novel smart delivery paradigm.

PURPOSE: Matrix metalloproteinases (MMP) are a family of proteolytic enzymes, the expression of which in a key step of tumor progression has been better defined recently. The studies highlighted the ongoing need for very specific inhibitors, substrates or release devices designed to be selective for one or at least very few MMPs. METHODS: This report deals with the design, synthesis and in vitro evaluation of linear and especially novel cyclic peptidic moieties, embodying MMP cleavable sequences designed to answer these questions. FRET (fluorescence resonance energy transfer) labelling via chromophore-modified amino-acids was used to give access to enzyme kinetics. RESULTS: Evaluation of these peptides showed that cyclisation gives rise to high specificity for certain MMP, suggesting that this approach could provide very specific MMP substrate. Moreover, cyclic structures present a very good plasma stability. CONCLUSIONS: These original derivatives could allow the design of MMP-controlled delivery devices, the specificity of which will be retained in complex biological media and in vivo.