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A redox active Ni-Pd alloy nanocluster [Ni22-xPd20+x(CO)48]6-(x= 0.62) ([>1>]6-) was obtained from the redox condensation of [NBu4]2[Ni6(CO)12] with 0.7-0.8 equivalents of Pd(Et2S)2Cl2in CH2Cl2. Conversely, [Ni29-xPd6+x(CO)42]6-(x= 0.09) ([>2>]6-) and [Ni29+xPd6-x(CO)42]6-(x= 0.27) ([>3>]6-) were obtained by employing [NEt4]2[Ni6(CO)12] and 0.6-0.7 equivalents of Pd(Et2S)2Cl2in CH3CN. The molecular structures of these high nuclearity Ni-Pd carbonyl clusters were determined by single-crystal X-ray diffraction (SC-XRD). [>1>]6-adopted an M40ccpstructure comprising five close-packed ABCAB layers capped by two additional Ni atoms. Conversely, [>2>]6-and [>3>]6-displayed anhcpM35metal core composed of three compact ABA layers. [>1>]6-, [>2>]6-and [>3>]6-showed nanometric sizes, with the maximum lengths of their metal cores being 1.3 nm ([>1>]6-) and 1.0 nm ([>2>]6-and [>3>]6-), which increased up to 1.9 and 1.5 nm, after including also the CO ligands. Ni-Pd distribution within their metal cores was achieved by avoiding terminal Pd-CO bonding and minimizing Pd-CO coordination. As a consequence, site preference and partial metal segregation were observed, as well as some substitutional and compositional disorders. Electrochemical and spectroelectrochemical studies revealed that [>1>]6-and [>2>]6-were redox active and displayed four and three stable oxidation states, respectively. Even though several redox active high nuclearity metal carbonyl clusters have been previously reported, the nanoclusters described herein represent the first examples of redox active Ni-Pd carbonyl alloy nanoclusters.

Background and purpose Following the commercial availability of nusinersen, there have been a number of new referrals of adults with spinal muscular atrophy (SMA) not regularly followed in tertiary-care centers or enrolled in any disease registry. Methods We compared demographics and disease characteristics, including assessment of motor and respiratory function, in regularly followed patients and newcomers subdivided according to the SMA type. Results The cohort included 166 adult patients (mean age: 37.09 years): one type I, 65 type II, 99 type III, and one type IV. Of these 166, there were 67 newcomers. There was no significant difference between newcomers and regularly followed patients in relation to age and disease duration. The Hammersmith Functional Motor Scale Expanded and Revised Upper Limb Module scores were higher in the regularly followed patients compared to newcomers in the whole cohort and in both SMA II and II. A difference was also found on ventilatory status (p = 0.013) and Cobb's angle >50° (p = 0.039) between the two subgroups. No difference was found in scoliosis surgery prevalence (p > 0.05). Conclusions Our results showed differences between the two subgroups, even if less marked in the type III patients. In the type II patients, there was a higher proportion of newcomers who were in the severe end of the spectrum. Of the newcomers, only approximately a third initiated treatment, as opposed to the 51% in the regularly followed patients. The identification of patients who were not part of the registries will help to redefine the overall prevalence of SMA and the occurrence of different phenotypes.

Tommaso Susini,1 Barbara Berti,1 Carlo Carriero,1 Ketty Tavella,2 Jacopo Nori,3 Ermanno Vanzi,3 Cecilia Molino,1 Mariarosaria Di Tommaso,1 Marco Santini,1 Valeria Saladino,4 Simonetta Bianchi4 1Department of Health Science, Gynecology Section, 2Department of Health Science, Chemotherapy Section, University of Florence, Italy; 3Diagnostic Senology Unit, Azienda Ospedaliera-Universitaria Careggi, Florence, Italy; 4Department of Surgery and Translational Medicine, Pathology Unit, University of Florence, Italy Purpose: Anthracyclines and taxanes are considered the standard for neoadjuvant chemotherapy of breast cancer, although they are often associated with serious side effects and wide variability of individual response. In this study, we analyzed the value of topoisomerase II alpha (TOP2A) and transducin-like enhancer of split 3 (TLE3) as predictive markers of response to therapy with anthracyclines and taxanes. Materials and methods: TOP2A and TLE3 protein expressions were evaluated using immunohistochemistry on 28 samples, obtained by core needle biopsy in patients with locally advanced breast carcinoma, subsequently subjected to epirubicin- and paclitaxel-based neoadjuvant chemotherapy. The immunohistochemical staining was correlated with the clinical response measured by the tumor size reduction evaluated by breast magnetic resonance imaging, prior and after chemotherapy, and by pathologic evaluation of the surgical specimen. Results: Neoadjuvant chemotherapy achieved a size reduction in 26/28 tumors (92.9%), with an average percentage decrease of 45.6%. A downstaging was achieved in 71.4% of the cases of locally advanced carcinoma. TOP2A positivity was correlated with a greater reduction in tumor diameter (P=0.06); negative staining for TLE3 was predictive of a better response to neoadjuvant chemotherapy (P=0.07). A higher reduction in tumor diameter (P=0.03) was also found for tumors that were concurrently TLE3-negative and TOP2A-positive. Conclusion: TOP2A and TLE3 showed a correlation with response to neoadjuvant chemotherapy. While TOP2A is a well-known marker of response to anthracyclines-based chemotherapy, TLE3 is a new putative predictor of response to taxanes. Data from the current study suggest that TOP2A and TLE3 warrant further investigation in a larger series as predictors of response to neoadjuvant chemotherapy for locally advanced breast carcinoma. Keywords: breast carcinoma, advanced stage disease, immunohistochemical markers

Two and half decades after the fall of the Berlin Wall, Europe has made signifi cant headway in unifi cation “despite its diversity”. In unprecedented “big bang” rounds of EU enlargement, eight Central and East European (CEE) countries joined the European Union in 2004; two Eastern Balkan countries, Bulgaria and Romania, in 2007; and the fi rst Western Balkan country, Croatia, became the EU’s 28th member state in July 2013. As of early 2015, the rest of the Western Balkans (WB) 2 has obtained either a candidate status (Albania, the Former Yugoslav Republic of Macedonia-FYROM, Montenegro and Serbia) or a potential candidate status (Bosnia and Herzegovina and Kosovo).

Conference on Nuclear Physics - Extremes of the Nuclear Landscape -- AUG 30-SEP 05, 2010 -- Zakopane, POLAND, WOS: 000289009300049, A deep-inelastic reaction experiment with a Xe-136 beam impinging on a Pb-208 target was performed. Gamma rays were detected with the AGATA Demonstrator. The beam-like fragments were identified with the PRISMA spectrometer on event-by-event basis. Doppler corrected gamma-ray spectra were obtained for both the identified beam-like nuclei and for the target-like binary partners. This cross-coincidence method can be used to study heavy target-like nuclei which cannot be unambiguously identified in the spectrometer due to their large masses and low velocities., Science and Technology Facilities Council [ST/F006950/1, ST/I504932/1, ST/F012012/1, ST/F004176/1]

A deep-inelastic reaction experiment with a 136Xe beam impinging on a 208Pb target was performed. Gamma rays were detected with the AGATA Demonstrator. The beam-like fragments were identified with the PRISMA spectrometer on event- by-event basis. Doppler corrected \gamma -ray spectra were obtained for both the identified beam-like nuclei and for the target-like binary partners. This cross-coincidence method can be used to study heavy target-like nuclei which cannot be unambiguously identified in the spectrometer due to their large masses and low velocities.

Background: Risdiplam is an orally administered therapy that modifies pre-mRNA splicing of the survival of motor neuron 2 (SMN2) gene and is approved for the treatment of spinal muscular atrophy. The FIREFISH study is investigating the safety and efficacy of risdiplam in treated infants with type 1 spinal muscular atrophy versus historical controls. The primary endpoint of part 2 of the FIREFISH study showed that infants with type 1 spinal muscular atrophy attained the ability to sit without support for at least 5 s after 12 months of treatment. Here, we report on the safety and efficacy of risdiplam in FIREFISH part 2 over 24 months of treatment. Methods: FIREFISH is an ongoing, multicentre, open-label, two-part study. In FIREFISH part 2, eligible infants (aged 1-7 months at enrolment, with a genetically confirmed diagnosis of spinal muscular atrophy, and two SMN2 gene copies) were enrolled in 14 hospitals in ten countries across Europe, North America, South America, and Asia. Risdiplam was orally administered once daily at 0·2 mg/kg for infants between 5 months and 2 years of age; once an infant reached 2 years of age, the dose was increased to 0·25 mg/kg. Infants younger than 5 months started at 0·04 mg/kg (infants between 1 month and 3 months old) or 0·08 mg/kg (infants between 3 months and 5 months old), and this starting dose was adjusted to 0·2 mg/kg once pharmacokinetic data were available for each infant. The primary and secondary endpoints included in the statistical hierarchy and assessed at month 12 have been reported previously. Here we present the remainder of the secondary efficacy endpoints that were included in the statistical hierarchy at month 24: the ability to sit without support for at least 30 s, to stand alone, and to walk alone, as assessed by the Bayley Scales of Infant and Toddler Development, third edition gross motor subscale. These three endpoints were compared with a performance criterion of 5% that was defined based on the natural history of type 1 spinal muscular atrophy; the results were considered statistically significant if the lower limit of the two-sided 90% CI was above the 5% threshold. FIREFISH is registered with ClinicalTrials.gov, NCT02913482. Recruitment is closed; the 36-month extension period of the study is ongoing. Findings: Between March 13 and Nov 19, 2018, 41 infants were enrolled in FIREFISH part 2. After 24 months of treatment, 38 infants were ongoing in the study and 18 infants (44% [90% CI 31-58]) were able to sit without support for at least 30 s (p

The thermal reactions of [NEt4][Fe(CO)4(AuNHC)] [NHC = IMes ([NEt4][1]) or IPr ([NEt4][2]); IMes = C3N2H2(C6H2Me3)2; IPr = C3N2H2(C6H3iPr2)2], Fe(CO)4(AuNHC)2 [NHC = IMes (3) or IPr (4)], Fe(CO)4(AuIMes)(AuIPr) (5), and Fe(CO)4(AuNHC)(AuPPh3) [NHC = IMes (6) or IPr (7)] were investigated in different solvents [CH2Cl2, CH3CN, dimethylformamide, and dimethyl sulfoxide (dmso)] and at different temperatures (50–160 °C) in an attempt to obtain higher-nuclearity clusters. 1 and 2 completely decomposed in refluxing CH2Cl2, resulting in [Fe2(CO)8(AuNHC)]− [NHC = IMes (10) or IPr (11)]. Traces of [Fe3(CO)10(CCH3)]− (12) were obtained as a side product. Conversely, 6 decomposed in refluxing CH3CN, affording the new cluster [Au3{Fe(CO)4}2(PPh3)2]− (15). The relative stability of the two isomers found in the solid state structure of 15 was computationally investigated. 4 was very stable, and only after prolonged heating above 150 °C in dmso was limited decomposition observed, affording small amounts of [Fe3S(CO)9]2– (9), [HFe(CO)4]− (16), and [Au16S{Fe(CO)4}4(IPr)4]n+ (17). A dicationic nature for 17 was proposed on the basis of density functional theory calculations. All of the other reactions examined led to species that were previously reported. The molecular structures of the new clusters 11, 12, 15, and 17 were determined by single-crystal X-ray diffraction as their [NEt4][11]·1.5toluene, [Au(IMes)2][15]·0.67CH2Cl2, [NEt4][12], and [17][BF4]n·solvent salts, respectively., The nuclearity of Au−Fe molecular clusters has been increased by thermal methods, resulting in heterometallic species stabilized by CO, NHC, and phosphine ligands.

The direct reactions of homometallic [Ni6(CO)12]2– and [Pt6(CO)12]2– Chini carbonyl clusters result in heterometallic Ni–Pt Chini-type clusters of the general formula [Pt6–xNix(CO)12]2– (x = 0–6). Their molecular structures have been determined by single-crystal X-ray diffraction (SC-XRD), showing a common octahedral (staggered, D3d) structure analogous to that of [Ni6(CO)12]2–, whereas [Pt6(CO)12]2– displays a trigonal-prismatic (eclipsed, D3h) structure. This structural change after replacing one single Pt with Ni may be classified as an alloying effect, and it has been theoretically investigated by DFT methods. Spectroscopic (IR and 195Pt and 13C NMR) and ESI-MS studies indicate that mixtures of [Pt6–xNix(CO)12]2– (x = 0–6) clusters are actually present in solution, whose compositions may be varied in an almost continuous way. Thus, they may be viewed as random alloy clusters whose overall compositions depend on the stoichiometry of the reagents., Molecular Pt−Ni random alloy clusters adopting a Chini-type structure have been obtained upon mixing related homometallic clusters and investigated by structural, spectroscopic, and theoretical methods.

The reaction of [Co(CO)4]− (1) with M(I) compounds (M = Cu, Ag, Au) was reinvestigated unraveling an unprecedented case of polymerization isomerism. Thus, as previously reported, the trinuclear clusters [M{Co(CO)4}2]− (M = Cu, 2, Ag, 3, Au, 4) were obtained by reacting 1 with M(I) in a 2:1 molar ratio. Their molecular structures were corroborated by single-crystal X-ray diffraction (SC-XRD) on isomorphous [NEt4][M{Co(CO)4}2] salts. [NEt4](3)represented the first structural characterization of 3. More interestingly, changing the crystallization conditions of solutions of 3, the hexanuclear cluster [Ag2{Co(CO)4}4]2− (5) was obtained in the solid state instead of 3. Its molecular structure was determined by SC-XRD as Na2(5)·C4H6O2, [PPN]2(5)·C5H12 (PPN = N(PPh3)2]+), [NBu4]2(5) and [NMe4]2(5) salts. 5 may be viewed as a dimer of 3 and, thus, it represents a rare case of polymerization isomerism (that is, two compounds having the same elemental composition but different molecular weights) in cluster chemistry. The phenomenon was further studied in solution by IR and ESI-MS measurements and theoretically investigated by computational methods. Both experimental evidence and density functional theory (DFT) calculations clearly pointed out that the dimerization process occurs in the solid state only in the case of Ag, whereas Cu and Au related species exist only as monomers.

The molecular nanocluster [Ni36–xPd5+x(CO)46]6– (x = 0.41) (16–) was obtained from the reaction of [NMe3(CH2Ph)]2[Ni6(CO)12] with 0.8 molar equivalent of [Pd(CH3CN)4][BF4]2 in tetrahydrofuran (thf). In contrast, [Ni37–xPd7+x(CO)48]6– (x = 0.69) (26–) and [HNi37–xPd7+x(CO)48]5– (x = 0.53) (35–) were obtained from the reactions of [NBu4]2[Ni6(CO)12] with 0.9–1.0 molar equivalent of [Pd(CH3CN)4][BF4]2 in thf. After workup, 35– was extracted in acetone, whereas 26– was soluble in CH3CN. The total structures of 16–, 26–, and 35– were determined with atomic precision by single-crystal X-ray diffraction. Their metal cores adopted cubic close packed structures and displayed both substitutional and compositional disorder, in light of the fact that some positions could be occupied by either Ni or Pd. The redox behavior of these new Ni–Pd molecular alloy nanoclusters was investigated by cyclic voltammetry and in situ infrared spectroelectrochemistry. All three compounds 16–, 26–, and 35– displayed several reversible redox processes and behaved as electron sinks and molecular nanocapacitors. Moreover, to gain insight into the factors that affect the current–potential profiles, cyclic voltammograms were recorded at both Pt and glassy carbon working electrodes and electrochemical impedance spectroscopy experiments performed for the first time on molecular carbonyl nanoclusters., The synthesis, molecular structure, electrochemical, and infrared spectroelectrochemical behavior of three new atomically precise Ni−Pd alloy carbonyl nanoclusters are reported, together with the first electrochemical impedance spectroscopy investigation of redox active carbonyl nanoclusters.

The reaction of Na[Co(CO)4] with M(IPr)Cl (M = Cu, Ag, and Au; IPr = C3N2H2(C6H3iPr2)2) affords the neutral heterometallic complexes [Co(CO)4{M(IPr)}] (M = Cu, 1; Ag, 2; and Au, 3). Formation of 2 is accompanied by traces of [Ag(IPr)2][Ag{Co(CO)4}2] (4). The reaction of Na[Co(CO)4] with M(IMes)Cl (IMes = C3N2H2(C6H2Me3)2) results in mixtures of [Co(CO)4{M(IMes)}] (M = Cu, 5; Ag, 6; and Au, 7) and [M(IMes)2][M{Co(CO)4}2] (M = Cu, 8; Ag, 9; and Au, 10). In the cases of Cu and Ag, ionic complexes 8 and 9 are the major products, whereas neutral species 7 is the major product for Au. All species 1-10 have been spectroscopically characterized by IR and 1H and 13C{1H} NMR spectroscopy. Moreover, the molecular structures of 2, 3, and 8 have been determined by single-crystal X-ray diffraction (SC-XRD). Bimetallic Co-M-NHC complexes 1-3 and 7-9 have been tested as catalysts for the dehydrogenation of ammonia-borane (AB) in THF as solvent, and their performances compared to [Fe(CO)4{M(NHC)}2], M(NHC)Cl, and Na[Co(CO)4]. DFT computations have been performed to provide information on the structure, IR spectroscopy, and the thermodynamics of Co-M carbonyl clusters.

The reaction of [HFe4(CO)12(IrCOD)]2− (1) with CO at ambient conditions afforded [HFe4Ir(CO)14]2− (2), that, in turn, reacted with HBF4·Et2O affording [Fe4Ir(CO)15]− (3). 1 reacted with a slight excess of PPh3 resulting in a mixture of [HFe2Ir2(CO)10(PPh3)2]− (ca. 37%) (5) and [H2Fe3Ir(CO)10(PPh3)2]− (ca. 63%) (6). 5 and 6 co-crystallized as their [NEt4][H1+xFe2+xIr2-x(CO)10(PPh3)2]·CH2Cl2 (x = 0.63) salt. The reaction of 1 with Au(PPh3)Cl afforded [Fe3Ir(CO)12(AuPPh3)]2− (7). The related hydride [HFe3Ir(CO)12]2− (9) was prepared from the reaction of [HFe4(CO)12]3− (8) with [Ir(COE)2Cl]2 (COE = cyclo-octene). For sake of comparison, [HFe3Co(CO)12]2− (10) was obtained from 8 and Co2(CO)8. All the new clusters have been fully characterized via IR, 1H,13C{1H} and 31P{1H} NMR spectroscopies and their structures determined by means of single crystal X-ray crystallography. Possible isomers have been investigated by DFT calculations.

Carbon-fiber-reinforced polymers (CFRPs) are increasingly used in a variety of applications demanding a unique combination of mechanical properties and lightweight characteristics such as automotive and aerospace, wind turbines, and sport and leisure equipment. This growing use, however, has not yet been accompanied by the setting of an adequate recycling industry, with landfilling still being the main management route for related waste and end-of-life products. Considering the fossil-based nature of carbon fibers, the development of recovery and recycling technologies is hence prioritized to address the environmental sustainability challenges in a bid to approach mitigating the climate emergency and achieving circularity in materials’ life cycles. To this aim, we scaled up and tested a novel semi-industrial pilot plant to pyrolysis and subsequent oxidation of uncured prepreg offcuts and cured waste of CFRPs manufacturing. The environmental performance of the process proposed has been evaluated by means of a life cycle assessment to estimate the associated carbon footprint and cumulative energy demand according to three scenarios. The scale-up of the process has been performed by investigating the influence of the main parameters to improve the quality of the recovered fibers and the setting of preferable operating conditions. The pyro-gasification process attested to a reduction of 40 kgCO2eq per kg of recycled CFs, compared to virgin CFs. If the pyro-gasification process was implemented in the current manufacturing of CFRPs, the estimated reduction of the carbon footprint, depending on the composite breakdown, would result in 12% and 15%. This reduction may theoretically increase up to 59–73% when cutting and trimming waste-optimized remanufacturing is combined with circular economy strategies based on the ideal recycling of CFRPs at end-of-life.

Miscellaneous 2-D molecular alloy clusters of the type [MxM′5-xFe4(CO)16]3- (M, M′ = Cu, Ag, Au; M ≠ M′) have been prepared through the reactions of [Cu3Fe3(CO)12]3-, [Ag4Fe4(CO)16]4- or [M5Fe4(CO)16]3- (M = Cu, Ag) with M′(I) salts (M′ = Cu, Ag, Au). Their formation involves a combination of oxidation, condensation, and substitution reactions. The total structures of several [MxM′5-xFe4(CO)16]3- clusters with different compositions have been determined by means of single crystal X-ray diffraction (SC-XRD) and their nature in solution elucidated by electron spray ionization mass spectrometry (ESI-MS) and IR and UV-visible spectroscopy. Substitutional and compositional disorder is present in the solid state structures, and ESI-MS analyses point out that mixtures of isostructural clusters differing by a few M/M′ coinage metals are present. SC-XRD studies indicate some site preferences of the coinage metals within the metal cores of these clusters, with Au preferentially in corner sites and Cu in the central site. DFT studies give theoretical support to the experimental structural evidence. The site preference is mainly dictated by the strength of the Fe-M bonds that decreases in the order Fe-Au > Fe-Ag > Fe-Cu, and the preferred structure is the one that maximizes the number of stronger Fe-M interactions. Overall, the molecular nature of these clusters allows their structures to be fully revealed with atomic precision, resulting in the elucidation of the bonding parameters that determine the distribution of the different metals within their metal cores.

In the present work, Pt and Pt/Sn nanoparticles (NPs), synthesized from carbonyl cluster precursors were deposited on TiO2 and the resulting materials were tested as catalysts in selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). The work was mainly focused on the study of the formation of bimetallic or mixed oxide-metal nanoparticles on TiO2 starting with Pt/Sn carbonyl clusters and on the structure-activity relationship in the reaction of HMF oxidation in base-free conditions. The developed synthesis procedure allowed to obtain very small mono and bimetallic particles characterized by a narrow particle size distribution. Promising results in base-free FDCA production have been achieved using the prepared samples. In particular, the introduction of Sn in an equimolar amount with Pt improved the catalyst activity as well as its time stability upon operation, demonstrating that the modification of Pt electronic configuration by Sn is a key factor for the mastering of functional performances.