Precursor Design Strategies for the Low-Temperature Synthesis of Functional Oxides: It's All in the Chemistry

Solution-based (multi)metal oxide synthesis has been carried out employing a large diversity of precursor routes. The selection of an appropriate synthesis strategy is frequently dictated by the resulting material properties, although this choice should also be based on green chemistry principles, atom economy considerations and energy efficiency. In order to limit the required energy budget to convert the chemical precursor to the target oxide material, various approaches were recently reported. This Review summarizes some frequently encountered low-temperature routes, critically assessing their application window and advantages. More specifically, auto-combustion synthesis, UV-assisted decomposition routes, sol–gel network adjustments and precursor complex design concepts are discussed. It is expected that this toolbox of low-temperature strategies may assist further progress in the field, stimulating novel applications, such as flexible electronics or organic–oxide hybrid materials, which are very sensitive to the temperature requirements.     

Near-Infrared BODIPY-Acridine Dyads Acting as Heavy-Atom-Free Dual-Functioning Photosensitizers

Boron dipyrromethene (BODIPY) dyes represent a particular class within the broad array of potential photosensitizers. Their highly fluorescent nature opens the door for theragnostic applications, combining imaging and therapy using a single, easily synthesized chromophore. However, near-infrared absorption is strongly desired for photodynamic therapy to enhance tissue penetration. Furthermore, singlet oxygen should preferentially be generated without the incorporation of heavy atoms, as these often require additional synthetic efforts and/or afford dark cytotoxicity. Solutions for both problems are known, but have never been successfully combined in one simple BODIPY material. Here, we present a series of compact BODIPY-acridine dyads, active in the phototherapeutic window and showing balanced brightness and phototoxic power. Although the donor–acceptor design was envisioned to introduce a charge transfer state to assist in intersystem crossing, quantum-chemical calculations refute this. Further photophysical investigations suggest the presence of exciplex states and their involvement in singlet oxygen formation.     

Synthesis,structure and solid state NMR analysis of a new templated titanium(III/IV) fluorophosphate

The title compound MIL-131 (MIL stands for Material from Institut Lavoisier) was prepared hydrothermally (4 days, 473 K, autogenous pressure) in the presence of an organic base (N((CH₂)₂NH₂)₃). The structure of MIL-131 or Ti^IIITi^IV(OH)F₄(HPO₄)·(PO₄)·(N((CH₂)₂NH₃)₃) has been determined ab initio from X-Ray synchrotron powder diffraction data using simulated annealing methods and was refined in the triclinic space group P-1 (no. 2). MIL-131 exhibits a one-dimensional structure built up from inorganic chains of corner sharing TiO₅(OH) titanium(III) octahedra and PO₄ and HPO₄ phosphate tetrahedra, related to TiO₂F₄ titanium octahedra. Protonated triamine cations are located between the inorganic motifs, and interact strongly with the mineral network through hydrogen bondings both with terminal fluorine atoms and hydroxo or oxo groups. Multinuclear solid state NMR has allowed a clear attribution of the protons, fluoride, and phosphate groups environment within the framework of MIL-131. The large values of chemical shift anisotropy together with the absence of any ¹³C NMR response confirmed the presence of paramagnetic titanium(III) species deduced from the crystal structure. Finally, 2D MAS ¹H-³¹P CP-HETCOR NMR correlation experiment gives some insight on the nature of the intra-framework hydrogen bonding.Crystal data for MIL-131: a = 14.109(1) Å, b = 8.462(3) Å, c = 7.179(1) Å, α = 93.772(1)°, β = 96.566(2)°, γ = 98.004(1)°, V = 840.36(2) ų, z = 2.     

What is double parton scattering?

Processes such as double Drell–Yan and same-sign WW   production have contributions from double parton scattering, which are not well-defined because of a δ⁽²⁾(_z⊥=0)${\delta }^{(2)}({\mathbf{z}}_{\perp }=0)$ singularity that is generated by QCD evolution. We study the single and double parton contributions to these processes, and show how to handle the singularity using factorization and operator renormalization. We compute the QCD evolution of double parton distribution functions (PDFs) due to mixing with single PDFs. The modified evolution of dPDFs at _z⊥=0${\mathbf{z}}_{\perp }=0$, including generalized dPDFs for the non-forward case, is given in Appendix A. We include a brief discussion of the experimental interpretation of dPDFs and how they can probe flavor, spin and color correlations of partons in hadrons.     

Dynamic covalent assembly of stimuli responsive vesicle gels

We describe the reversible formation of stimuli-responsive vesicle gels from polymerised dynamic covalent surfactants, by simple mixing of soluble surfactant precursors in water under ambient conditions.     

Newton polygons and curve gonalities

We give a combinatorial upper bound for the gonality of a curve that is defined by a bivariate Laurent polynomial with given Newton polygon. We conjecture that this bound is generically attained, and provide proofs in a considerable number of special cases. One proof technique uses recent work of M. Baker on linear systems on graphs, by means of which we reduce our conjecture to a purely combinatorial statement.     

Conformational studies of cyclopropylmethyl isothiocyanate from temperature-dependent FT-IR spectra of rare gas solutions and ab initio calculations

Variable temperature (-55 to -150 degrees C) studies of the infrared spectra (3200-100 cm(-1)) of cyclopropylmethyl isothiocyanate, c-C(3)H(5)CH(2)NCS, dissolved in liquefied rare gases (Xe and Kr), have been carried out. The infrared spectra of the gas and solid, as well as the Raman spectrum of the liquid, have also been recorded from 3200 to 100 cm(-1). By analyzing six conformer pairs in xenon solutions, a standard enthalpy difference of 228 +/- 23 cm(-1) (2.73 +/- 0.27 kJ.mol(-1)) was obtained with the gauche-cis (the first designation indicates the orientation of the CNCS group with respect to the three-membered ring, the second designation indicates the relative orientation of the NCS group with respect to the bridging C-C bond) rotamer the more stable form, and it is also the only form present in polycrystalline solid. Given statistical weights of 2:1 for the gauche-cis and cis-trans forms (the only stable conformers predicted); the abundance of cis-trans conformer present at ambient temperature is 14 +/- 2%. The potential surface describing the conformational interchange has been analyzed, and the corresponding two-dimensional Fourier coefficients were obtained. From MP2 ab initio calculations utilizing various basis sets with diffuse functions, the gauche-cis conformer is predicted to be more stable by 159-302 cm(-1), which is consistent with the experimental results. However, without diffuse functions, the conformational energy differences are nearly zero even with large basis sets. For calculations with density functional theory by the B3LYP method, basis sets without diffuse functions also predict smaller energy differences between the conformers, although not nearly as small as the MP2 results. A complete vibrational assignment for the gauche-cis conformer is proposed, and several fundamentals for the cis-trans conformer have been identified. The structural parameters, dipole moments, conformational stability, vibrational frequencies, and infrared and Raman intensities have been predicted from ab initio calculations and compared to the experimental values when applicable; the r(0) structural parameters are also estimated. The energies for the linear CNCS moiety were calculated. These experimental and theoretical results are compared to the corresponding quantities of some similar molecules.     

Intermolecular association of tetrahydrofuran-2-carboxylic acid in solution: a vibrational circular dichroism study

Carboxylic acids are known for their strong intermolecular associations. With chiral carboxylic acids, this behavior can be studied using vibrational circular dichroism (VCD). Tetrahydrofuran-2-carboxylic acid 1, a chiral building block for beta-lactam antibiotics, is studied by emphasizing the effect of the dimerization. Experimental results indicate that for solutions of 1 in CDCl3 and CS2, a complex equilibrium exists between the monomers and dimers. B3LYP/aug-cc-pVTZ calculations are performed on both monomer and dimer structures. To simulate IR and VCD spectra, populations for monomer and dimers were approximated using a semiquantitative model. A good agreement between experimental and simulated spectra is obtained by taking into account both the monomeric and the dimeric structures, weighted using the experimentally determined populations.     

A micromachined interface for airborne sample-to-liquid transfer and its application in a biosensor system

A novel micromachined interface for airborne sample-to-liquid adsorption and droplet-to-liquid transfer was designed and fabricated. It enables a robust sheet liquid flow serving as an adsorption site. The interface was characterised for flow and pressure properties and tested successfully for the transfer/adsorption of different samples. A qualitative theoretical model of the device characteristics is presented. We also used the interface to introduce a novel method and system for fast detection of dust- and vapour-based narcotics and explosives traces. The microfluidic vapour-to-liquid adsorption interface was coupled to a set of downstream QCM sensors. The system was tested successfully, with 50 ng cocaine samples rendering 15 Hz frequency shifts and with 100 ng heroine samples rendering 50 Hz frequency shifts. Gravitation invariance of the open liquid interface was demonstrated successfully, with the interface mounted upside down as well as vertically. The detection time was reduced to half of the time needed in previous systems. Machine size, weight and cost were reduced.     

Sheared force networks: anisotropies, yielding, and geometry

A scenario for the yielding of granular matter is presented by considering the ensemble of force networks for a given contact network and applied shear stress tau. As tau is increased, the probability distribution of contact forces becomes highly anisotropic, the difference between average contact forces along minor and major axes grows, and the allowed networks span a shrinking subspace of all force networks. Eventually, contacts start to break, and at the maximal shear stress the packing becomes effectively isostatic. The size of the allowed subspace exhibits simple scaling properties, which lead to a prediction for the yield stress for packings of an arbitrary contact number.