| 1. |
- Ferrando, Carlos, et al.
(författare)
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Effects of oxygen on post-surgical infections during an individualised perioperative open-lung ventilatory strategy : a randomised controlled trial
- 2020
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Ingår i: British Journal of Anaesthesia. - : ELSEVIER SCI LTD. - 0007-0912 .- 1471-6771. ; 124:1, s. 110-120
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Tidskriftsartikel (refereegranskat)abstract
- Background: We aimed to examine whether using a high fraction of inspired oxygen (FIO2) in the context of an individualised intra- and postoperative open-lung ventilation approach could decrease surgical site infection (SSI) in patients scheduled for abdominal surgery. Methods: We performed a multicentre, randomised controlled clinical trial in a network of 21 university hospitals from June 6, 2017 to July 19, 2018. Patients undergoing abdominal surgery were randomly assigned to receive a high (0.80) or conventional (0.3) FIO2 during the intraoperative period and during the first 3 postoperative hours. All patients were mechanically ventilated with an open-lung strategy, which included recruitment manoeuvres and individualised positive end-expiratory pressure for the best respiratory-system compliance, and individualised continuous postoperative airway pressure for adequate peripheral oxyhaemoglobin saturation. The primary outcome was the prevalence of SSI within the first 7 postoperative days. The secondary outcomes were composites of systemic complications, length of intensive care and hospital stay, and 6-month mortality. Results: We enrolled 740 subjects: 371 in the high FIO2 group and 369 in the low FIO2 group. Data from 717 subjects were available for final analysis. The rate of SSI during the first postoperative week did not differ between high (8.9%) and low (9.4%) FIO2 groups (relative risk [RR]: 0.94; 95% confidence interval [CI]: 0.59-1.50; P=0.90]). Secondary outcomes, such as atelectasis (7.7% vs 9.8%; RR: 0.77; 95% CI: 0.48-1.25; P=0.38) and myocardial ischaemia (0.6% [n=2] vs 0% [n=0]; P=0.47) did not differ between groups. Conclusions: An oxygenation strategy using high FIO2 compared with conventional FIO2 did not reduce postoperative SSIs in abdominal surgery. No differences in secondary outcomes or adverse events were found.
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| 2. |
- Erbing, Elis, et al.
(författare)
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General, Simple, and Chemoselective Catalysts for the Isomerization of Allylic Alcohols : The Importance of the Halide Ligand
- 2016
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 22:44, s. 15659-15663
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Tidskriftsartikel (refereegranskat)abstract
- Remarkably simple Ir-III catalysts enable the isomerization of primary and sec-allylic alcohols under very mild reaction conditions. X-ray absorption spectroscopy (XAS) and mass spectrometry (MS) studies indicate that the catalysts, with the general formula [Cp*Ir-III], require a halide ligand for catalytic activity, but no additives or additional ligands are needed.
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| 3. |
- Bermejo Gomez, Antonio, et al.
(författare)
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Iridium-Catalyzed Isomerization/Bromination of Allylic Alcohols : Synthesis of alpha-Bromocarbonyl Compounds
- 2014
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 20:34, s. 10703-10709
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Tidskriftsartikel (refereegranskat)abstract
- alpha-Brominated ketones and aldehydes, with two adjacent electrophilic carbon atoms, are highly valuable synthetic intermediates in organic synthesis, however, their synthesis from unsymmetrical ketones is very challenging, and current methods suffer from low selectivity. We present a new, reliable, and efficient method for the synthesis of alpha-bromocarbonyl compounds in excellent yields and with excellent selectivities. Starting from allylic alcohols as the carbonyl precursors, the combination of a 1,3-hydrogen shift catalyzed by iridium(III) with an electrophilic bromination gives alpha-bromoketones and aldehydes in good to excellent yields. The selectivity of the process is determined by the structure of the starting allylic alcohol; thus, alpha-bromoketones formally derived from unsymmetrical ketones can be synthesized in a straightforward and selective manner.
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| 4. |
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| 5. |
- Carboni, Andrea, et al.
(författare)
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Success and Hindrance Factors of AHA-Oriented Open Service Platforms
- 2021
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Ingår i: ADVANCES IN COMPUTATIONAL COLLECTIVE INTELLIGENCE (ICCCI 2021). - Cham : SPRINGER INTERNATIONAL PUBLISHING AG. - 9783030881139 - 9783030881122 ; , s. 656-668
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Konferensbidrag (refereegranskat)abstract
- In the past years, there has been a flourishing of platforms dedicated to Active Assisted Living (AAL) and Active and Healthy Ageing (AHA). Most of them feature as their core elements intelligent systems for the analysis of multisource and multimodal data coming from sensors of various nature inserted in suitable IoT ecosystems. While progress in signal processing and artificial intelligence has shown how these platforms may have a great potential in improving the daylife of seniors or frail subjects, there are still several technological and non-technological barriers that should be torn down before full uptake of the existing solutions. In this paper, we address specifically this issue describing the outcome and creation process of a methodology aimed at evaluating the successful uptake of existing platforms in the field of AHA. We propose a pathway (as part of an overarching methodology) to define and select for Key Performance Indicators (KPIs), taking into account an extensive amount of parameters related to success, uptake and evolution of platforms. For this, we contribute a detailed analysis structured along with the 4 main actions of mapping, observing, understanding, and defining. Our analysis focuses on Platforms, defined as operating environments, under which various applications, agents and intelligent services are designed, implemented, tested, released and maintained. By following the proposed pathway, we were able to define a practical and effective methodology for monitoring and evaluating the uptake and other success indicators of AHA platforms. Besides, by the same token, we were able to provide guidelines and best practices for the development of the next-generation platforms in the AHA domain.
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| 6. |
- Carson, Fabian, et al.
(författare)
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Influence of the Base on Pd@MIL-101-NH2(Cr) as Catalyst for the Suzuki-Miyaura Cross-Coupling Reaction
- 2015
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 21:30, s. 10896-10902
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Tidskriftsartikel (refereegranskat)abstract
- The chemical stability of metal-organic frameworks (MOFs) is a major factor preventing their use in industrial processes. Herein, it is shown that judicious choice of the base for the Suzuki-Miyaura cross-coupling reaction can avoid decomposition of the MOF catalyst Pd@MIL-101-NH2(Cr). Four bases were compared for the reaction: K2CO3, KF, Cs2CO3 and CsF. The carbonates were the most active and achieved excellent yields in shorter reaction times than the fluorides. However, powder XRD and N-2 sorption measurements showed that the MOF catalyst was degraded when carbonates were used but remained crystalline and porous with the fluorides. XANES measurements revealed that the trimeric chromium cluster of Pd@MIL-101-NH2(Cr) is still present in the degraded MOF. In addition, the different countercations of the base significantly affected the catalytic activity of the material. TEM revealed that after several catalytic runs many of the Pd nanoparticles (NPs) had migrated to the external surface of the MOF particles and formed larger aggregates. The Pd NPs were larger after catalysis with caesium bases compared to potassium bases.
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| 7. |
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| 8. |
- González Miera, Greco, 1983-, et al.
(författare)
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Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange
- 2017
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 56:8, s. 4576-4583
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Tidskriftsartikel (refereegranskat)abstract
- Here we describe the topological transformation of the pores of a new framework in the bio-MOF-100 family (dia-c) into the known isomer (lcs) by doubling the pore volume, which occurs during postsynthesis modifications. During this transformation, reassembling of the metal–organic framework (MOF) building blocks into a completely different framework occurs, involving breaking/forming of metal–ligand bonds. MOF crystallinity and local structure are retained, as determined by powder X-ray diffraction (PXRD) and pair distribution function (PDF) analyses, respectively. We exploited the inherent dynamism of bio-MOF-100 by coupling chemical decorations of the framework using solvent-assisted ligand exchange to the topological change. Following this method and starting from the pristine dense dia-c phase, open lcs-bio-MOF-100 was prepared and functionalized in situ with an iridium complex (IrL). Alternatively, the dia-c MOF could be modified with wide-ranging amounts of IrL up to ca. 50 mol %, as determined by solution 1H NMR spectroscopy, by tuning the concentration of the solutions used and with no evidence for isomer transformation. The single-site nature of the iridium complexes within the MOFs was assessed by X-ray absorption spectroscopy (XAS) and PDF analyses. Ligand exchanges occurred quantitatively at room temperature, with no need of excess of the iridium metallolinker.
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| 9. |
- Koleček, Jaroslav, et al.
(författare)
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Cross-continental migratory connectivity and spatiotemporal migratory patterns in the great reed warbler
- 2016
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Ingår i: Journal of Avian Biology. - : Wiley. - 0908-8857 .- 1600-048X. ; 47:6, s. 756-767
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Tidskriftsartikel (refereegranskat)abstract
- Migratory connectivity describes to which degree different breeding populations have distinct (non-overlapping) non-breeding sites. Uncovering the level of migratory connectivity is crucial for effective conservation actions and for understanding of the evolution of local adaptations and migratory routes. Here we investigate migration patterns in a passerine bird, the great reed warbler Acrocephalus arundinaceus, over its wide Western Palearctic breeding range using geolocators from Spain, Sweden, Czech Republic, Bulgaria and Turkey. We found moderate migratory connectivity: a highly significant spatial structure in the connections between breeding and sub-Saharan non-breeding grounds, but at the same time a partial overlap between individual populations, particularly along the Gulf of Guinea where the majority of birds from the Spanish, Swedish and Czech populations spent their non-breeding period. The post-breeding migration routes were similar in direction and rather parallel for the five populations. Birds from Turkey showed the most distinctive migratory routes and sub-Saharan non-breeding range, with a post-breeding migration to east Africa and, together with birds from Bulgaria, a previously unknown pre-breeding migration over the Arabian Peninsula indicating counter-clockwise loop migration. The distances between breeding and sub-Saharan non-breeding sites, as well as between first and final sub-Saharan non-breeding sites, differed among populations. However, the total speed of migration did not differ significantly between populations; neither during post-breeding migration in autumn, nor pre-breeding migration in spring. There was also no significant relationship between the total speed of migration and distance between breeding and non-breeding sites (neither post- nor pre-breeding) and, surprisingly, the total speed of migration generally did not differ significantly between post-breeding and pre-breeding migration. Future challenges include understanding whether non-breeding environmental conditions may have influenced the differences in migratory patterns that we observed between populations, and to which extent non-breeding habitat fluctuations and loss may affect population sizes of migrants.
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| 10. |
- Martinez-Erro, Samuel, et al.
(författare)
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2,2-Diiododimedone : a mild electrophilic iodinating agent for the selective synthesis of alpha-iodoketones from allylic alcohols
- 2017
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Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1359-7345 .- 1364-548X. ; 53:71, s. 9842-9845
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Tidskriftsartikel (refereegranskat)abstract
- 2,2-Diiodo-5,5-dimethylcyclohexane-1,3-dione is reported as a new electrophilic iodinating agent that selectively iodinates electron-rich aromatics. In contrast to other common electrophilic iodinating reagents, its mild nature allows it to be used for the selective synthesis of alpha-iodinated carbonyl compounds from allylic alcohols through a 1,3-hydrogen shift/iodination process catalyzed by iridium(III) complexes.
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| 11. |
- Martinez-Erro, Samuel, et al.
(författare)
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Base-Catalyzed Stereospecific Isomerization of Electron-Deficient Allylic Alcohols and Ethers through Ion-Pairing
- 2016
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 138:40, s. 13408-13414
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Tidskriftsartikel (refereegranskat)abstract
- A mild base-catalyzed strategy for the isomerization of allylic alcohols and allylic ethers has been developed. Experimental and computational investigations indicate that transition metal catalysts are not required when basic additives are present. As in the case of using transition metals under basic conditions, the isomerization catalyzed solely by base also follows a stereospecific pathway. The reaction is initiated by a rate-limiting deprotonation. Formation of an intimate ion pair between an allylic anion and the conjugate acid of the base results in efficient transfer of chirality. Through this mechanism, stereochemical information contained in the allylic alcohols is transferred to the ketone products. The stereospecific isomerization is also applicable for the first time to allylic ethers, yielding synthetically valuable enantioenriched (up to 97% ee) enol ethers.
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| 12. |
- Morganti, Michelangelo, et al.
(författare)
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Effect of light-level geolocators on apparent survival of two highly aerial swift species
- 2018
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Ingår i: Journal of Avian Biology. - : Wiley. - 0908-8857. ; 49:1
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Tidskriftsartikel (refereegranskat)abstract
- Light-level geolocators are currently widely used to track the migration of small-sized birds, but their potentially detrimental effects on survival of highly aerial species have been poorly investigated so far. We recorded capture–recapture histories of 283 common swifts Apus apus and 107 pallid swifts Apus pallidus breeding in 14 colonies in Italy, Spain, Sweden and Switzerland that were equipped with 10 different types of geolocators (‘geolocator birds’), and compared their survival with that of, respectively, 215 common and 101 pallid swifts not equipped with geolocators (‘control birds’). Data were analysed using both GLMMs with return rate as a proxy for survival and mark–recapture models to estimate survival while accounting for recapture probability. In all the analyses, geolocator birds showed reduced apparent survival compared to controls. Geolocator weight was always lower than 3% of body mass, and did not affect survival per se. Geolocators with a light-stalk, which is used in some geolocator models to reduce light sensor shading by feathers, decreased apparent survival more than models without light-stalk. Apparent survival of geolocator birds significantly varied among sites, being much higher in northern Europe. Despite in our analyses we could only partly account for variable recapture probabilities among sites and for inter-annual variability in survival, our results generally showed that equipping swifts with geolocators decreased their survival prospects, but also that the magnitude of this effect may depend on species-specific traits. These conclusions are in line with those of other studies on aerial foragers. We suggest that future studies tracking the movements of aerial insectivorous birds should use devices designed to minimize drag.
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| 13. |
- Pascanu, Vlad, et al.
(författare)
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Double-Supported Silica-Metal-Organic Framework Palladium Nanocatalyst for the Aerobic Oxidation of Alcohols under Batch and Continuous Flow Regimes
- 2015
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Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 5:2, s. 472-479
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Tidskriftsartikel (refereegranskat)abstract
- Stable and easily synthesized metal-organic framework MIL-88B-NH2 represents an attractive support for catalysts employed in oxidation reactions, which are typically performed under relatively harsh conditions. However, MIL-88B-NH2, the thermodynamic polymorph of the more popular MIL-101-NH2, has been rarely employed in catalytic applications because of a difficult impregnation process caused by the flexible nature of the framework. We report herein a new catalyst denoted Pd@MIL-88B-NH2 (8 wt % Pd), the first example of metallic nanoparticles successfully impregnated in the pores of MIL-88B-NH2. Furthermore, by enclosing the MOF crystals in a tailored protective coating of SiO2 nanoparticles, an even more enduring material was developed and applied to the aerobic oxidation of benzylic alcohols. This doubly supported catalyst Pd@MIL-88B-NH2@nano-SiO2 displayed high activity and excellent performance in terms of endurance and leaching control. Under batch conditions, a very convenient and efficient recycling protocol is illustrated, using a teabag approach. Under continuous flow, the catalyst was capable of withstanding 7 days of continuous operation at 110 degrees C without deactivation. During this time, no leaching of metallic species was observed, and the material maintained its structural integrity.
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| 14. |
- Pascanu, Vlad, et al.
(författare)
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Highly Functionalized Biaryls via Suzuki-Miyaura Cross-Coupling Catalyzed by Pd@MOF under Batch and Continuous Flow Regimes
- 2015
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 8:1, s. 123-130
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Tidskriftsartikel (refereegranskat)abstract
- A diverse set of more than 40 highly functionalized biaryls was synthesized successfully through the Suzuki-Miyaura cross-coupling reaction catalyzed by Pd nanoparticles supported in a functionalized mesoporous MOF (8 wt% Pd@MIL-101(Cr)-NH2). This could be achieved under some of the mildest conditions reported to date and a strong control over the leaching of metallic species could be maintained, despite the presence of diverse functional groups and/or several heteroatoms. Some of the targeted molecules are important intermediates in the synthesis of pharmaceuticals and we clearly exemplify the versatility of this catalytic system, which affords better yields than currently existing commercial procedures. Most importantly, Pd@MIL-101-NH2 was packed in a micro-flow reactor, which represents the first report of metallic nanoparticles supported on MOFs employed in flow chemistry for catalytic applications. A small library of 11 isolated compounds was created in a continuous experiment without replacing the catalyst, demonstrating the potential of the catalyst for large-scale applications.
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| 15. |
- Platero-Prats, Ana E., et al.
(författare)
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Functionalising metal-organic frameworks with metal complexes : the role of structural dynamics
- 2015
-
Ingår i: CrystEngComm. - : Royal Society of Chemistry (RSC). - 1466-8033. ; 17:40, s. 7632-7635
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Tidskriftsartikel (refereegranskat)abstract
- A series of iridium-functionalised UiO-67 metal-organic frameworks (MOFs) were synthesised under conditions that simulate kinetically- and thermodynamically-controlled regimes. The degree of functionalisation depends on the reaction time and relative acidity of the native- and metallo-linkers, and can be optimised by controlling the reaction time.
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| 16. |
- Platero-Prats, Ana E., et al.
(författare)
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The First One-Pot Synthesis of Metal-Organic Frameworks Functionalised with Two Transition-Metal Complexes
- 2015
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Ingår i: Chemistry - A European Journal. - : Wiley-VCH Verlagsgesellschaft. - 0947-6539 .- 1521-3765. ; 21:2, s. 861-866
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis of a metal-organic framework (UiO-67) functionalised simultaneously with two different transition metal complexes (Ir and Pd or Rh) through a one-pot procedure is reported for the first time. This has been achieved by an iterative modification of the synthesis parameters combined with characterisation of the resulting materials using different techniques, including X-ray absorption spectroscopy (XAS). The method also allows the first synthesis of UiO-67 with a very wide range of loadings (from 4 to 43 mol%) of an iridium complex ([IrCp*(bpydc)(Cl)Cl](2-); bpydc=2,2'-bipyridine-5,5'-dicarboxylate, Cp* = pentamethylcyclopentadienyl) through a pre-functionalisation methodology.
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| 17. |
- Postigo, Andrea, et al.
(författare)
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Assessment Of Blood Flow Transport In The Left Ventricle Using Ultrasound. Validation Against 4-D Flow Cardiac Magnetic Resonance
- 2022
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Ingår i: Ultrasound in Medicine and Biology. - : Elsevier Science Inc. - 0301-5629 .- 1879-291X. ; 48:9, s. 1822-1832
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Tidskriftsartikel (refereegranskat)abstract
- Four-dimensional flow cardiac magnetic resonance (CMR) is the reference technique for analyzing blood transport in the left ventricle (LV), but similar information can be obtained from ultrasound. We aimed to validate ultrasound-derived transport in a head-to-head comparison against 4D flow CMR. In five patients and two healthy volunteers, we obtained 2D + t and 3D + t (4D) flow fields in the LV using transthoracic echocardiog-raphy and CMR, respectively. We compartmentalized intraventricular blood flow into four fractions of end -dia-stolic volume: direct flow (DF), retained inflow (RI), delayed ejection flow (DEF) and residual volume (RV). Using ultrasound we also computed the properties of LV filling waves (percentage of LV penetration and percent-age of LV volume carried by E/A waves) to determine their relationships with CMR transport. Agreement between both techniques for quantifying transport fractions was good for DF and RV (Ric [95% confidence inter-val]: 0.82 [0.33, 0.97] and 0.85 [0.41, 0.97], respectively) and moderate for RI and DEF (Ric= 0.47 [-0.29, 0.88] and 0.55 [-0.20, 0.90], respectively). Agreement between techniques to measure kinetic energy was variable. The amount of blood carried by the E-wave correlated with DF and RV (R = 0.75 and R = 0.63, respectively). There-fore, ultrasound is a suitable method for expanding the analysis of intraventricular flow transport in the clinical setting. (E-mail: javier.bermejo@salud.madrid.org) (c) 2022 The Author(s). Published by Elsevier Inc. on behalf of World Federation for Ultrasound in Medicine & Biology.
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| 18. |
- Vazquez-Romero, Ana, et al.
(författare)
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Acid- and Iridium-Catalyzed Tandem 1,3-Transposition/3,1-Hydrogen Shift/Chlorination of Allylic Alcohols
- 2015
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Ingår i: ACS Catalysis. - : American Chemical Society (ACS). - 2155-5435. ; 5:2, s. 708-714
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Tidskriftsartikel (refereegranskat)abstract
- A method for the selective synthesis of alpha-chlorocarbonyls from allylic alcohols is presented. The reaction occurs through an acid- and iridium-catalyzed tandem process that combines a 1,3-transposition, a 3,1-hydrogen shift, and a chlorination process, and can be applied to a wide range of alpha-aromatic and heteroaromatic secondary allylic alcohols. Saturated non-chlorinated ketones or other side-products derived from overchlorination were not detected.
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| 19. |
- Åkesson, Susanne, et al.
(författare)
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Evolution of chain migration in an aerial insectivorous bird, the common swift Apus apus
- 2020
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Ingår i: Evolution. - : Wiley. - 0014-3820 .- 1558-5646. ; 74:10, s. 2377-2391
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Tidskriftsartikel (refereegranskat)abstract
- Spectacular long-distance migration has evolved repeatedly in animals enabling exploration of resources separated in time and space. In birds, these patterns are largely driven by seasonality, cost of migration, and asymmetries in competition leading most often to leapfrog migration, where northern breeding populations winter furthest to the south. Here, we show that the highly aerial common swift Apus apus, spending the nonbreeding period on the wing, instead exhibits a rarely found chain migration pattern, where the most southern breeding populations in Europe migrate to wintering areas furthest to the south in Africa, whereas the northern populations winter to the north. The swifts concentrated in three major areas in sub-Saharan Africa during the nonbreeding period, with substantial overlap of nearby breeding populations. We found that the southern breeding swifts were larger, raised more young, and arrived to the wintering areas with higher seasonal variation in greenness (Normalized Difference Vegetation Index) earlier than the northern breeding swifts. This unusual chain migration pattern in common swifts is largely driven by differential annual timing and we suggest it evolves by prior occupancy and dominance by size in the breeding quarters and by prior occupancy combined with diffuse competition in the winter.
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