Electronic Wires Research Articles

Simulation of two nanoparticle melting to understand the conductivity drop of 3D-printed silver nanowires

The future flexible sensor technology will require low-temperature, fast processing 3D printing techniques that will rely heavily on the quality of nanoparticle (NP) Ink. Electrical conductivity has been found to decrease in majority of the 3D printed electronic wires. Herein we report a fundamental understanding in drop of electrical conductivity in processed silver (Ag) line wire, generally found in Ag-nanoparticle Ink, using large-scale atomistic molecular dynamics (MD) simulations of sintering of five different sizes of Ag NPs. To preserve the high conductivity of pure silver wires, the integrity of the pristine face-centered cubic (FCC) crystalline structure must be retained in the processed line wires. Simulations show that the pristine Ag FCC structures of the nanoparticles are not recovered after melting and resolidification, instead, the resolidified material is paracrystaline. The breakdown of pristine FCC structures might be the cause of the drop in conductivity of processed Ag wires. Simulation results suggest that the intermediate size nanoparticles retain highest percentage of the pristine silver face-centered cubic (FCC) structure after pulse treatments. Our results show that the most promising Ag-Ink should contain smaller to medium size silver NPs that can retain FCC structure after 3D printing of the Ag-Ink.

Liquid-metal/NdFeB/Ni composites for high wettability, patternable, stretchable electronic wire

Room-temperature liquid-metal (LM) has high conductivity, which is an ideal material for manufacturing stretchable electronic wires. However, its high surface tension and fluidity make it extremely difficult to adhere to or encapsulate on flexible substrates. This work developed LM/NdFeB/Ni composites for stretchable electronic wires. The composites were composed of Ga68.5In21.5Sn10 (with a melting point at −19 °C) alloys, Nd2Fe14B (5 μm), and Ni (50–500 nm) microparticles. The SEM and EDS results showed the porous structure of the composites. Ni particles were added to improve the magnetic properties of LM/NdFeB composites, as well as the porous structure composed of magnetized NdFeB particles. Thereby the structure exhibited a heightened capacity for LM locking. Test results indicate that the liquid metal wires have good wettability and adhesion on different surfaces and could be manufactured using different patterning methods. Moreover, its anti-extrusion and anti-leakage characteristics were suitable for constructing stretchable circuits in open channels or on flat surfaces. The proposed LM/NdFeB/Ni composites are expected to manufacture low-cost, patternable, and anti-extrusion stretchable electronic wires.

Designing Long and Highly Conducting Molecular Wires with Multiple Nontrivial Topological States.

Molecular one-dimensional topological insulators (1D TIs), described by the Su-Schrieffer-Heeger (SSH) model, are a new class of molecular electronic wires whose low-energy topological edge states endow them with high electrical conductivity. However, when these 1D TIs become long, the high conductance is not sustained because the coupling between the edge states decreases with increasing length. Here, we present a new design where we connect multiple short 1D SSH TI units linearly or in a cycle to create molecular wires with a continuous topological state density. Using a tight-binding method, we show that the linear system gives a length-independent conductance. The cyclic systems show an interesting odd-even effect, with unit transmission in the topological limit, but zero transmission in the trivial limit. Furthermore, based on our calculations, we predict that these systems can support resonant transmission with a quantum of conductance. We can further expand these results to phenylene-based linear and cyclic 1D TI systems and confirm the length-dependent conductance in such systems.

Preparation of binder‐free spherical submicron‐sized platinum particles using laser melting in liquids

AbstractSpherical‐shaped submicron‐sized particles (SMPs) of noble metals are an ideal material to prepare electronic wires using ink‐jet printing. Platinum SMPs (PtSMPs) must be a better material than gold SMPs (AuSMPs) used in high temperature conditions, because of the higher melting point of platinum than that of gold. However, differing from AuSMPs, no convenient PtSMP preparation method have been developed so far. In the present study, we have applied the laser melting in liquids method (LML), which has been used to prepare SMPs of various materials, on the preparation of PtSMPs. The results showed that PtSMPs were successfully obtained by laser irradiation at 266 nm for platinum nanoparticles stabilized by a small amount of sodium citrate via the laser‐induced agglomeration. It was also found that PtSMPs of the similar size were obtained when laser wavelength was changed to 355 nm, although the irradiation time necessary to induce NP agglomeration using 355 nm laser irradiation became longer than that using 266 nm laser irradiation. This laser wavelength dependence was explained in terms of the size‐dependent heating efficiency of platinum particles.

Mechanical Valves for On-Board Flow Control of Inflatable Robots.

Inflatable robots are becoming increasingly popular, especially in applications where safe interactions are a priority. However, designing multifunctional robots that can operate with a single pressure input is challenging. A potential solution is to couple inflatables with passive valves that can harness the flow characteristics to create functionality. In this study, simple, easy to fabricate, lightweight, and inexpensive mechanical valves are presented that harness viscous flow and snapping arch principles. The mechanical valves can be fully integrated on‐board, enabling the control of the incoming airflow to realize multifunctional robots that operate with a single pressure input, with no need for electronic components, cables, or wires. By means of three robotic demos and guided by a numerical model, the capabilities of the valves are demonstrated and optimal input profiles are identified to achieve prescribed functionalities. The study enriches the array of available mechanical valves for inflatable robots and enables new strategies to realize multifunctional robots with on‐board flow control.

Tunable Kondo screening length at a Y-junction of three inhomogeneous spin chains

We derive the topological Kondo Hamiltonian describing a Y junction of three XX-spin chains connected to outer quantum Ising chains with different tilting angles for the Ising axis. We show that the tilting angles in the spin models play the role of the phases of the superconducting order parameters at the interfaces between bulk superconductors and one-dimensional conducting normal electronic wires. As a result, different tilting angles induce nonzero equilibrium spin (super)currents through the junction. Employing the renormalization group approach to the topological Kondo model, we derive the scaling formulas for the equilibrium spin currents. We argue that, by monitoring the crossover in the currents induced by the Kondo effect, it is possible to estimate the Kondo screening length. In particular, we prove how it is possible to tune the Kondo length by acting on the applied phases only; this enables us to map out the scaling properties by just tuning the tilting angles and the Kondo length accordingly.

Polypeptides with Pendant Porphyrins: From the Recognition of Bidentate Bases to Inter-Digitated Photo-Active Strands

In natural photosynthetic systems, the solar energy is collected by pigment molecules attached to the light harvesting complexes. In these units, the chlorophylls are held in a favored spacing and orientation by fairly short a-helical polypeptides. In this way, the energy contained in a single photon is conducted in a very short time and with minimal loss of energy from the point where it is absorbed to where it is needed. The extraordinary efficiency of the energy migration over long distances with minimal loss of energy is ascribed to the favored spacing and orientation of the chlorophylls which are held in an appropriate parallel conformation. Beyond the control of the structure of multi-chromophoric arrays, monitoring the spatial orientation of the chromophores in artificial light harvesting devices is a challenge of growing interest. Indeed, multi-porphyrinic arrays attract more and more attention for the elaboration of photonic and electronic wires. An octapeptide and a hexadecapeptide derived from the L-lysine and functionalized with porphyrins have been prepared. Beyond a certain degree of oligomerisation, we observed the development of a secondary structure such as a 310 helix which forces the porphyrins to arrange in a defined spatial arrangement. Due to the overlap of the porphyrins in such a conformation, the chromophores undergo a sufficient electronic coupling to favor a good exciton migration. The ability of these peptides to accomodate guests was investigated through ligand binding studies carried out in dichloromethane with DABCO as bidentate base. The complexation of DABCO by these peptides was monitored by UV-visible spectrophotometric titration in CH2Cl2. We showed that the enhanced stability of the complexe octapeptide/DABCO can be ascribed to a pre-organization of the octapeptide forming cavities, and provides convincing evidence that the bidentate base is inserted into the cavities of the octapeptide via host/guest interactions. Acknowledgements This work was supported by the CNRS and the French Ministry of Research.

Paired parton quantum Hall states: A coupled wire construction

The Pfaffian fractional quantum Hall (FQH) states are incompressible non-Abelian topological fluids present in a half-filled electron Landau level, where there is a balanced population of electrons and holes. They give rise to half-integral quantum Hall plateaus that divide critical transitions between integer quantum Hall (IQH) states. On the other hand, there are Abelian FQH states, such as the Laughlin state, that can be understood using partons, which are fermionic divisions of the electron. In this paper, we propose a new family of incompressible paired parton FQH states at filling $\nu=1/6$ (modulo 1) that emerge from critical transitions between IQH states and Abelian FQH states at filling $\nu=1/3$ (modulo 1). These paired parton states are originated from a half-filled parton Landau level, where there is an equal amount of partons and holes. They generically support Ising-like anyonic quasiparticle excitations and carry non-Abelian Pfaffian topological orders (TO) for partons. We prove the principle existence of these paired parton states using exactly solvable interacting arrays of electronic wires under a magnetic field. Moreover, we establish a new notion of particle-hole (PH) symmetry for partons and relate the PH symmetric parton Pfaffian TO with the gapped symmetric surface TO of a fractional topological insulator in three dimension.

Amino-acid-encoded biocatalytic self-assembly enables the formation of transient conducting nanostructures.

Aqueous compatible supramolecular materials hold promise for applications in environmental remediation, energy harvesting and biomedicine. One remaining challenge is to actively select a target structure from a multitude of possible options, in response to chemical signals, while maintaining constant, physiological conditions. Here, we demonstrate the use of amino acids to actively decorate a self-assembling core molecule in situ, thereby controlling its amphiphilicity and consequent mode of assembly. The core molecule is the organic semiconductor naphthalene diimide, functionalized with D- and L- tyrosine methyl esters as competing reactive sites. In the presence of α-chymotrypsin and a selected encoding amino acid, kinetic competition between ester hydrolysis and amidation results in covalent or non-covalent amino acid incorporation, and variable supramolecular self-assembly pathways. Taking advantage of the semiconducting nature of the naphthalene diimide core, electronic wires could be formed and subsequently degraded, giving rise to temporally regulated electro-conductivity.

Inter-Digitated Photo-Active Strands

In natural photosynthetic systems, the solar energy is collected by pigment molecules attached to the light harvesting complexes. In these units, the chlorophylls are held in a favored spacing and orientation by fairly short a-helical polypeptides.1 When a photon hits one of the chlorophylls, the absorbed energy spreads extremely rapidly to the others until the reaction center is reached within the cell membrane, where the solar energy is converted into chemical energy used by the cell to grow. In this way, the energy contained in a single photon is conducted in a very short time and with minimal loss of energy from the point where it is absorbed to where it is needed. The extraordinary efficiency of the energy migration over long distances with minimal loss of energy is ascribed to the favored spacing and orientation of the chlorophylls which are held in an appropriate parallel conformation. Beyond the control of the structure of multi-chromophoric arrays, monitoring the spatial orientation of the chromophores in artificial light harvesting devices is a challenge of growing interest. Indeed, multi-porphyrinic arrays attract more and more attention for the elaboration of photonic and electronic wires.2 An octapeptide3 and an hexadecapeptide4 derived from the L-lysine and functionalized with porphyrins have been prepared. Beyond a certain degree of oligomerisation, we observed the development of a secondary structure such as a 310 helix which forces the porphyrins to arrange in a defined spatial arrangement. Due to the overlap of the porphyrins in such a conformation, the chromophores undergo a sufficient electronic coupling to favor a good exciton migration.5 The ability of these peptides to accomodate guests was investigated through ligand binding studies carried out in dichloromethane with DABCO as bidentate base. The complexation of DABCO by these peptides was monitored by UV-visible spectrophotometric titration in CH2Cl2. We showed that the enhanced stability of the complexe octapeptide/DABCO can be ascribed to a pre-organization of the octapeptide forming cavities, and provides convincing evidence that the bidentate base is inserted into the cavities of the octapeptide via host/guest interactions. Acknowledgements This work was supported by the CNRS and the French Ministry of Research. References W. Kühlbrandt, Nature 1995, 374, 497-498.a) R. W. Wagner, J. S. Lindsey, J. Seth, V. Palaniappan, D. F. Bocian, J. Am. Chem. Soc. 1996, 118, 3996-3997 and ref. cited therein. b) M. J. Crossley, P. L. Burn, S. J. Langford, J. K Prashar, J. Chem. Soc., Chem. Commun. 1995, 1921-1923. c) A. Osuka, H. Shimidzu, Angew. Chem. Int. Ed. Engl. 1997, 36, 135-137.N. Solladié, A. Hamel, M. Gross, Tet. Lett. 2000, 41, 6075-6078.Unpublished results.a) M. Fujitsuka, M. Hara, S. Tojo, A. Okada, V. Troiani, N. Solladié, T. Majima, J. Phys. Chem B. 2005, 109, 33-35. b) M. Fujitsuka, D. W. Cho, N. Solladié, V. Troiani, H. Qiu, T. Majima, J. Photochem. Photobiol. A 2007, 188, 346-350. Figure 1

(Invited) Multiscale Morphological and Electrical Characterization of Charge Transport and Charge Transfer Limitations to Power Performance of Positive Electrode for Li-Ion Batteries

Composite materials consisting of several interpenetrated and percolating phases are widely used as electrodes for a variety of electrochemical cells. Such electrodes are generally mixed ionic−electronic conductors, in which ions and electrons are confined to transport within the specific conducting network. In particular, for electrochemical storage and energy transformation devices, the transport properties play critical roles in determining their performance, which is pivotal to improve them for service as power sources. To reach this goal, an increased fundamental understanding of the factors that play on the transport properties within such composite materials is still required. The transport of the electrons and ions through Li-ion battery electrode and their transfer to the active matter depend on the electrode architecture (nano- and microstructure) through the interfacial areas, materials connectivity, and the transport length scales. Novel opportunity for progressing in this direction and exploring relationships between electrode architecture, charge transport and electrochemical performance is implementation of X-ray computed tomography (XRCT) and focused ion beam in combination with scanning electron microscopy (FIB-SEM) techniques to characterize and quantify the 3D architecture of composite electrodes. In particular, tortuosity, a critical parameter with respect to ionic transport, has been exhaustively studied. Comparatively, factors that play on the electrons transport and wiring to the active mass have been much less considered. Moreover, attempts to correlate quantified 3D geometries with measured electrochemical power performance or electrical transport properties of same real electrodes remain rare. We intend to fill this gap in this presentation. We have undertaken exhaustive characterizations of 3D geometries of LiNi1/3Mn1/3Co1/3O2 (NMC), LiFePO4 (LFP), and NMC/LFP blended electrodes and rationally interpreted their measured electrical properties and electrochemical performance. A combination of X-Ray tomography and FIB-SEM tomography are used for a multiscale analysis of electrodes 3D geometries, in particular the distribution of the conductive additive and the binder that perform as electronic wires, the tortuous pores distribution, which after electrolyte impregnation perform as ionic wires, and the inter-connectivity between the active matter phase and the electronic and the ionic wires [1]. The electrical properties (permittivity and conductivity) are measured from low (a few Hz) to microwave (a few GHz) frequencies by the broadband dielectric spectroscopy technique [2]. This one is very sensitive to the different scales of the electrode architecture involved in electronic transport, from interatomic distances to macroscopic sizes, as well as to the morphology at these scales, coarse or fine distribution of the constituents [2,3]. In addition to the geometry of the electrode architecture, the interfaces (adsorption of ions to the surface of active material and carbon nanoparticles), and interactions at such interfaces lead to a reciprocal influence of ionic and electronic transfers at the different scales of the electrode [4]. Finally, discharge rate performance is analyzed by simple, yet efficient methods. This approach allows discriminating between the contributions of the electronic and ionic wiring networks as the performance limiting factors, depending on the electrode geometry and discharge rate. [5] Acknowledgements Financial funding from the ANR Program No. ANR-15-CE05-0001-01 (PEPITE) is acknowledged. We also thank the CLYM (Centre Lyonnais de Microscopie) supported by the CNRS, the “Grand Lyon” and the Rhône-Alpes Region for use of the Zeiss NVision40 FIB/SEM. The IMD (Institut de la Mobilité Durable – Sustainable Mobility Institute) is also acknowledged for financial support.

Self-Sensitization and Photo-Polymerization of Diacetylene Molecules Self-Assembled on a Hexagonal-Boron Nitride Nanosheet.

Long poly-diacetylene chains are excellent candidates for planar, on-surface synthesized molecular electronic wires. Since hexagonal-Boron Nitride (h-BN) was identified as the best available atomically flat insulator for the deposition of poly-diacetylene precursors, we demonstrate the polymerization patterns and rate on it under UV-light irradiation, with subsequent polymer identification by atomic force microscopy. The results on h-BN indicate self-sensitization which yields blocks comprised of several polymers, unlike on the well-studied graphite/diacetylene system, where the polymers are always isolated. In addition, the photo-polymerization proceeds at least 170 times faster on h-BN, where it also results in longer polymers. Both effects are explained by the h-BN bandgap, which is larger than the diacetylene electronic excitation energy, thus allowing the transfer of excess energy absorbed by polymerized wires to adjacent monomers, triggering their polymerization. This work sets the stage for conductance measurements of single molecular poly-diacetylene wires on h-BN.

Modelling and Product customization of PVC Coating Machine

In industrial markets, however, customization is nothing new, and has always been significant. Product customization has recently attracted interest due to the emergence of ‘‘mass customization'' used the categories make-to-stock, make-to-order and engineer-to-order, which combines logistics design issues and notes that ‘‘exceptions/specials'' are the biggest problem in a make-to-stock environment. (Martin Spring et.al 2000)A coating is a covering that is applied to the surface of an object, usually referred to as the substrate. The purpose of applying coating maybe decorative surface treatment, rust prevention and durability. Polyvinyl chloride coating technique is used in industries from last 40 years as a proven technology for surface coating. The advantages of this coatings are rust prevention anti-bacterial growth protection, better adhesion to steel surface, good scratch finish properties. The cost-effective technique for rust prevention and durability is need of today’s competitive engineering world. Many of the processes are used for surface treatment like surface plating, Powder coating, Painting, PVC coating. PVC Coating technique is used for coating mechanical components, construction applications, automobile applications, sports, electronic wires and cables. The advantage of this coatings are rust prevention, anti-bacterial growth protection, better adhesion to steel surface, good scratch finish properties.

Multiplexed aptasensor for simultaneous detection of carcinoembryonic antigen and mucin-1 based on metal ion electrochemical labels and Ru(NH3)63+ electronic wires

In this paper, a dual-target electrochemical aptasensor has been developed for simultaneous detection of carcinoembryonic antigen and mucin-1 based on metal ion electrochemical labels and Ru(NH3)63+ electronic wires. When targets are present, the interaction between targets and their respective aptamers leads to the dissociation of double-strand DNA because the targets have higher affinity to its aptamer than the complementary strand. And the qualitative and quantitative analyses of the two targets are realized by the differential pulse voltammetry (DPV) peaks generated by metal ion electrochemical labels. For the effective loading of a large number of metal ions, Au/bovine serum albumin (Au/BSA) nanospheres are employed as carriers to develop Au/BSA–metal ions. After Ru(NH3)63+ complexes are embedded into double-strand DNA to form the electronic wires, the electrical conductivity and the electron transfer of the detection system are greatly improved. The detection limit of the proposed assay was calculated as 3.33fM ranging from 0.01pM to 100nM. Therefore, this novel sensing assay provides a new and sensitive platform for detecting several targets simultaneously in biochemical research and clinical diagnosis.

Spin analogs of superconductivity and integer quantum Hall effect in an array of spin chains

Motivated by the successful idea of using weakly-coupled quantum electronic wires to realize the quantum Hall effects and the quantum spin Hall effects, we theoretically construct two systems composed of weakly-coupled quantum spin chains, which can exhibit spin analogues of superconductivity and the integer quantum Hall effect. Specifically, a certain bilayer of two arrays of interacting spin chains is mapped, via the Jordan-Wigner transformation, to a negative-$U$ Hubbard model that exhibits superconductivity. In addition, an array of spin-orbit-coupled spin chains in the presence of an suitable external magnetic field is transformed to an array of quantum wires that exhibits the integer quantum Hall effect. The resultant spin superconductivity and spin integer quantum Hall effect can be characterized by their ability to transport spin without any resistance.

Inter-Digitated Photo-Active Strands

In natural photosynthetic systems, the solar energy is collected by pigment molecules attached to the light harvesting complexes. In these units, the chlorophylls are held in a favored spacing and orientation by fairly short α-helical polypeptides.1 When a photon hits one of the chlorophylls, the absorbed energy spreads extremely rapidly to the others until the reaction center is reached within the cell membrane, where the solar energy is converted into chemical energy used by the cell to grow. In this way, the energy contained in a single photon is conducted in a very short time and with minimal loss of energy from the point where it is absorbed to where it is needed. The extraordinary efficiency of the energy migration over long distances with minimal loss of energy is ascribed to the favored spacing and orientation of the chlorophylls which are held in an appropriate parallel conformation. Beyond the control of the structure of multi-chromophoric arrays, monitoring the spatial orientation of the chromophores in artificial light harvesting devices is a challenge of growing interest. Indeed, multi-porphyrinic arrays attract more and more attention for the elaboration of photonic and electronic wires.2 An octapeptide3 and an hexadecapeptide4 derived from the L-lysine and functionalized with porphyrins have been prepared. Beyond a certain degree of oligomerisation, we observed the development of a secondary structure such as a 310 helix which forces the porphyrins to arrange in a defined spatial arrangement. Due to the overlap of the porphyrins in such a conformation, the chromophores undergo a sufficient electronic coupling to favor a good exciton migration.5 The ability of these peptides to accomodate guests was investigated through ligand binding studies carried out in dichloromethane with DABCO as bidentate base. The complexation of DABCO by these peptides was monitored by UV-visible spectrophotometric titration in CH2Cl2. We showed that the enhanced stability of the complexe octapeptide/DABCO can be ascribed to a pre-organization of the octapeptide forming cavities, and provides convincing evidence that the bidentate base is inserted into the cavities of the octapeptide via host/guest interactions. Acknowledgements This work was supported by the CNRS and the French Ministry of Research. References W. Kühlbrandt, Nature 1995, 374, 497-498. a) R. W. Wagner, J. S. Lindsey, J. Seth, V. Palaniappan, D. F. Bocian, J. Am. Chem. Soc. 1996, 118, 3996-3997 and ref. cited therein. b) M. J. Crossley, P. L. Burn, S. J. Langford, J. K Prashar, J. Chem. Soc., Chem. Commun. 1995, 1921-1923. c) A. Osuka, H. Shimidzu, Angew. Chem. Int. Ed. Engl. 1997, 36, 135-137. N. Solladié, A. Hamel, M. Gross, Tet. Lett. 2000, 41, 6075-6078. Unpublished results. a) M. Fujitsuka, M. Hara, S. Tojo, A. Okada, V. Troiani, N. Solladié, T. Majima, J. Phys. Chem B. 2005, 109, 33-35. b) M. Fujitsuka, D. W. Cho, N. Solladié, V. Troiani, H. Qiu, T. Majima, J. Photochem. Photobiol. A 2007, 188, 346-350. Figure 1

In situ twisting for stabilizing and toughening conductive graphene yarns.

Graphene fibres are of great interest for diverse applications such as their use in supercapacitors, batteries, stimulus-responsive actuators and smart textiles. However, previously reported graphene-based fibres commonly have very low toughness and poor stretchability, which can limit many of their possible applications. We demonstrate an efficient approach for preparing super-tough yarns of reduced graphene oxides via the in situ twisting of multiplied graphene oxide fibres during fibre extrusion and coagulation, followed by chemical reduction and drying. These twisted multiplied yarns have a toughness of 46.3 J m-3, much higher than previous results for graphene-based fibres and films, and benefit from the retention of high strength and a significant increase in the failure strain due to the stably twisted hollow structure of the yarns. These yarns also show very stable electrical resistance when subjected to cyclic stretching at a large tensile strain. We demonstrate the utilization of such yarns for stretchable conducting electronic wires.

Polypeptides with Pendant Porphyrins: From the Recognition of Bidentate Bases to Inter-Digitated Photo-Active Strands

In natural photosynthetic systems, the solar energy is collected by pigment molecules attached to the light harvesting complexes. In these units, the chlorophylls are held in a favored spacing and orientation by fairly short a-helical polypeptides.1 When a photon hits one of the chlorophylls, the absorbed energy spreads extremely rapidly to the others until the reaction center is reached within the cell membrane, where the solar energy is converted into chemical energy used by the cell to grow. In this way, the energy contained in a single photon is conducted in a very short time and with minimal loss of energy from the point where it is absorbed to where it is needed. The extraordinary efficiency of the energy migration over long distances with minimal loss of energy is ascribed to the favored spacing and orientation of the chlorophylls which are held in an appropriate parallel conformation. Beyond the control of the structure of multi-chromophoric arrays, monitoring the spatial orientation of the chromophores in artificial light harvesting devices is a challenge of growing interest. Indeed, multi-porphyrinic arrays attract more and more attention for the elaboration of photonic and electronic wires.2 An octapeptide3 and an hexadecapeptide4 derived from the L-lysine and functionalized with porphyrins have been prepared. Beyond a certain degree of oligomerisation, we observed the development of a secondary structure such as a 310 helix which forces the porphyrins to arrange in a defined spatial arrangement. Due to the overlap of the porphyrins in such a conformation, the chromophores undergo a sufficient electronic coupling to favor a good exciton migration.5 The ability of these peptides to accomodate guests was investigated through ligand binding studies carried out in dichloromethane with DABCO as bidentate base. The complexation of DABCO by these peptides was monitored by UV-visible spectrophotometric titration in CH2Cl2. We showed that the enhanced stability of the complexe octapeptide/DABCO can be ascribed to a pre-organization of the octapeptide forming cavities, and provides convincing evidence that the bidentate base is inserted into the cavities of the octapeptide via host/guest interactions. Acknowledgements This work was supported by the CNRS and the French Ministry of Research. References W. Kühlbrandt, Nature 1995, 374, 497-498.a) R. W. Wagner, J. S. Lindsey, J. Seth, V. Palaniappan, D. F. Bocian, J. Am. Chem. Soc. 1996, 118, 3996-3997 and ref. cited therein. b) M. J. Crossley, P. L. Burn, S. J. Langford, J. K Prashar, J. Chem. Soc., Chem. Commun. 1995, 1921-1923. c) A. Osuka, H. Shimidzu, Angew. Chem. Int. Ed. Engl. 1997, 36, 135-137. N. Solladié, A. Hamel, M. Gross, Tet. Lett. 2000, 41, 6075-6078.Unpublished results.a) M. Fujitsuka, M. Hara, S. Tojo, A. Okada, V. Troiani, N. Solladié, T. Majima, J. Phys. Chem B. 2005, 109, 33-35. b) M. Fujitsuka, D. W. Cho, N. Solladié, V. Troiani, H. Qiu, T. Majima, J. Photochem. Photobiol. A 2007, 188, 346-350. Figure 1

Wiring of Glucose Oxidizing Flavin Adenine Dinucleotide-Dependent Enzymes by Methylene Blue-Modified Third Generation Poly(amidoamine) Dendrimers Attached to Spectroscopic Graphite Electrodes

Electro-enzymatic biotransformation requires an efficient and robust electronic communication between the biomolecules and electrodes, often performed by the relevant electron transfer (ET) mediating systems. Of those, redox-labeled dendrimeric structures, biocompatible and bearing spatially ordered multiple redox centers, represent an advanced alternative to the existing approaches. Here we show that methylene blue (MB)-labeled G3 PAMAM dendrimers covalently attached to the high-surface area spectroscopic graphite (Gr) electrodes form stable and spatially resolved electronic wires, characterized by the heterogeneous ET rate constant of 7.1±0.1s−1; they can be used for electronic wiring of glucose-oxidizing FAD-containing enzymes, such as hexose oxidase (HOX), and further bioelectrocatalysis of glucose oxidation, starting, at pH 7, from -100mV vs. Ag/AgCl. Thus, dendrimer-templated electronic wires, comprising MB molecules conjugated to the periphery of the PAMAM and anchored to the surface of cost-effective Gr electrodes represent an efficient and robust tool for protein wiring to electrodes for their perspective bioelectronic applications in biosensors and biofuel cells.

Routing of individual polymers in designed patterns.

Synthetic polymers are ubiquitous in the modern world, but our ability to exert control over the molecular conformation of individual polymers is very limited. In particular, although the programmable self-assembly of oligonucleotides and proteins into artificial nanostructures has been demonstrated, we currently lack the tools to handle other types of synthetic polymers individually and thus the ability to utilize and study their single-molecule properties. Here we show that synthetic polymer wires containing short oligonucleotides that extend from each repeat can be made to assemble into arbitrary routings. The wires, which can be more than 200 nm in length, are soft and bendable, and the DNA strands allow individual polymers to self-assemble into predesigned routings on both two- and three-dimensional DNA origami templates. The polymers are conjugated and potentially conducting, and could therefore be used to create molecular-scale electronic or optical wires in arbitrary geometries.