Implementation of the FSI was associated with reduced mortality, suggesting the feasibility of widespread screening of patients preoperatively to identify frailty and the efficacy of system-level initiatives aimed at improving their surgical outcomes. Additional investigation is required to establish a causal connection.

Our data suggest that a systematic frailty-screening program effectively identifies at-risk surgical patients and is associated with a significant reduction in mortality for patients undergoing palliative care consultation. Analysis also suggests that preoperative palliative care consultations ordered by surgeons are associated with reduced mortality rates.

The phase diagram and microstructure of the ternary system ionic, liquid benzylpyridinium bis(trifluoromethanesulfonyl)imide)/nonionic surfactant (octylphenol ethoxylate)/toluene, were studied by using conductivity measurements, dynamic light scattering, pulse field gradient spin-echo NMR, and small-angle neutron scattering. Three microregions were identified by conductivity measurements according to the percolation theory. The sizes of IL-in-oil microemulsions with various IL fractions were then determined by NMR and DLS and were found to be in accordance with the radii of gyration (approximately 2 or 3 nm) determined by SANS. The reverse IL-in-oil microemulsions were used as nanoreactors to perform a Matsuda-Heck reaction between p-methoxyphenyl diazonium salt and 2,3-dihydrofurane in the presence of a palladium catalyst. The reaction yields obtained were greater in microemulsions (67%) than in bulk IL (33%), highlighting a strong effect of confinement. Moreover, a direct correlation between the quantity of IL and the reaction yield was observed.

The synthesis of the four possible diastereoisomers of α,β‐D‐CNA 5′‐XT (X = A, T, G and C) building units of nucleic acids, in which the α and β torsional angles are stereocontrolled by a dioxaphosphorinane ring structure (D‐CNA family) is described. The crystal structure analysis of the (RC5′,SP)‐configured α,β‐D‐CNA TT dimer demonstrates that the α and β torsional angles are restricted to the canonical {gauche(–),trans} conformation typically observed in DNA duplexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

π-Allyl complexes play a prominent role in organometallic chemistry and have attracted considerable attention, in particular the π-allyl Pd­(II) complexes which are key intermediates in the Tsuji–Trost allylic substitution reaction. Despite the huge interest in π-complexes of gold, π-allyl Au­(III) complexes were only authenticated very recently. Herein, we report the reactivity of (P,C)-cyclometalated Au­(III) π-allyl complexes toward β-diketo enolates. Behind an apparently trivial outcome, i.e. the formation of the corresponding allylation products, meticulous NMR studies combined with DFT calculations revealed a complex and rich mechanistic picture. Nucleophilic attack can occur at the central and terminal positions of the π-allyl as well as the metal itself. All paths are observed and are actually competitive, whereas addition to the terminal positions largely prevails for Pd­(II). Auracyclobutanes and π-alkene Au­(I) complexes were authenticated spectroscopically and crystallographically, and Au­(III) σ-allyl complexes were unambiguously characterized by multinuclear NMR spectroscopy. Nucleophilic additions to the central position of the π-allyl and to gold are reversible. Over time, the auracyclobutanes and the Au­(III) σ-allyl complexes evolve into the π-alkene Au­(I) complexes and release the C-allylation products. The relevance of auracyclobutanes in gold-mediated cyclopropanation was demonstrated by inducing C–C coupling with iodine. The molecular orbitals of the π-allyl Au­(III) complexes were analyzed in-depth, and the reaction profiles for the addition of β-diketo enolates were thoroughly studied by DFT. Special attention was devoted to the regioselectivity of the nucleophilic attack, but C–C coupling to give the allylation products was also considered to give a complete picture of the reaction progress.

Branched thermotropic liquid crystals were successfully obtained from ionic interactions between hyperbranched polyamidoamine and sodium dodecylsulfate. These complexes present columnar rectangular and lamellar thermotropic mesophases as demonstrated by polarized optical microscopy, differential scanning calorimetry, and small-angle X-ray scattering. The relationships between the structural characteristics of the polymers (size of the hyperbranched core, hyperbranched or dendritic nature of the core, and substitution ratio) and the mesomorphic properties were studied. In situ formation of gold nanoparticles was then performed. The templating effect of the liquid crystal mesophase resulted in the formation of isotropic nanoparticles, the size of which was dictated by the local organization of the mesophase and by the molar mass of the hyperbranched complex.

Over the last 5−10 years, gold(III) catalysis has developed rapidly. It often shows complementary if not unique features compared to gold(I) catalysis. While recent work has enabled major synthetic progress in terms of scope and efficiency, very little is yet known about the mechanism of Au(III)-catalyzed transformations and the relevant key intermediates have rarely been authenticated. Here, we report a detailed experimental/computational mechanistic study of the recently reported intermolecular hydroarylation of alkynes catalyzed by (P,C)-cyclometalated Au(III) complexes. The cationic (P,C)Au(OAc F ) + complex (OAc F = OCOCF 3 ) was authenticated by mass spectrometry (MS) in the gas phase and multi-nuclear NMR spectroscopy in solution at low temperatures. According to density functional theory (DFT) calculations, the OAc F moiety is κ 2 -coordinated to gold in the ground state, but the corresponding κ 1 -forms featuring a vacant coordination site sit only slightly higher in energy. Side-on coordination of the alkyne to Au(III) then promotes nucleophilic addition of the arene. The energy profiles for the reaction between trimethoxybenzene (TMB) and diphenylacetylene (DPA) were computed by DFT. The activation barrier is significantly lower for the outer-sphere pathway than for the alternative inner-sphere mechanism involving C−H activation of the arene followed by migratory insertion. The π-complex of DPA was characterized by MS. An unprecedented σ-arene Au(III) complex with TMB was also authenticated both in the gas phase and in solution. The cationic complexes [(P,C)Au(OAc F )] + and [(P,C)Au(OAc F )(σ-TMB)] + stand as active species and off-cycle resting state during catalysis, respectively. This study provides a rational basis for the further development of Au(III) catalysis based on π-activation.

P‐CNAs are dinucleotide building blocks in which the torsional angles α and β of the sugar/phosphate backbone are constrained to non‐canonical values within a cyclic phosphonate structure (phostone) synthesised by diastereoselective intramolecular Arbuzov reaction. The reaction has been improved through the use of microwave activation and addition of lithium bromide.