C−H Bond Activation by Dicationic Platinum(II) Complexes

Double protonolysis of diimine platinum dimethyls [(N-N)PtMe_2] (N-N ═ ArNC(Me)C(Me) ═ NAr) generates dicationic Pt(II) complexes that can activate a variety of C−H bonds, liberating 1 equiv of acid and forming organoplatinum species that are moderately stable to the resulting acidic conditions. Ethylbenzenes lead to η^3-benzyl complexes; mechanistic experiments suggest that η^3-benzyl product formation proceeds via C−H bond activation at the benzylic methylene position. In some cases π-arene complexes can be observed, but their role in the C−H activation process is not clear. Cyclohexane and 1-pentene react to give η^3-allyl complexes; allylbenzene gives a chelated phenyl-η^2-olefin structure, as determined by X-ray diffraction. No stable C−H activation products are obtained from methylbenzenes, benzene itself, or alkanes

Formation of the coherent heavy fermion liquid at the 'hidden order' transition in URu2Si2

In this article we present high-resolution angle-resolved photoemission (ARPES) spectra of the heavy-fermion superconductor URu$_2$Si$_2$. Measurements as a function of both excitation energy and temperature allow us to disentangle a variety of spectral features, revealing the evolution of the low energy electronic structure across the hidden order transition. Already above the hidden order transition our measurements reveal the existence of weakly dispersive states below the Fermi level that exhibit a large scattering rate. Upon entering the hidden order phase, these states transform into a coherent heavy fermion liquid that hybridizes with the conduction bands.Comment: 5 pages, 4 figure

Using Semantic Similarity and Text Embedding to Measure the Social Media Echo of Strategic Communications

Online discourse covers a wide range of topics and many actors tailor their content to impact online discussions through carefully crafted messages and targeted campaigns. Yet the scale and diversity of online media content make it difficult to evaluate the impact of a particular message. In this paper, we present a new technique that leverages semantic similarity to quantify the change in the discussion after a particular message has been published. We use a set of press releases from environmental organisations and tweets from the climate change debate to show that our novel approach reveals a heavy-tailed distribution of response in online discourse to strategic communications.Comment: 12 pages, 5 figure

Comparison of three methods for the methylation of aliphatic and aromatic compounds

Rationale: Methylation protocols commonly call for acidic, hot conditions that are known to promote organic ^1H/^2H exchange in aromatic and aliphatic C—H bonds. Here we tested two such commonly-used methods and compared a third that avoids these acidic conditions, to quantify isotope effects with each method and to directly determine acidic-exchange rates relevant to experimental conditions. Methods: We compared acidic and non-acidic methylation approaches catalyzed by hydrochloric acid, acetyl chloride and EDCI (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide) / DMAP (4-dimethylaminopyridine) respectively. These were applied to two analytes: phthalic acid (an aromatic) and octacosanoic acid (an aliphatic). We analyzed yield by gas chromatography flame ionization (GC/FID) and hydrogen and carbon isotopic composition by isotope ratio mass spectrometry (GC/IRMS). We quantified the ^1H/^2H exchange rate on dimethyl phthalate under acidic conditions with proton nuclear magnetic resonance (^1H-NMR) measurements. Results: The δ^2H and δ^(13)C values and yield were equivalent among the three methods for methyl octacosanoate. The two acidic methods resulted in comparable yield and isotopic composition of dimethyl phthalate; however, the non-acidic method resulted in lower δ^2H and δ^(13)C values perhaps due to low yields. Concerns over acid-catalyzed ^1H/^2H exchange are unwarranted as the effect was trivial over a 12-hour reaction time. Conclusions: We find product isolation yield and evaporation to be the main concerns in the accurate determination of isotopic composition. ^1H/^2H exchange reactions are too slow to cause measurable isotope fractionation over the typical duration and reaction conditions used in methylation. Thus, we are able to recommend continued use of acidic catalysts in such methylation reactions for both aliphatic and aromatic compounds

Biomechanical Evaluation of fracture Fixation Constructs using a Variable-angle Locked Periprosthetic Femur Plate System

BackgroundIn the United States there are more than 230,000 total hip replacements annually, and periprosthetic femoral fractures occur in 0.1–4.5% of those patients. The majority of these fractures occur at the tip of the stem (Vancouver type B1). The purpose of this study was to compare the biomechanically stability and strength of three fixation constructs and identify the most desirable construct.MethodsFifteen medium adult synthetic femurs were implanted with a hip prosthesis and were osteotomized in an oblique plane at the level of the implant tip to simulate a Vancouver type B1 periprosthetic fracture. Fractures were fixed with a non-contact bridging periprosthetic proximal femur plate (Zimmer, Inc., Warsaw, IN). Three proximal fixation methods were used: Group 1, bicortical screws; Group 2, unicortical screws and one cerclage cable; and Group 3, three cerclage cables. Distally, all groups had bicortical screws. Biomechanical testing was performed using an axial-torsional testing machine in three different loading modalities (axial compression, lateral bending, and torsional/sagittal bending), next in axial cyclic loading to 10,000 cycles, again in the three loading modalities, and finally to failure in torsional/sagittal bending.ResultsGroup 1 had significantly greater load to failure and was significantly stiffer in torsional/sagittal bending than Groups 2 and 3. After cyclic loading, Group 2 had significantly greater axial stiffness than Groups 1 and 3. There was no difference between the three groups in lateral bending stiffness. The average energy absorbed during cyclic loading was significantly lower in Group 2 than in Groups 1 and 3.ConclusionsBicortical screw placement achieved the highest load to failure and the highest torsional/sagittal bending stiffness. Additional unicortical screws improved axial stiffness when using cable fixation. Lateral bending was not influenced by differences in proximal fixation.Clinical RelevanceTo treat periprosthetic fractures, bicortical screw placement should be attempted to maximize load to failure and torsional/sagittal bending stiffness