Infrared (810 nm) low-level laser therapy in rat achilles tendinitis: a consistent alternative to drugs

Nonsteroidal anti-inflammatory drugs (NSAIDs) are widely used and can reduce musculoskeletal pain in spite of the cost of adverse reactions like gastrointestinal ulcers or cardiovascular events. The current study investigates if a safer treatment such as low-level laser therapy (LLLT) could reduce tendinitis inflammation, and whether a possible pathway could be through inhibition of either of the two-cyclooxygenase (COX) isoforms in inflammation. Wistar rats (six animals per group) were injected with saline (control) or collagenase in their Achilles tendons. Then, we treated them with three different doses of IR LLLT (810 nm; 100 mW; 10 s, 30 s and 60 s; 3.57 W cm(-2); 1 J, 3 J, 6 J) at the sites of the injections, or intramuscular diclofenac, a nonselective COX inhibitor/NSAID. We found that LLLT dose of 3 J significantly reduced inflammation through less COX-2-derived gene expression and PGE(2) production, and less edema formation compared to nonirradiated controls. Diclofenac controls exhibited significantly lower PGE(2) cytokine levels at 6 h than collagenase control, but COX isoform 1-derived gene expression and cytokine PGE(2) levels were not affected by treatments. As LLLT seems to act on inflammation through a selective inhibition of the COX-2 isoform in collagenase-induced tendinitis, LLLT may have potential to become a new and safer nondrug alternative to coxibs.     

Bismuth in Dynamic Covalent Chemistry: Access to a Bowl-Type Macrocycle and a Barrel-Type Heptanuclear Complex Cation

Dynamic covalent chemistry (DCvC) is a powerful and widely applied tool in modern synthetic chemistry, which is based on the reversible cleavage and formation of covalent bonds. One of the inherent strengths of this approach is the perspective to reversibly generate in an operationally simple approach novel structural motifs that are difficult or impossible to access with more traditional methods and require multiple bond cleaving and bond forming steps. To date, these fundamentally important synthetic and conceptual challenges in the context of DCvC have predominantly been tackled by exploiting compounds of lighter p-block elements, even though heavier p-block elements show low bond dissociation energies and appear to be ideally suited for this approach. Here we show that a dinuclear organometallic bismuth compound, containing BiMe₂ groups that are connected by a thioxanthene linker, readily undergoes selective and reversible cleavage of its Bi−C bonds upon exposure to external stimuli. The exploitation of DCvC in the field of organometallic heavy p-block chemistry grants access to unprecedented macrocyclic and barrel-type oligonuclear compounds.     

LiMn3(SeO3)2(HSeO3)6

The title compound, lithium trimanganese bis­[trioxo­selenate(IV)] hexa­kis[hydrogentrioxoselenate(IV)], is built up from a vertex‐sharing network of distorted Mn^IIIO₆ octa­hedra, SeO₃ and HSeO₃ pyramids and unusual Li(OH)₆ octa­hedra, resulting in a dense three‐dimensional structure. Mn, Li and one Se atom have site symmetries of , , and 3, respectively. An O—H⋯O hydrogen bond helps to establish the crystal packing.     

Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields as well as excellent enantioselectivities and diastereoselectivities. The high value of the aza‐Piancatelli rearrangement was demonstrated by the synthesis of a cyclopentane‐based hNK1 antagonist analogue.     

Photon energy dependence of fragmentation of small argon clusters

Photofragmentation of small argon clusters with size below ten atoms is reported. In this size range significant modifications from the electronic properties and geometry take place. When tuning the photon energy through the argon 2p edge, the fragmentation pattern is changed. Specifically, cation dimer production is enhanced at the 2p(32)-->4s resonance, while above the 2p edge almost complete atomization is observed. In both cases, the widths of the peaks in the mass spectra indicate that a large amount of kinetic energy is imparted to the fragment due to the formation of multiply charged clusters. A model based on "Coulomb explosion"-charge separation, simply resulting in a complete atomization of the cluster with no dependence on the photon energy-is insufficient to explain the observed photofragmentation of small clusters.     

Oriented crosslinked polyethylene pipes by a novel extrusion method

Crosslinking and stretching (2.5 times along the circumferential direction) of the molten polymer during extrusion produced pipes with dominantly circumferential orientation and a lower degree of axial chain orientation. Differential scanning calorimetry (crystallinity and crystal thickness), density measurements (crystallinity), X-ray diffraction (c-axis orientation), infrared dichroism measurements (crystalline and amorphous chain orientation) and contraction measurements (molecular draw ratio) assessed the microstructure of the pipe material. The mechanical properties of the oriented material were assessed by uniaxial tensile tests. The orientation was biaxial with the main orientation in the circumferential direction and a lesser orientation in the axial direction. The maximum degree of circumferential orientation was obtained at the inner wall of the pipe. The lower degree of crosslinking of the core material allowed slippage of chains during the stretching of the molten polymer and it is suggested that this is the cause of the lower degree of orientation of the core material. The oriented pipe material exhibited a 5-10% higher degree of crystallinity and higher crystal thickness than conventionally crosslinked material. The tensile modulus and the tensile strength of the oriented, cross-linked material was greater along the axial direction than along the circumferential direction. The circumferential and axial moduli for the oriented, crosslinked pipe were greater than the corresponding moduli of the non-oriented cross-linked pipe material. Another pipe based on crosslinked PE that were first circumferentially stretched 2.5 times and later axially stretched 10 times (in the molten state) showed, despite the fact that it exhibited pronounced axial orientation almost a balanced tensile modulus (4.3±0.2 GPa) in the axial-circumferential plane. Atomistic modelling showed that the orientational dependence of the density of the amorphous phase is small.     

The Impact of Retinal Configuration on the Protein–Chromophore Interactions in Bistable Jumping Spider Rhodopsin-1

Bistable rhodopsins have two stable forms that can be interconverted by light. Due to their ability to act as photoswitches, these proteins are considered as ideal candidates for applications such as optogenetics. In this work, we analyze a recently crystalized bistable rhodopsin, namely the jumping spider rhodopsin-1 (JSR1). This rhodopsin exhibits identical absorption maxima for the parent and the photoproduct form, which impedes its broad application. We performed hybrid QM/MM simulations to study three isomers of the retinal chromophore: the 9-cis, 11-cis and all-trans configurations. The main aim was to gain insight into the specific interactions of each isomer and their impact on the absorption maximum in JSR1. The absorption spectra were computed using sampled snapshots from QM/MM molecular dynamics trajectories and compared to their experimental counterparts. The chromophore–protein interactions were analyzed by visualizing the electrostatic potential of the protein and projecting it onto the chromophore. It was found that the distance between a nearby tyrosine (Y126) residue plays a larger role in the predicted absorption maximum than the primary counterion (E194). Geometric differences between the isomers were also noted, including a structural change in the polyene chain of the chromophore, as well as changes in the nearby hydrogen bonding network.     

Impact of Surface Defects on LaNiO3 Perovskite Electrocatalysts for the Oxygen Evolution Reaction

Perovskite oxides are regarded as promising electrocatalysts for water splitting due to their cost-effectiveness, high efficiency and durability in the oxygen evolution reaction (OER). Despite these advantages, a fundamental understanding of how critical structural parameters of perovskite electrocatalysts influence their activity and stability is lacking. Here, we investigate the impact of structural defects on OER performance for representative LaNiO₃ perovskite electrocatalysts. Hydrogen reduction of 700 °C calcined LaNiO₃ induces a high density of surface oxygen vacancies, and confers significantly enhanced OER activity and stability compared to unreduced LaNiO₃; the former exhibit a low onset overpotential of 380 mV at 10 mA cm⁻² and a small Tafel slope of 70.8 mV dec⁻¹. Oxygen vacancy formation is accompanied by mixed Ni²⁺/Ni³⁺ valence states, which quantum-chemical DFT calculations reveal modify the perovskite electronic structure. Further, it reveals that the formation of oxygen vacancies is thermodynamically more favourable on the surface than in the bulk; it increases the electronic conductivity of reduced LaNiO₃ in accordance with the enhanced OER activity that is observed.     

Vibrational spectroscopic and force field studies of copper(II) chloride and bromide compounds,and crystal structure of KCuBr3

Vibrational spectroscopic and force field studies have been performed of 15 related copper(II) chloride and copper(II) bromide compounds, including hydrated salts crystallizing in ternary aqueous systems with alkali and ammonium halides. For halocuprates with distorted octahedral coordination characteristic stretching Raman wavenumbers, corresponding to symmetric stretching Cu^II X modes in the equatorial plane, were found in the ranges 247–288 cm⁻¹ for X = Cl, and 173–189 cm⁻¹ for X = Br, while the low‐wavenumber stretching modes for the weaker axial Cu X interactions varied considerably. The tetrahedral coordination for Cs₂CuCl₄ and Cs₂CuBr₄ leads to somewhat lower Cu X symmetric stretching wavenumbers, 295 and 173 cm⁻¹, respectively. The assignments of the copper–ligand stretching vibrations were performed with the aid of normal coordinate calculations. Correlations between force constants, averaged Cu X stretching wavenumbers and bond distances have been evaluated considering the following aspects: (1) Jahn–Teller tetragonal distortion (axial elongation) of the octahedral copper(II) coordination environment, (2) differences between terminal and bridging halide ligands (3) effects of coordinated water and the influence of outer‐sphere cations. Force constant ratios for terminal and bridging metal–halide bonds reveal characteristic differences between planar and tetrahedrally coordinated M₂X₆ species. In the hydrated copper(II) halide complexes, the halide ligands are more strongly bound than coordinated water molecules. The crystal structure of KCuBr₃ (K₂Cu₂Br₆), which was determined to provide structural information for the force field analyses, contains stacks of planar dimeric [Cu₂Br₆]²⁻ complexes held together by weak axial Cu Br interactions. Copyright © 2007 John Wiley & Sons, Ltd.