Metal-Ion Oxidative Decarboxylations. 10. Substituent Effects In The Cerium(IV)-Benzilic Acids Reaction

The rates of oxidation by cerium (IV) of several substituted benzylic acids (unsubstituted, 2,2′-dichloro, 4,4′-dichloro, 4,4′-dimethyl, 4,4′-dimethoxy, and 4,4′-dinitro) to the corresponding benzophenones have been studied spectrophotometrically in aqueous H2SO4, aqueous HClO4-HOAc, and acetonitrile. The rates are much slower in H2SO4 than in the other two media, probably because of heavy sulfato complexation of cerium(IV). The px as of the various acids were determined potentiometrically. The Hammett p values in acetonitrile and HClO4-HOAc media, derived from correlations with several sets of σ constants and with the newly determined pKas, are about -0.7 and -0.35 in the two media, respectively. These values rule out the possibility of positive charge development at the benzhydrilic carbon, at or prior to the rate-determining step. Instead, a mechanism involving free (?) radicals is proposed. © 1977, American Chemical Society. All rights reserved

Metal-Ion Oxidative Decarboxylations. 9. Reaction Of Benzilic Acid With Cerium(IV) In Acidic Perchlorate And Sulfate Media

The kinetics of oxidation of benzylic acid (HLH) to benzophenone by cerium (IV) has been studied in several media using the stopped-flow technique. In HClO4-Na2SO4-NaClO4 media, which allow for the variation and control of the concentrations of the various Ce(IV) species at constant [H+] and ionic strength, the rate data suggest CeSO42+ as the kinetically relevant species. In HClO4 the observed first-order rate constants, tetrad, first increase with increasing HLH concentration, then decrease slightly at higher substrate concentrations suggesting the intermediacy of two complexes: a reactive [Ce(IV)HL] and a [Ce(IV)(HL)2] which resists reaction. The rate law which best describes the observed kinetics in HClO4 media is given by [formula ommitted] where K7 ′ and K8′ are H+-dependent equilibrium constants for the formation of the 1:1 and 1:2 complexes, respectively. The kinetic parameters kα and kβ are the rate constants for the intramolecular redox reaction of the 1:1 and 1:2 complexes, respectively. The rates in H2SO4 are much slower than those in HClO4 and do not reflect strong complex formation before electron transfer. Whereas H+ had an inhibiting effect in the above-mentioned media, catalysis by H+ was manifest in HClO4-HOAc media, possibly through decreasing acetato complexation of Ce(IV). © 1977, American Chemical Society. All rights reserved

Fabrication of metastable crystalline nanocomposites by flash annealing of Cu47.5Zr47.5Al5 metallic glass using joule heating

Flash Joule-heating was applied to the Cu47.5Zr47.5Al5 metallic glass for designing fully crystalline metastable nanocomposites consisting of the metastable B2 CuZr and low-temperature equilibrium Cu10Zr7 phases. The onset of crystallization was in situ controlled by monitoring resistivity changes in the samples. The effect of heating rate and annealing time on the volume fraction of the crystalline phases and mechanical properties of the nanocomposites was studied in detail. Particularly, an increase of the heating rate and a decrease of the annealing time lead to a lower number of equilibrium Cu10Zr7 precipitates and an increase of tensile ductility. Tailoring of these non-equilibrium microstructures and mechanical properties may not be possible unless one starts with a fully glassy material that opens new perspectives for designing metastable nanomaterials with unique physical properties

Fabrication of metastable crystalline nanocomposites by flash annealing of Cu47.5Zr47.5Al5 metallic glass using joule heating

Flash Joule-heating was applied to the Cu47.5Zr47.5Al5 metallic glass for designing fully crystalline metastable nanocomposites consisting of the metastable B2 CuZr and low-temperature equilibrium Cu10Zr7 phases. The onset of crystallization was in situ controlled by monitoring resistivity changes in the samples. The effect of heating rate and annealing time on the volume fraction of the crystalline phases and mechanical properties of the nanocomposites was studied in detail. Particularly, an increase of the heating rate and a decrease of the annealing time lead to a lower number of equilibrium Cu10Zr7 precipitates and an increase of tensile ductility. Tailoring of these non-equilibrium microstructures and mechanical properties may not be possible unless one starts with a fully glassy material that opens new perspectives for designing metastable nanomaterials with unique physical properties. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.EC 111/26-1, MA 3333/13-105K2012European Research Council, ERC: ERC-2013-ADG-340025Funding: This research was funded by the German Federal Ministry of Education and Science BMBF, grant number 05K2012, the German Science Foundation under the Leibniz Program, grant numbers EC 111/26-1 and MA 3333/13-1, and the European Research Council (ERC) under the ERC Advanced Grant INTELHYB, grant number ERC-2013-ADG-340025

New-generation biocompatible Ti-based metallic glass ribbons for flexible implants

We introduce five new biocompatible Ti-based metallic glass (MG) compositions with different metalloid and soft metal content for a synergistic improvement in corrosion properties. Without any potentially harmful elements such as Cu, Ni or Be, these novel alloys can eliminate the risk of inflammatory reaction when utilized for permanent medical implants. Excluding Cu, Ni or Be, which are essential for Ti-based bulk MG production, on the other hand, confines the glass-forming ability of novel alloys to a moderate level. In this study, toxic-element free MG alloys with significant metalloid (Si–Ge–B, 15–18 at.%) and minor soft element (Sn, 2–5 at.%) additions are produced in ribbon form using conventional single-roller melt spinning technique. Their glass-forming abilities and their structural and thermal properties are comparatively investigated using X-ray diffraction (XRD), synchrotron XRD and differential scanning calorimetry. Their corrosion resistance is ascertained in a biological solution to analyze their biocorrosion properties and compare them with other Ti-based bulk MGs along with energy dispersive X-ray. Ti60Zr20Si8Ge7B3Sn2 and Ti50Zr30Si8Ge7B3Sn2 MG ribbons present a higher pitting potential and passivation domain compared with other Ti-based MG alloys tested in similar conditions. Human mesenchymal stem cell metabolic activity and cytocompatibility tests confirm their outstanding cytocompatibility, outperforming Ti-Al6-V4

Psychological response and quality of life after transplantation: a comparison between heart, lung, liver and kidney recipients

PRINCIPLES: Various non-specific questionnaires were used to measure quality of life and psychological wellbeing of patients after organ transplantation. At present cross-organ studies dealing specifically with the psychological response to a transplanted organ are non-existent in German-speaking countries. METHODS: The Transplant Effects Questionnaire TxEQ-D and the SF-36 Quality of Life Questionnaire were used to examine the psychological response and quality of life of 370 patients after heart, lung, liver or kidney transplantation. The organ groups were compared with regard to psychosocial parameters. RESULTS: 72% of patients develop a feeling of responsibility for the received organ and its function. This feeling is even stronger towards the patient's key relationships i.e. family, friends, the treatment team and the donor. 11.6% worry about the transplanted organ. Heart and lung patients report significantly fewer concerns than liver and kidney patients. Overall, only a minority of patients report feelings of guilt towards the donor (2.7%), problems in disclosing their transplant to others (2.4%), or difficulties in complying with medical orders (3.5%). Lung transplant patients show significantly better adherence. CONCLUSIONS: A feeling of responsibility towards those one is close to and towards the donor is a common psychological phenomenon after transplantation of an organ. Conscious feelings of guilt and shame are harboured by only a minority of patients. The fact that heart and lung patients worry less about their transplant might have primarily to do with the greater medical and psychosocial support in this group

Soft Magnetic Properties and Electromagnetic Shielding Performance of Fe40Ni40B20 Microfibers

Fi(40)Ni(40)B(20) metallic glass is a key material among the many amorphous systems investigated thus far, owing to its high strength and appealing soft magnetic properties that make it suitable for use as transformer cores. In this study, Fi(40)Ni(40)B(20) microfibers are fabricated down to 5 mu m diameter. Three different melt-spinning wheel velocities: approximate to 51 m s(-1), approximate to 59 m s(-1), and approximate to 63 m s(-1) (MG1, MG2, MG3) are used. Their fully amorphous structure is confirmed using X-ray diffraction, and differential scanning calorimetry (DSC) traces reveal a larger relaxation profile for the higher-quenched microfiber. Vibrating sample magnetometer measurements showed a higher saturation magnetization of 136 emug(-1) for annealed metallic glass microfibers with a wheel velocity of 59.66 ms(-1). Cylindrical magnetic field shields are obtained by aligning and wrapping the fibers around a cast. The observed anisotropic static field shielding behavior is in accordance with the microfibers' anisotropic nature. Composite samples are also produced by embedding the microfibers in an epoxy matrix to investigate their electromagnetic properties at GHz frequencies. Inclusion of the microfibers increase the composite's attenuation constant by 20 to 25 times, making it an ideal candidate for applications in the communications frequency range

European Medicines Agency review of ixazomib (Ninlaro) for the treatment of adult patients with multiple myeloma who have received at least one prior therapy

On 21 November 2016, the European Commission issued a marketing authorisation valid throughout the European Union for ixazomib in combination with lenalidomide and dexamethasone for the treatment of adult patients with multiple myeloma who have received at least one prior therapy. Ixazomib was evaluated in one, randomised, double-blind, phase III study comparing ixazomib plus lenalidomide and dexamethasone (n=360; ixazomib arm) versus placebo plus lenalidomide and dexamethasone (n=362; placebo arm) in adult patients with relapsed and/or refractory multiple myeloma who had received at least one prior therapy. The median progression-free survival (PFS) in the intent-to-treat population was 20.6 months in patients treated with ixazomib compared with 14.7 months for patients in the placebo arm (stratified HR=0.742, 95% CI 0.587 to 0.939, stratified p-value=0.012). The most frequently reported adverse reactions (≥20%) within the ixazomib and placebo arms were diarrhoea (42% vs 36%), constipation (34% vs 25%), thrombocytopaenia (28% vs 14%), peripheral neuropathy (28% vs 21%), nausea (26% vs 21%), peripheral oedema (25% vs 18%), vomiting (22% vs 11%) and back pain (21% vs 16%). The scientific review concluded that the gain in PFS of 5.9 months observed with ixazomib was considered clinically meaningful. Concerning the possible uncertainty about the magnitude of the effect, this uncertainty was acceptable given the favourable toxicity profile, and considering that ixazomib is the first agent to allow oral triple combination therapy in this patient population which represents a therapeutic innovation in terms of convenience for patients. Therefore, the benefit-risk for ixazomib in combination with lenalidomide and dexamethasone was considered positive, although the efficacy evidence was not as comprehensive as normally required

Charmed Exotics in Heavy Ion Collisions

Based on the color-spin interaction in diquarks, we argue that charmed multiquark hadrons are likely to exist. Because of the appreciable number of charm quarks produced in central nucleus-nucleus collisions at ultrarelativistic energies, production of charmed multiquark hadrons is expected to be enhanced in these collisions. Using both the quark coalescence model and the statistical hadronization model, we estimate the yield of charmed tetraquark meson $T_{cc}$ and pentaquark baryon $\Theta_{cs}$ in heavy ion collisions at RHIC and LHC. We further discuss the decay modes of these charmed exotic hadrons in order to facilitate their detections in experiments

Apium plants: Beyond simple food and phytopharmacological applications

Apium plants belong to the Apiaceae family and are included among plants that have been in use in traditional medicine for thousands of years worldwide, including in the Mediterranean, as well as the tropical and subtropical regions of Asia and Africa. Some highlighted medical benefits include prevention of coronary and vascular diseases. Their phytochemical constituents consist of bergapten, flavonoids, glycosides, furanocoumarins, furocoumarin, limonene, psoralen, xanthotoxin, and selinene. Some of their pharmacological properties include anticancer, antioxidant, antimicrobial, antifungal, nematocidal, anti-rheumatism, antiasthma, anti-bronchitis, hepatoprotective, appetizer, anticonvulsant, antispasmodic, breast milk inducer, anti-jaundice, antihypertensive, anti-dysmenorrhea, prevention of cardiovascular diseases, and spermatogenesis induction. The present review summarizes data on ecology, botany, cultivation, habitat, medicinal use, phytochemical composition, preclinical and clinical pharmacological efficacy of Apium plants and provides future direction on how to take full advantage of Apium plants for the optimal benefit to mankind.N. Martins would like to thank the Portuguese Foundation for Science and Technology (FCT-Portugal) for the strategic project ref. UID/BIM/04293/2013 and “NORTE2020-Northern Regional Operational Program” (NORTE-01-0145-FEDER-000012)