Reactions of Tris(oxazolinyl)phenylborato Rhodium(I) with C−X (X = Cl, Br, OTf) Bonds: Stereoselective Intermolecular Oxidative Addition

The achiral and enantiopure chiral compounds ToMRh(CO)2 (3) and ToPRh(CO)2 (4) (ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate; ToP = tris(4S-isopropyl-2-oxazolinyl)phenylborate) were prepared to investigate stereoselective oxidative addition reactions and develop new catalytic enantioselective bond functionalization and cross-coupling chemistry. Reactivity at the rhodium center is first shown by the substitution of the carbonyl ligands in 3 and 4 in the presence of the appropriate ligand; thus treatment of ToMRh(CO)2 with P(OMe)3 provides ToMRh(CO)[P(OMe)3] (5). However, reaction of ToMRh(CO)2 and MeOTf (Tf = SO2CF3) affords the complex [{N-Me-κ2-ToM}Rh(CO)2]OTf (6), resulting from N-oxazoline methylation rather than oxidative addition to rhodium(I). In contrast, ToMRh(CO)2 reacts with allyl bromide and chloroform, forming the rhodium(III) species (κ3-ToM)Rh(η1-C3H5)Br(CO) (7) and (κ3-ToM)Rh(CHCl2)Cl(CO) (8), respectively. Interestingly, the chiral ToPRh(CO)2 and CHCl3 react to give one diastereomer of (κ3-ToP)Rh(CHCl2)Cl(CO) (9; 100:3 dr) almost exclusively. To evaluate the reactivity of these rhodium(I) compounds, the carbonyl stretching frequencies have been examined. The data for the mono- and trivalent rhodium oxazolinylborate compounds indicate that the electron-donating ability of [ToM]− is slightly greater than that of [ToP]−, and both ligands provide electronic environments that can be compared to the tris(pyrazolyl)borate ligand family

Combinatorial generation via permutation languages

In this work we present a general and versatile algorithmic framework for exhaustively generating a large variety of different combinatorial objects, based on encoding them as permutations. This approach provides a unified view on many known results and allows us to prove many new ones. In particular, we obtain the following four classical Gray codes as special cases: the Steinhaus-Johnson-Trotter algorithm to generate all permutations of an $n$-element set by adjacent transpositions; the binary reflected Gray code to generate all $n$-bit strings by flipping a single bit in each step; the Gray code for generating all $n$-vertex binary trees by rotations due to Lucas, van Baronaigien, and Ruskey; the Gray code for generating all partitions of an $n$-element ground set by element exchanges due to Kaye. We present two distinct applications for our new framework: The first main application is the generation of pattern-avoiding permutations, yielding new Gray codes for different families of permutations that are characterized by the avoidance of certain classical patterns, (bi)vincular patterns, barred patterns, Bruhat-restricted patterns, mesh patterns, monotone and geometric grid classes, and many others. We thus also obtain new Gray code algorithms for the combinatorial objects that are in bijection to these permutations, in particular for five different types of geometric rectangulations, also known as floorplans, which are divisions of a square into $n$ rectangles subject to certain restrictions. The second main application of our framework are lattice congruences of the weak order on the symmetric group~$S_n$. Recently, Pilaud and Santos realized all those lattice congruences as $(n-1)$-dimensional polytopes, called quotientopes, which generalize hypercubes, associahedra, permutahedra etc. Our algorithm generates the equivalence classes of each of those lattice congruences, by producing a Hamilton path on the skeleton of the corresponding quotientope, yielding a constructive proof that each of these highly symmetric graphs is Hamiltonian. We thus also obtain a provable notion of optimality for the Gray codes obtained from our framework: They translate into walks along the edges of a polytope

t1-Noise Eliminated Dipolar Heteronuclear Multiple-Quantum Coherence Solid-State NMR Spectroscopy

Heteronuclear correlation (HETCOR) spectroscopy is one of the key tools in the arsenal of the solid-state NMR spectroscopist to probe spatial proximity between two different nuclei and enhance spectral resolution. Dipolar heteronuclear multiple-quantum coherence (D-HMQC) is a powerful technique that can be potentially utilized to obtain 1H detected 2D HETCOR solid-state NMR spectra of any NMR active nucleus. A long-standing problem in 1H detected D-HMQC solid-state NMR experiments is the presence of t1-noise which reduces sensitivity and impedes spectral interpretation. In this contribution, we describe novel pulse sequences, termed t1-noise eliminated (TONE) D-HMQC, that suppress t1-noise and can provide higher sensitivity and resolution than conventional D-HMQC. Monte-Carlo and numerical simulations confirm that t1-noise in conventional D-HMQC primarily occurs because random MAS frequency fluctuations cause variations in the NMR signal amplitude from scan to scan, leading to imperfect cancellation of uncorrelated signals by phase cycling. The TONE D-HMQC sequence uses 1H p-pulses to refocus the evolution of 1H CSA across each recoupling block, improving the stability of the pulse sequence to random MAS frequency fluctuations. The 1H refocusing pulses also restore the orthogonality of in-phase and anti-phase magnetization for all crystallite orientations, enabling the use of 90° flip-back or LG spin-lock trim pulses to reduce the intensity of uncorrelated signals. We demonstrate the application of these methods to acquire detected 2D 1H-35Cl and 1H-13C HETCOR spectra of histidine•HCl•H2O with reduced t1-noise. To show generality, we also apply these methods to obtain 2D 1H-17O spectra of 20%-17O fmoc-alanine and for the first time at natural abundance, 2D 1H-25Mg HETCOR spectra of magnesium hydroxide. The TONE D-HMQC sequences are also used to probe 1H-25Mg and 1H-27Al proximities in Mg-Al layered double hydroxides and confirm the even mixing of Mg and Al in these materials

KINEMATICS AND PHYSIOLOGICAL EFFECT OF A SYNCHRONIZED BIPEDAL “RISE-SIT-GO” CYCLING EXERCISE

This study demonstrated the kinematics and physiological effect of a synchronized bipedal cycling exercise. Fifteen male subjects performed a 30-minutes exercise on a synchronized bipedal stationary bike and a conventional stationary bike at same cycling speed. The performance was evaluated by a metabolic testing system, a subjective rating of perceived exertion, an electromyography system and a motion analysis system, and was compared by paired t-tests. Results showed significant increases in oxygen uptake, energy expenditure, rating of perceived exertion, muscle activity in triceps, biceps, rectus abdominis, left gluteus maximus, left medial gastrocnemius, right tibialis anterior and left tibialis anterior, and range of motion of left hip, left and right knees, shoulders, elbows and wrists. The synchronized bipedal cycling exercise was more physically demanding

Variations of the ISM Compactness Across the Main Sequence of Star-Forming Galaxies: Observations and Simulations

(abridged) The majority of star-forming galaxies follow a simple empirical correlation in the star formation rate (SFR) versus stellar mass ($M_*$) plane, usually referred to as the star formation Main Sequence (MS). Here we combine a set of hydro-dynamical simulations of interacting galactic disks with state-of-the-art radiative transfer codes to analyze how the evolution of mergers is reflected upon the properties of the MS. We present \textsc{Chiburst}, a Markov Chain Monte Carlo (MCMC) Spectral Energy Distribution (SED) code that fits the multi-wavelength, broad-band photometry of galaxies and derives stellar masses, star formation rates, and geometrical properties of the dust distribution. We apply this tool to the SEDs of simulated mergers and compare the derived results with the reference output from the simulations. Our results indicate that changes in the SEDs of mergers as they approach coalescence and depart from the MS are related to an evolution of dust geometry in scales larger than a few hundred parsecs. This is reflected in a correlation between the specific star formation rate (sSFR), and the compactness parameter $\mathcal{C}$, that parametrizes this geometry and hence the evolution of dust temperature ($T_{\rm{dust}}$) with time. As mergers approach coalescence, they depart from the MS and increase their compactness, which implies that moderate outliers of the MS are consistent with late-type mergers. By further applying our method to real observations of Luminous Infrared Galaxies (LIRGs), we show that the merger scenario is unable to explain these extreme outliers of the MS. Only by significantly increasing the gas fraction in the simulations are we able to reproduce the SEDs of LIRGs.Comment: 18 pages, 10 figures, accepted in Ap

Kirigami-inspired, highly stretchable micro-supercapacitor patches fabricated by laser conversion and cutting.

The recent developments in material sciences and rational structural designs have advanced the field of compliant and deformable electronics systems. However, many of these systems are limited in either overall stretchability or areal coverage of functional components. Here, we design a construct inspired by Kirigami for highly deformable micro-supercapacitor patches with high areal coverages of electrode and electrolyte materials. These patches can be fabricated in simple and efficient steps by laser-assisted graphitic conversion and cutting. Because the Kirigami cuts significantly increase structural compliance, segments in the patches can buckle, rotate, bend and twist to accommodate large overall deformations with only a small strain (<3%) in active electrode areas. Electrochemical testing results have proved that electrical and electrochemical performances are preserved under large deformation, with less than 2% change in capacitance when the patch is elongated to 382.5% of its initial length. The high design flexibility can enable various types of electrical connections among an array of supercapacitors residing in one patch, by using different Kirigami designs

Dynamical coupled-channel model of meson production reactions in the nucleon resonance region

A dynamical coupled-channel model is presented for investigating the nucleon resonances in the meson production reactions induced by pions and photons. The model is based on an energy-independent Hamiltonian which is derived from a set of Lagrangians by using a unitary transformation method. By applying the projection operator techniques,we derive a set of coupled-channel equations which satisfy the unitarity conditions within the channel space spanned by the considered two-particle meson-baryon states and the three-particle $\pi\pi N$ state. We present and explain in detail a numerical method based on a spline-function expansion for solving the resulting coupled-channel equations which contain logarithmically divergent one-particle-exchange driving terms resulted from the $\pi\pi N$ unitarity cut. We show that this driving term can generate rapidly varying structure in the reaction amplitudes associated with the unstable particle channels. It also has large effects in determining the two-pion production cross sections. Our results indicate that cautions must be taken to interpret the $N^*$ parameters extracted from using models which do not include $\pi\pi N$ cut effects.Comment: 73 pages, 20 figure

Multi-center, randomized, placebo-controlled trial of nocturnal oxygen therapy in chronic obstructive pulmonary disease: a study protocol for the INOX trial

Abstract\ud \ud Background\ud Long-term oxygen therapy (LTOT) is the only component of the management of chronic obstructive pulmonary disease (COPD) that improves survival in patients with severe daytime hypoxemia. LTOT is usually provided by a stationary oxygen concentrator and is recommended to be used for at least 15–18 h a day. Several studies have demonstrated a deterioration in arterial blood gas pressures and oxygen saturation during sleep in patients with COPD, even in those not qualifying for LTOT. The suggestion has been made that the natural progression of COPD to its end stages of chronic pulmonary hypertension, severe hypoxemia, right heart failure, and death is dependent upon the severity of desaturation occurring during sleep. The primary objective of the International Nocturnal Oxygen (INOX) trial is to determine, in patients with COPD not qualifying for LTOT but who present significant nocturnal arterial oxygen desaturation, whether nocturnal oxygen provided for a period of 3 years decreases mortality or delay the prescription of LTOT.\ud \ud \ud Methods\ud The INOX trial is a 3-year, multi-center, placebo-controlled, randomized trial of nocturnal oxygen therapy added to usual care. Eligible patients are those with a diagnosis of COPD supported by a history of past smoking and obstructive disease who fulfill our definition of significant nocturnal oxygen desaturation (i.e., ≥ 30% of the recording time with transcutaneous arterial oxygen saturation < 90% on either of two consecutive recordings). Patients allocated in the control group receive room air delivered by a concentrator modified to deliver 21% oxygen. The comparison is double blind. The primary outcome is a composite of mortality from all cause or requirement for LTOT. Secondary outcomes include quality of life and utility measures, costs from a societal perspective and compliance with oxygen therapy. The follow-up period is intended to last at least 3 years.\ud \ud \ud Discussion\ud The benefits of LTOT have been demonstrated whereas those of nocturnal oxygen therapy alone have not. The INOX trial will likely determine whether supplemental oxygen during sleep is effective in reducing mortality, delaying the need for LTOT and improving health-related quality of life in patients with COPD who desaturate overnight.\ud \ud \ud Trial registration\ud Current Controlled Trials \ud ISRCTN50085100\ud \ud ; ClinicalTrials.gov \ud NCT01044628\ud \ud (date of registration: January 6, 2010)

Minimum Rank of Graphs with Loops

A loop graph S is a finite undirected graph that allows loops but does not allow multiple edges. The set S(S) of real symmetric matrices associated with a loop graph of order n is the set of symmetric matrices A = [a(ij)] is an element of R-nxn such that a(ij) not equal 0 if and only if ij is an element of E(S). The minimum (maximum) rank of a loop graph is the minimum (maximum) of t he ranks of the matrices in S(S). Loop graphs having minimum rank at most two are characterized (by forbidden induced subgraphs and graph complements) and loop graphs having minimum rank equal to the order of the graph are characterized. A Schur complement reduction technique is used to determine the minimum ranks of cycles with various loop configurations; the minimum ranks of complete graphs and paths with various configurations of loops are also determined. Unlike simple graphs, loop graphs can have maximum rank less than the order of the graph. Some results are presented on maximum rank and which ranks between minimum and maximum can be realized. Interesting open questions remain