To compare the effects of spinal thrust manipulation and electrical dry needling (TMEDN group) to those of nonthrust peripheral joint/soft tissue mobilization, exercise, and interferential current (NTMEX group) on pain and disability in patients with subacromial pain syndrome (SAPS). U DESIGN: Randomized, single-blinded, multicenter parallel-group trial. U METHODS: Patients with SAPS were randomized into the TMEDN group (n = 73) or the NTMEX group (n = 72). Primary outcomes included the Shoulder Pain and Disability Index and the numeric pain-rating scale. Secondary outcomes included the global rating of change scale (GROC) and medication intake. The treatment period was 6 weeks, with follow-ups at 2 weeks, 4 weeks, and 3 months. U RESULTS: At 3 months, the TMEDN group experienced greater reductions in shoulder pain and disability (P<.001) compared to the NTMEX group. Effect sizes were large in favor of the TMEDN group. At 3 months, a greater proportion of patients within the TMEDN group achieved a successful outcome (GROC score of 5 or greater) and stopped taking medication (P<.001). U CONCLUSION: Cervicothoracic and upper-rib thrust manipulation combined with electrical dry needling resulted in greater reductions in pain, disability, and medication intake than nonthrust peripheral joint/soft tissue mobilization, exercise, and interferential current in patients with SAPS. The effects were maintained at 3 months.
The C^N^C ligand 2,6-bis(2,3-dialkoxyphenyl)pyridine forms dimercury and orthopalladated complexes, both of which may be transmetallated to gold(III) complexes; the gold complexes may also be formed directly in a Rh(III)-catalysed process,...
The optical and electrochemical properties of quadruply
bonded
dimolybdenum paddlewheel complexes (Mo2PWCs) make them
ideal candidates for incorporation into functional materials or devices,
but one of the greatest bottlenecks for this is their poor stability
toward atmospheric oxygen. By tuning the potential at which the Mo2 core is oxidized, it was possible to increase the tolerance
of Mo2PWCs to air. A series of homoleptic Mo2PWCs bearing fluorinated formamidinate ligands have been synthesized
and their electrochemical properties studied. The oxidation potential
of the complexes was tuned in a predictable fashion by controlling
the positions of the fluorine substituents on the ligands, as guided
by a Hammett relationship. Studies into the air stability of the resulting
complexes by multinuclear NMR spectroscopy show an increased tolerance
to atmospheric oxygen with increasingly electron-withdrawing ligands.
The heteroleptic complex Mo2(DFArF)3(OAc) [where DFArF = 3,5-(difluorophenyl)formamidinate]
shows remarkable tolerance to oxygen in the solid state and in chloroform
solutions. Through the employment of easily accessible ligands, the
stability of the Mo2 core toward oxygen has been enhanced,
thereby making Mo2PWCs with electron-withdrawing ligands
more attractive candidates for the development of functional materials.
The hydrogen/halogen exchange of phosphines has been exploited to establish a truly useable substrate scope and straightforward methodology for the formation of cyclopolyphosphines. Starting from a single dichlorophosphine, a sacrificial proton "donor phosphine" makes the rapid, mild synthesis of cyclopolyphosphines possible: reactions are complete within 10 min at room temperature. Novel (aryl)cyclopentaphosphines (ArP) 5 have been formed in good conversion, with the crystal structures presented. The use of catalytic quantities of iron(III) acetylacetonate provides significant improvements in conversion in the context of diphosphine (Ar 2 P) 2 and alkyl-substituted cyclotetra-or cyclopentaphosphine ((AlkylP) n , where n = 4 or 5) formation. Both iron-free and iron-mediated reactions show high levels of selectivity for one specific ring size. Finally, investigations into the reactivity of Fe(acac) 3 suggest that the iron species is acting as a sink for the hydrochloric acid byproduct of the reaction.
The
complex bis(tetrabutylammonium) (trans-μ2:η2,η2-1,3-butadiene)bis(trichloroplatinate(II)),
identified from its X-ray single-crystal structure, is formed when
tetrabutylammonium hexachloroplatinate(IV) is irradiated in solution.
In principle, the complex can exist in one of four conformers (combining cis and trans isomers of the butadiene
and syn and anti arrangements of
the two PtCl3
– moieties) and DFT calculations
suggest that three of these ought to be stable in solution in CDCl3. However, dissolving the anti,trans conformer
(identified from both crystallography and 13C{1H} MAS NMR spectroscopy) in solution leads to the formation of a
second conformer, identified by a combination of NMR experiments,
in amounts that depend on the solvent used. Then, on standing in solution,
a third species forms that contains a single PtCl3
– moiety. The identification and interconversion of
these various species are discussed.
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