Synthesis and characterization of octa- and hexanuclear polyoxomolybdate wheels: role of the inorganic template and of the counterion

Eight new compounds based on [O3PCH2PO3]4- ligands and {MoV2O4} dimeric units have been synthesized and structurally characterized. Octanuclear wheels encapsulating various guests have been isolated with different counterions. With NH4+, a single wheel was obtained, as expected, with the planar CO32- guest, (NH4)12[(MoV2O4)4(O3PCH2PO3)4(CO3)2].24H2O (1a), while with the pyramidal SO32- guest, only the syn isomer (NH4)12[(MoV2O4)4(O3PCH2PO3)4(SO3)2].26H2O (2a) was characterized. The corresponding anti isomer was obtained with Na+ as counterions, Na12[(MoV2O4)4(O3PCH2PO3)4(SO3)2]39H2O (2b), and with mixed Na+ and NH4(+) counterions, Na+(NH4)11[(MoV2O4)4(O3PCH2PO3)4(SO3)2].13H2O (2d). With [O3PCH2PO3]4- extra ligands, the octanuclear wheel Li12(NH4)2[(MoV2O4)4(O3PCH2PO3)4(HO3PCH2PO3)2].31H2O (4a) was isolated with Li+ and NH4+ counterions and Li14[(MoV2O4)4(O3PCH2PO3)4(HO3PCH2PO3)2].34H2O (4c) as a pure Li+ salt. A new rectangular anion, formed by connecting two MoV dimers and two MoVI octahedra via methylenediphosphonato ligands with NH4+ as counterions, (NH4)10[(MoV2O4)2(MoVIO3)2(O3PCH2PO3)2(HO3PCH2PO3)2].15H2)O (3a), and Li9(NH4)2Cl[(MoV2O4)2(MoVIO3)2(O3PCH2PO3)2]. 22H2O (3d) as a mixed NH4+ and Li+ salt have also been synthesized. The structural characterization of the compounds, combined with a study of their behavior in solution, investigated by 31P NMR, has allowed a discussion on the influence of the counterions on the structure of the anions and their stability. Density functional theory calculations carried out on both isomers of the [(MoV2O4)4(O3PCH2PO3)4(SO3)2]12- anion (2), either assumed isolated or embedded in a continuum solvent model, suggest that the anti form is favored by approximately 2 kcal mol(-1). Explicit insertion of two solvated counterions in the molecular cavity reverses this energy difference and reduces it to less than 1 kcal mol(-1), therefore accounting for the observed structural versatility.     

High-power laser with Nd:YAG single-crystal fiber grown by the micro-pulling-down technique

We present optical characterization and laser results achieved with single-crystal fibers directly grown by the micro-pulling-down technique. We investigate the spectroscopic and optical quality of the fiber, and we present the first laser results. We achieved a cw laser power of 10 W at 1064 nm for an incident pump power of 60 W at 808 nm and 360 kW peak power for 12 ns pulses at 1 kHz in the Q-switched regime. It is, to the best of our knowledge, the highest laser power ever achieved with directly grown single-crystal fibers.     

Light‐Responsive Block Copolymers

Stimuli‐responsive polymers are the subject of intense research because they are able to show responses to various environmental changes. Among those stimuli, light has attracted much attention since it can be localized in time and space and it can also be triggered from outside of the system. In this paper, we review light‐responsive block copolymers (LRBCs) that combine characteristic features of block copolymers, e.g., self‐assembly behavior, and light‐responsive systems. The different photo‐responsive moieties that have been incorporated so far in block copolymers as well as the proposed applications are discussed.

     

On a Lagrangian formulation of gravitoelectromagnetism

We examine a Lagrangian formulation of gravity based on an approach analogous to electromagnetism, called Gravitoelectromagnetism (GEM). The gravitational analogue of the electromagnetic field tensor is a three-index tensor, \({\mathcal {F}_{\mu\nu\lambda}}\), defined in terms of a two-index gravitoelectromagnetic potential, \({\mathcal {A}_{\mu\nu}}\). The energy-momentum tensor is derived and is symmetric. We construct a Lagrangian which allows us to describe interactions between fermions, photons and gravitons. We calculate transition amplitudes of various processes involving gravitons: gravitational Møller scattering, gravitational Compton scattering, and the graviton photoproduction.     

Validation and Limits of Finite Inflatable Beam Elements

Although nowadays inflatable tubular beams are often used in the field of civil engineering, by now there are only few publications dealing with finite deformation inflatable beam elements, see e.g. [1], [2] and [3]. All formulations of inflatable beams have several assumptions in common, as constant cross sections throughout the deformation, a constant internal gas pressure and the negligence of circumferential stresses. These assumptions have to be validated either by experiments or numerical analysis. In the current contribution beam–like structures are investigated using a finite element shell or membrane formulation and featuring a volume dependent gas loading, see e.g. [5] and [4]. In general the formulation substitutes the internal gas pressure by an energetically equivalent volume dependent loading and thus enables to check for potential gas pressure changes during the deformation process of the inflated beam as a consequence of volume changes. Further local deformations as occurring in the vicinity of supports or almost single loads can be considered. In this paper the focus will be only on the initial assumption of the beam theory that the biaxial stress state is neglected. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Shadowgraph, Schlieren and interferometry in a 2D cavitating channel flow

Cavitation plays an important role in fuel atomization mechanisms, but the physics of cavitation and its impact on spray formation and injector efficiency are not well documented yet. Experimental investigations are required to support the development and the validation of numerical models and the design of tomorrow??s injectors, in the context of pollutant and fuel consumption reduction. The complexity of modern injectors and the extreme conditions of injection do not facilitate experimental investigations. In this paper, experiments are conducted in a simplified geometry. The model nozzle consists of a transparent 2D micro-channel supplied with a test oil (ISO 4113). Three different optical techniques are proposed to investigate the channel flow, with the pressure drop between upstream and downstream chambers as a parameter. A shadowgraph-like imaging technique allows the observation of cavitation inception and vapor cavities development throughout the channel. The technique also reveals the presence of density gradients (pressure or temperature) in the channel flow. However, this additional information is balanced by difficulties in image interpretation, which are discussed in the paper. In addition, a combination of Schlieren technique and interferometric imaging is used to measure the density fields inside the channel. The three techniques results are carefully analyzed and confronted. These results reveal a wealth of information on the flow, with pressure waves generated by bubble collapses, turbulence in the wake of vapor cavities and bubble survival in flow regions of high pressure. Our results also show that cavitation inception is located in the shear layers between the recirculation zones and the main flow, relatively far from the inlet corner, where the pressure is minimum in average. To explain this behavior, we propose a scenario of cavitation inception based on the occurrence and the growing of instabilities in the shear layers.     

Replica Bounds by Combinatorial Interpolation for Diluted Spin Systems

In two papers Franz et al. proved bounds for the free energy of diluted random constraints satisfaction problems, for a Poisson degree distribution (Franz and Leone in J Stat Phys 111(3–4):535–564, 2003) and a general distribution (Franz et al. in J Phys A 36(43), 10967, 2003). Panchenko and Talagrand (Probab Theo Relat Fields 130(3):319–336, 2004) simplified the proof and generalized the result of Franz and Leone (J Stat Phys 111(3–4):535–564, 2003) for the Poisson case. We provide a new proof for the general degree distribution case and as a corollary, we obtain new bounds for the size of the largest independent set (also known as hard core model) in a large random regular graph. Our proof uses a combinatorial interpolation based on biased random walks (Salez in Combin Probab Comput 25(03):436–447, 2016) and allows to bypass the arguments in Franz et al. (J Phys A 36(43):10967, 2003) based on the study of the Sherrington–Kirkpatrick (SK) model.     

Fermi field and Dirac oscillator in a Som–Raychaudhuri space-time

We investigate the relativistic dynamics of a Dirac field in the Som–Raychaudhuri space-time, which is described by a Gödel-type metric and a stationary cylindrical symmetric solution of Einstein field equations for a charged dust distribution in rigid rotation. In order to analyze the effect of various physical parameters of this space-time, we solve the Dirac equation in the Som–Raychaudhuri space-time and obtain the energy levels and eigenfunctions of the Dirac operator by using the Nikiforov–Uvarov method. We also examine the behaviour of the Dirac oscillator in the Som–Raychaudhuri space-time, in particular, the effect of its frequency and the vorticity parameter.     

Crystal Structure of the Radical-Cation Salt (<Emphasis Type="Italic">o</Emphasis>-Me<Subscript>2</Subscript>TTF)I<Subscript>3</Subscript> with Close Intermolecular Sulfur Contacts

Abstract  The synthesis and crystal structure of the organic radical-cation salt (o-Me₂TTF)I₃ is described. The salt crystallizes in the monoclinic space group P2 ₁ /n with a = 10.927(2) ?, b = 11.904(2) ?, c = 12.660(2) ?, β = 115.174(5)°. The bond length of the central C=C bond in o-Me₂TTF is 1.401(1) ?, indicating an approximate oxidation state of +1 for the o-Me₂TTF radical cation. Graphical Abstract  The X-ray crystallographic structure of the radical cation salt (o-Me₂TTF)I₃ has been determined and its structural properties and synthetic preparation are discussed.      

Synthesis and characterization of a biphenyl perfluorocyclobutyl (BP‐PFCB) polyethylene glycol (PEG) blend compatibilizer

Polyethylene glycol (PEG) end‐capped trifluorovinyl ether (TFVE) telechelomer was synthesized in one step via esterification of 4‐(trifluorovinyloxy) benzoic acid. The new telechelomer was characterized by attenuated total reflectance Fourier transform infrared (ATR‐FTIR), elemental analysis, and by ¹⁹F and ¹H nuclear magnetic resonance (NMR) spectroscopy. The telechelomer and 4,4′‐bis(4‐trifluorovinyloxy)biphenyl (BPVE) were thermally copolymerized via step‐growth [2 + 2] cycloaddition at 160°C. The polymerization afforded PEG enchained biphenyl perfluorocyclobutyl (BP‐PFCB) copolymers that are solution processable and film forming. These copolymers were characterized by ATR‐FTIR, ¹⁹F NMR, and ¹H NMR. Gel permeation chromatography (GPC) gave number‐average molecular weight (M_n) ranging 11,000 to 12,000. Compatibilization of PEG and a commercial polymer BP‐PFCB was achieved utilizing the new PEG BP‐PFCB copolymer, 3‐co2‐4 . It was found that 5 wt% of 3 ‐ co2 ‐ 4 was ideal to reduce interfacial tension by scanning electron microscope (SEM). In addition, phase homogeneity was studied by differential scanning calorimetry (DSC). Copyright © 2016 John Wiley & Sons, Ltd.