Engineering Directional Charge Carrier Transport Using Ferroelectric Polarization for Enhanced Photoelectrochemical Water Oxidation.

Introducing ferroelectric polarization has shown great potential to facilitate interfacial charge separation in photoelectrochemical (PEC) water splitting. However, unambiguous evidence of the actual influence of spontaneous ferroelectric polarization, as compared to heterojunction formation, on electron extraction and PEC water splitting is still lacking to date. Herein, core-shell BaTiO3/TiO2 nanostructures are designed as photoanodes based on paraelectric cubic and ferroelectric tetragonal phases BaTiO3 (BTO) perovskite. The cubic and tetragonal crystalline phases are stabilized using selected elaboration methods. Compared to the paraelectric cubic (c-BTO), the ferroelectric tetragonal (t-BTO) leads to a favorable ferroelectric polarization, enhancing directional charge separation and as a consequence to increased photocurrent up to a factor of 1.95. More interestingly, the charge separation efficiency can be tuned by applying positive or negative polarization, with the highest charge separation obtained for the positive one. When loading Ni(OH)2 as a cocatalyst on the t-BTO@TiO2 photoanode, the Ni(OH)2/TiO2/t-BTO exhibits a high performance and superior stability toward PEC water oxidation with a photocurrent almost 6.7 times that of the reference SiO2@TiO2. The proposed facilitation may open an avenue to engineer charge separation and transport for high-performance PEC water oxidation.

A simple and efficient process for the synthesis of 2D carbon nitrides and related materials.

We describe here a new process for the synthesis of very high quality 2D Covalent Organic Frameworks (COFs), such a C2N and CN carbon nitrides. This process relies on the use of a metallic surface as both a reagent and a support for the coupling of small halogenated building blocks. The conditions of the assembly reaction are chosen so as to leave the inorganic salts by-products on the surface, to further confine the assembly reaction on the surface and increase the quality of the 2D layers. We found that under these conditions, the process directly returns few layers material. The structure/quality of these materials is demonstrated by extensive cross-characterizations at different scales, combining optical microscopy, Scanning Electron Microscopy (SEM)/Transmission Electron Microscopy (TEM) and Energy Dispersive Spectroscopy (EDS). The availability of such very large, high-quality layers of these materials opens interesting perspectives, for example in photochemistry and electronics (intrinsic transport properties, high gap substrate for graphene, etc...).

On the microstructure and texture of intermetallics in Al/Mg/Al multi-layer composite fabricated by Accumulative Roll Bonding.

The microstructure and texture of the intermetallics in Al/Mg/Al multi-layer composite fabricated by Accumulative Roll Bonding (ARB) at 400 °C up to 6 cycles were investigated using Electron BackScatter Diffraction (EBSD) and Synchrotron X-ray Diffraction (SXRD). EBSD and SXRD analysis have shown that ARB processing leads to the formation of Al3Mg2 and Mg17Al12 intermetallics soon after the second ARB cycle with a global thickness of 12 (N = 2) to 22 µm (N = 6). The polycrystalline intermetallics plates growth was columnar and normal to the bonding interface. A constitutional liquefaction region was depicted ahead of the plates with an unusual rugged migration front. The Al3Mg2 and Mg17Al12 intermetallic compounds which formed after 2 ARB cycles have approximately the same average grain size (1.0 µm) at this cycle. After 4 ARB cycles, the grain refinement of Al3Mg2 is more than 4 times higher than in Mg17Al12. The average grain size of Al3Mg2 and Mg17Al12 reach 0.2 and 0.9 µm, respectively. After 6 cycles of ARB, the average grain size of both Al3Mg2 and Mg17Al12 increased to 1.5 µm and 2.8 µm, respectively. The dislocation density obeyed a ρAl3Mg2 > ρAZ31 > ρAl 1050 ∼ ρMg17Al12 hierarchy after N = 4 and 6 ARB cycles and the Al3Mg2 was shown to store more dislocations. Through the ARB processing, a usual strong basal (0002) texture was depicted in AZ31 layers and a weak rolling texture was shown in Al 1050 layers with a dominant Rotated Cube (001) 110 > component that vanished after upon increasing ARB cycles. The Al3Mg2 and Mg17Al12 intermetallics were characterized by a random texture.

Alkali magmatism on a carbonaceous chondrite planetesimal.

Recent isotopic and paleomagnetic data point to a possible connection between carbonaceous chondrites and differentiated planetary materials, suggesting the existence, perhaps ephemeral, of transitional objects with a layered structure whereby a metal-rich core is enclosed by a silicate mantle, which is itself overlain by a crust containing an outermost layer of primitive solar nebula materials. This idea has not received broad support, mostly because of a lack of samples in the meteoritic record that document incipient melting at the onset of planetary differentiation. Here, we report the discovery and the petrologic-isotopic characterization of UH154-11, a ferroan trachybasalt fragment enclosed in a Renazzo-type carbonaceous chondrite (CR). Its chemical and oxygen isotopic compositions are consistent with very-low-degree partial melting of a Vigarano-type carbonaceous chondrite (CV) from the oxidized subgroup at a depth where fluid-assisted metamorphism enhanced the Na content. Its microdoleritic texture indicates crystallization at an increasing cooling rate, such as would occur during magma ascent through a chondritic crust. This represents direct evidence of magmatic activity in a carbonaceous asteroid on the verge of differentiating and demonstrates that some primitive outer Solar System objects related to icy asteroids and comets underwent a phase of magmatic activity early in the Solar System. With its peculiar petrology, UH154-11 can be considered the long-sought first melt produced during partial differentiation of a carbonaceous chondritic planetary body, bridging a previously persistent gap in differentiation processes from icy cometary bodies to fully melted iron meteorites with isotopic affinities to carbonaceous chondrites.

Nanoparticles with high payloads of pipemidic acid, a poorly soluble crystalline drug: drug-initiated polymerization and self-assembly approach.

Nowadays, biodegradable polymers such as poly(lactic acid) (PLA), poly(D,L-lactic-co-glycolic acid) (PLGA) and poly(ε-caprolactone) (PCL) remain the most common biomaterials to produce drug-loaded nanoparticles (NPs). Pipemidic acid (PIP) is a poorly soluble antibiotic with a strong tendency to crystallize. PIP incorporation in PLA/PLGA NPs was challenging because of PIP crystals formation and burst release. As PIP had a poor affinity for the NPs, an alternative approach to encapsulation was used, consisting in coupling PIP to PCL. Thus, a PCL-PIP conjugate was successfully synthesized by an original drug-initiated polymerization in a single step without the need of catalyst. PCL-PIP was characterized by NMR, IR, SEC and mass spectrometry. PCL-PIP was used to prepare self-assembled NPs with PIP contents as high as 27% (w/w). The NPs were characterized by microscopy, DLS, NTA and TRPS. This study paves the way towards the production of NPs with high antibiotic payloads by drug-initiated polymerization. Further studies will deal with the synthesis of novel polymer-PIP conjugates with ester bonds between the drug and PCL. PIP can be considered as a model drug and the strategy developed here could be extended to other challenging antibiotics or anticancer drugs and employed to efficiently incorporate them in NPs.

Pulse energy dependence of refractive index change in lithium niobium silicate glass during femtosecond laser direct writing.

Femtosecond laser-induced refractive index changes in lithium niobium silicate glass were explored at high repetition rate (300 fs, 500 kHz) by polarized light microscopy, full-wave retardation plate, quantitative birefringence microscopy, and digital holographic microscopy. We found three regimes on energy increase. The first one corresponds to isotropic negative refractive index change (for pulse energy ranging 0.4-0.8 µJ/pulse, 0.6 NA, 5µm/s, 650µm focusing depth in the glass). The second one (0.8-1.2 µJ/pulse) corresponds to birefringence with well-defined slow axis orientation. The third one (above 1.2 µJ/pulse) is related to birefringence direction fluctuation. Interestingly, these regimes are consistent with crystallization ones. In addition, an asymmetric orientational writing effect has been detected on birefringence. These topics extend the possibility of controlling refractive index change in multi-component glasses.

Nd3+-doped transparent tellurite ceramics bulk lasers.

We report on the laser emission of the polycrystalline ceramic obtained from the full and congruent crystallization of the parent glass 1Nd3+:75TeO2-12.5Bi2O3-12.5Nb2O5 composition. In particular, the current work underlines the importance of carefully controlling the heat treatment in order to solely crystallize the Bi0.8Nb0.8Te2.4O8 cubic phase and consequently avoid the formation of the BiNbTe2O8 orthorhombic phase that would be detrimental for optical purpose. The structure, microstructure and photoluminescence properties of the resulting transparent tellurite ceramics are characterized. The continuous-wave and gain-switching laser performances reveal that the emission remains perfectly single transversal mode in the range of pump powers explored. The maximum output power achieved was ~28.5 mW, for a pump power threshold of ~67 mW, and with associated efficiency and slope efficiency of ~22.5% and ~50%, respectively. These data definitely stand among the best results obtained so far for bulk laser tellurite materials and thus demonstrate the potential of such polycrystalline transparent ceramics as optically active materials. Finally, the laser emission characteristics in pulsed regime, at low and high repetition rates, are also provided: more than 6.5 W of peak power at a repetition rate of 728 kHz can be obtained.

ß-Cyclodextrin-Mediated Enantioselective Photochemical Electrocyclization of 1,3-Dihydro-2H-azepin-2-one.

The photochemical electrocyclization reaction of the title compound in the presence of ß-cyclodextrin was examined in different conditions. No enantioselectivity was observed in solution, but solid-state reactions of a 1:1 complex as a suspension or a thin film, followed by reduction, provided (1R,5R)-2-azabicyclo[3.2.0]heptan-3-one in isolated yields up to 79% and with ee values up to 45%.

Conformational Effects through Hydrogen Bonding in a Constrained γ-Peptide Template: From Intraresidue Seven-Membered Rings to a Gel-Forming Sheet Structure.

A series of three short oligomers (di-, tri-, and tetramers) of cis-2-(aminomethyl)cyclobutane carboxylic acid, a γ-amino acid featuring a cyclobutane ring constraint, were prepared, and their conformational behavior was examined spectroscopically and by molecular modeling. In dilute solutions, these peptides showed a number of low-energy conformers, including ribbonlike structures pleated around a rarely observed series of intramolecular seven-membered hydrogen bonds. In more concentrated solutions, these interactions defer to an organized supramolecular assembly, leading to thermoreversible organogel formation notably for the tripeptide, which produced fibrillar xerogels. In the solid state, the dipeptide adopted a fully extended conformation featuring a one-dimensional network of intermolecularly H-bonded molecules stacked in an antiparallel sheet alignment. This work provides unique insight into the interplay between inter- and intramolecular H-bonded conformer topologies for the same peptide template.

Form birefringence induced in multicomponent glass by femtosecond laser direct writing.

We demonstrate a new kind of form birefringence in lithium niobium silicate glass induced by femtosecond laser direct writing. By combining electron backscatter diffraction and transmission electron microscopy, we reveal a self-assembled nanostructure consisting of periodic phase change: nonlinear optical nanocrystals embedded in a network of "walls" in a vitreous phase. These "walls" are aligned perpendicular to the laser polarization direction. This self-organized nanostructure may successfully explain the origin of the laser-induced birefringence in this multicomponent glass quite differently from pure silica. These findings highlight a spectacular modification of glass, and enable construction of a high contrast three-dimensional refractive index and birefringent structures at the micrometer scale in multicomponent glasses.

Giant Amplification of Photoswitching by a Few Photons in Fluorescent Photochromic Organic Nanoparticles.

Controlling or switching the optical signal from a large collection of molecules with the minimum of photons represents an extremely attractive concept. Promising fundamental and practical applications may be derived from such a photon-saving principle. With this aim in mind, we have prepared fluorescent photochromic organic nanoparticles (NPs), showing bright red emission, complete ON-OFF contrast with full reversibility, and excellent fatigue resistance. Most interestingly, upon successive UV and visible light irradiation, the NPs exhibit a complete fluorescence quenching and recovery at very low photochromic conversion levels (<5 %), leading to the fluorescence photoswitching of 420±20 molecules for only one converted photochromic molecule. This "giant amplification of fluorescence photoswitching" originates from efficient intermolecular energy-transfer processes within the NPs.

Copper Refinement from Anode to Cathode and then to Wire Rod: Effects of Impurities on Recrystallization Kinetics and Wire Ductility.

In this paper, the traceability of copper from the anode to the cathode and then the wire rod has been studied in terms of impurity content, microstructure, texture, recrystallization kinetics, and ductility. These characterizations were obtained based on secondary ion mass spectrometry, differential scanning calorimetry (DSC), X-ray diffraction, HV hardness, and electron backscattered diffraction. It is shown that the recrystallization was delayed by the total amount of impurities. From tensile tests performed on cold drawn and subsequently annealed wires for a given time, a simplified model has been developed to link tensile elongation to the chemical composition. This model allowed quantification of the contribution of some additional elements, present in small quantity, on the recrystallization kinetics. The proposed model adjusted for the cold-drawn wires was also validated on both the cathode and wire rod used for the study of traceability.

Towards bottom-up nanopatterning of Prussian blue analogues.

Ordered nanoperforated TiO2 monolayers fabricated through sol-gel chemistry were used to grow isolated particles of Prussian blue analogues (PBA). The elaboration of the TiO2/CoFe PBA nanocomposites involves five steps. The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), infrared spectroscopy and X-ray photoelectron spectroscopy (XPS) all along the synthesis process. Selected physico-chemical parameters have been varied in order to determine the key steps of the synthesis process and to optimize it. This study is an important step towards the full control of the fabrication process.

A nickel dimethyl glyoximato complex to form nickel based nanoparticles for electrocatalytic H2 production.

We report on the electrochemical alteration of a nickel(II) bis-glyoximato complex into nickel-based nanoparticles at a glassy carbon electrode under acid reducing conditions. These particles show electrocatalytic activity towards hydrogen production at +410 mV compared to the bare glassy carbon electrode. Mechanistic insights are discussed based on DFT calculations.

One-step photoinscription of asymmetrically oriented fresnoite-type crystals in glass by ultrafast laser.

Oriented fresnoite-type crystals (Sr(2)TiSi(2)O(8)) were photoinduced directly in bulk silica-based glass by femtosecond laser irradiation at high repetition rate (typ. 300 kHz). Unlike related results obtained from other researchers, asymmetrical polar-axis orientation of those nonlinear crystals in transverse direction of the cross section has been demonstrated by electron backscattered diffraction and micro-second-harmonic generation (SHG). The nonlinear optical property of laser lines has been further characterized by SHG measurement. We found that the preferential directions of the polar axis were in the laser motion direction with a small dispersion in part of the heated volume. The other part of the crystallized volume shows an axis perpendicular to the writing direction. The mechanism of asymmetric orientation of femtosecond-laser-induced crystallization also is discussed.

Cobalt-based particles formed upon electrocatalytic hydrogen production by a cobalt pyridine oxime complex.

An open-coordination-sphere cobalt(III) oximato-based complex was designed as a putative catalyst for the hydrogen evolution reaction (HER). Electrochemical alteration in the presence of acid occurs, leading to the formation of cobalt-based particles that act as an efficient catalyst for HER at pH 7. The exact chemical nature of these particles is yet to be determined. This study thus raises interesting issues regarding the fate of molecular-based complexes designed for the HER, and points to the challenging task of identifying the real catalytic species. Moreover, understanding and rationalizing the alteration pathways can be seen as a new route to reach catalytic particulates.

Synergy in photomagnetic/ferromagnetic sub-50 nm core-multishell nanoparticles.

Based on nickel hexacyanidochromate and cobalt hexacyanidoferrate Prussian blue analogues, two series of photomagnetic/ferromagnetic sub-50 nm core multishell coordination nanoparticles have been synthesized in a surfactant-free one-pot multistep procedure with good control over the dispersity (10% standard deviation) and good agreement with the targeted size at each step. The composition and the valence state of each shell have been probed by different techniques that have revealed the predominance of Co(II)-NC-Fe(III) pairs in a series synthesized without alkali while Co(III)-NC-Fe(II) photoswitchable pairs have been successfully obtained in the photoactive coordination nanoparticles by control of Cs(+) insertion. When compared, the photoinduced behavior of the latter compound is in good agreement with that of the model one. Exchange coupling favors a uniform reversal of the magnetization of the heterostructured nanoparticles, with a large magnetization brought by a soft ferromagnetic shell and a large coercivity due to a harder photomagnetic shell. Moreover, a persistent increase of the photoinduced magnetization is observed for the first time up to the ordering temperature (60 K) of the ferromagnetic component because of a unique synergy.

In situ electron backscatter diffraction investigation of recrystallization in a copper wire.

The microstructural evolution of a cold drawn copper wire (reduction area of 38%) during primary recrystallization and grain growth was observed in situ by electron backscatter diffraction. Two thermal treatments were performed, and successive scans were acquired on samples undergoing heating from ambient temperature to a steady state of 200°C or 215°C. During a third in situ annealing, the temperature was continuously increased up to 600°C. Nuclei were observed to grow at the expense of the deformed microstructure. This growth was enhanced by the high stored energy difference between the nuclei and their neighbors (driving energy in recrystallization) and by the presence of high-angle grain boundaries of high mobility. In the early stages of growth, the nuclei twin and the newly created orientations continue to grow to the detriment of the strained copper. At high temperatures, the disappearance of some twins was evidenced by the migration of the incoherent twin boundaries. Thermal grooving of grain boundaries is observed at these high temperatures and affects the high mobile boundaries but tends to preserve the twin boundaries of lower energy. Thus, grooving may contribute to the twin vanishing.

Original ß,γ-diamino acid as an inducer of a γ-turn mimic in short peptides.

Original αγα tripeptides containing one ß,γ-diamino acid have been synthesized and their conformation determined by extensive NMR and molecular dynamic studies. These studies revealed the presence of a C(9) hydrogen bonded turn around the ß,γ-diamino acid which was stabilized by bulky side chains of the preceding residue. This turn can be considered as a mimic of the well-known γ-turn.

Tuning the magnetic anisotropy in coordination nanoparticles: random distribution versus core-shell architecture.

Core-shell magnetic coordination nanoparticles made of a soft core and a hard magnetic shell, containing anisotropic Co(II) ions, display a dramatic increase in their average blocking temperature with a coercive field value 25 times larger than that of the soft core, due to a large enhancement of the magnetic anisotropy.