| 1. |
- Di Maria, Francesca, et al.
(författare)
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Controlling the Functional Properties of Oligothiophene Crystalline Nano/Microfibers via Tailoring of the Self-Assembling Molecular Precursors
- 2018
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Ingår i: Advanced Functional Materials. - : John Wiley & Sons. - 1616-301X .- 1616-3028. ; 28:32
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Tidskriftsartikel (refereegranskat)abstract
- Oligothiophenes are π-conjugated semiconducting and fluorescent molecules whose self-assembly properties are widely investigated for application in organic electronics, optoelectronics, biophotonics, and sensing. Here an approach to the preparation of crystalline oligothiophene nano/microfibers is reported based on the use of a “sulfur overrich” quaterthiophene building block, T4S4 , containing in its covalent network all the information needed to promote the directional, π–π stacking-driven, self-assembly of Y-T4S4-Y oligomers into fibers with hierarchical supramolecular arrangement from nano- to microscale. It is shown that when Y varies from unsubstituted thiophene to thiophene substituted with electron-withdrawing groups, a wide redistribution of the molecular electronic charge takes place without substantially affecting the aggregation modalities of the oligomer. In this way, a structurally comparable series of fibers is obtained having progressively varying optical properties, redox potentials, photoconductivity, and type of prevailing charge carriers (from p- to n-type). With the aid of density functional theory (DFT) calculations, combined with powder X-ray diffraction data, a model accounting for the growth of the fibers from molecular to nano- and microscale is proposed
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| 2. |
- Jung, Christian, et al.
(författare)
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A comparison of very old patients admitted to intensive care unit after acute versus elective surgery or intervention
- 2019
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Ingår i: Journal of critical care. - : W B SAUNDERS CO-ELSEVIER INC. - 0883-9441 .- 1557-8615. ; 52, s. 141-148
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Tidskriftsartikel (refereegranskat)abstract
- Background: We aimed to evaluate differences in outcome between patients admitted to intensive care unit (ICU) after elective versus acute surgery in a multinational cohort of very old patients (80 years; VIP). Predictors of mortality, with special emphasis on frailty, were assessed.Methods: In total, 5063 VIPs were induded in this analysis, 922 were admitted after elective surgery or intervention, 4141 acutely, with 402 after acute surgery. Differences were calculated using Mann-Whitney-U test and Wilcoxon test. Univariate and multivariable logistic regression were used to assess associations with mortality.Results: Compared patients admitted after acute surgery, patients admitted after elective surgery suffered less often from frailty as defined as CFS (28% vs 46%; p < 0.001), evidenced lower SOFA scores (4 +/- 5 vs 7 +/- 7; p < 0.001). Presence of frailty (CFS >4) was associated with significantly increased mortality both in elective surgery patients (7% vs 12%; p = 0.01), in acute surgery (7% vs 12%; p = 0.02).Conclusions: VIPs admitted to ICU after elective surgery evidenced favorable outcome over patients after acute surgery even after correction for relevant confounders. Frailty might be used to guide clinicians in risk stratification in both patients admitted after elective and acute surgery.
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| 3. |
- Backes, Claudia, et al.
(författare)
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Production and processing of graphene and related materials
- 2020
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Ingår i: 2D Materials. - : IOP Publishing. - 2053-1583. ; 7:2
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Tidskriftsartikel (refereegranskat)abstract
- We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resource-consuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown. Section VIII discusses advances in GRM functionalization. A broad range of organic molecules can be anchored to the sp(2) basal plane by reductive functionalization. Negatively charged graphene can be prepared in liquid phase (e.g. via intercalation chemistry or electrochemically) and can react with electrophiles. This can be achieved both in dispersion or on substrate. The functional groups of GO can be further derivatized. Graphene can also be noncovalently functionalized, in particular with polycyclic aromatic hydrocarbons that assemble on the sp(2) carbon network by pi-pi stacking. In the liquid phase, this can enhance the colloidal stability of SLG/FLG. Approaches to achieve noncovalent on-substrate functionalization are also discussed, which can chemically dope graphene. Research efforts to derivatize CNMs are also summarized, as well as novel routes to selectively address defect sites. In dispersion, edges are the most dominant defects and can be covalently modified. This enhances colloidal stability without modifying the graphene basal plane. Basal plane point defects can also be modified, passivated and healed in ultra-high vacuum. The decoration of graphene with metal nanoparticles (NPs) has also received considerable attention, as it allows to exploit synergistic effects between NPs and graphene. Decoration can be either achieved chemically or in the gas phase. All LMs,
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| 4. |
- Jin, Lei, et al.
(författare)
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Engineering Interfacial Structure in “Giant” PbS/CdS Quantum Dots for Photoelectrochemical Solar Energy Conversion
- 2016
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Ingår i: Nano Energy. - : Elsevier BV. - 2211-2855. ; 30, s. 531-541
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Tidskriftsartikel (refereegranskat)abstract
- The interfacial structure in “giant” PbS/CdS quantum dots (QDs) was engineered by modulating the Cd:S molar ratio during in situ growth. The control of the gradient interfacial layer could facilitate hole transfer, regulate the transition from double- to single-color emission, as a consequence. These QDs are optically active close-to-the near-infrared (NIR) spectral region and are candidates as absorber materials in solar energy conversion. Photoinduced charge transfer from “giant” QDs to electron scavenger can still take place despite the ultra-thick (~5 nm) shell. The hybrid architecture based on a TiO2 mesoporous framework sensitized by the “giant” QDs with alloyed interface can produce a saturated photocurrent density as high as ~5.3 mA/cm2 in a photoelectrochemical (PEC) cell under 1 Sun illumination, which is around 2 times higher than that of bare PbS and core/thin-shell PbS/CdS QDs sensitizer. The as-prepared PEC device presented very good stability thanks to the “giant” core/shell QDs architecture with tailored interfacial layer and a further coating of the ZnS shell. 78% of the initial current density is kept after 2-hour irradiation at 1 Sun. Engineering of electronic band structure plays a key role in boosting the functional properties of these composite systems, which hold great potential for H2 production in PEC devices.
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| 5. |
- Sirigu, Gianluca, et al.
(författare)
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Ultrafast exciton dynamics in doubly emitting asymmetric giant PbS/CdS/CdS Nanocrystals
- 2015
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Konferensbidrag (refereegranskat)abstract
- Semiconductor nanocrystals (NCs) are interesting optical materials that have been explored for a range of applications such as light emitting diodes (LEDs), photovoltaic cells, lasers and biologic markers. For practical optical uses heterostructured NCs with thick shells (“giant NCs”) offer the advantage of supressed photoluminescence intermittency and reduced rates of Auger recombination. Giant NCs with proper structures can present simultaneous two-colour emission, due to core and shell states [1-2]. These NCs can be convenient for example in very accurate and self-calibrating nanosystems.
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| 6. |
- Zhao, Haiguang, et al.
(författare)
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Dual emission in Asymmetric “Giant” PbS/CdS/CdS Core/Shell/Shell Quantum Dots
- 2016
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Ingår i: Nanoscale. - 2040-3364 .- 2040-3372. ; 8:7, s. 4217-4226
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Tidskriftsartikel (refereegranskat)abstract
- Semiconducting nanocrystals optically active in the infrared region of the electromagnetic spectrum enable exciting avenues in fundamental research and novel applications compatible with the infrared transparency windows of biosystems such as chemical and biological optical sensing, including nanoscale thermometry. In this context, quantum dots (QDs) with double color emission may represent ultra-accurate and self-calibrating nanosystems. We present the synthesis of giant core/shell/shell asymmetric QDs having a PbS/CdS Zincblende (Zb)/CdS Wurtzite (Wz) structure with double color emission close to the near-infrared (NIR)region. We show that the double emission depends on the excitation condition and analyze the electron-hole distribution responsible of the independent and simultaneous radiative exciton recombination in the PbS core and in the CdS Wz shell, respectively. These results highlight the importance of the driving force leading to preferential crystal growth in asymmetric QDs, and provide a pathway for a rational control of the synthesis of double color emitting giant QDs, leading to the effective exploitation of visible/NIR transparency windows.
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| 7. |
- Infantes-Molina, Antonia, et al.
(författare)
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Au-Decorated Ce–Ti Mixed Oxides for Efficient CO Preferential Photooxidation
- 2020
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 12:34, s. 38019-38030
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Tidskriftsartikel (refereegranskat)abstract
- We investigated the photocatalytic behavior of gold nanoparticles supported on CeO2–TiO2 nanostructured matrixes in the CO preferential oxidation in H2-rich stream (photo-CO-PROX), by modifying the electronic band structure of ceria through addition of titania and making it more suitable for interacting with free electrons excited in gold nanoparticles through surface plasmon resonance. CeO2 samples with different TiO2 concentrations (0–20 wt %) were prepared through a slow coprecipitation method in alkaline conditions. The synthetic route is surfactant-free and environmentally friendly. Au nanoparticles (<1.0 wt % loading) were deposited on the surface of the CeO2–TiO2 oxides by deposition–precipitation. A benchmarking sample was also considered, prepared by standard fast coprecipitation, to assess how a peculiar morphology can affect the photocatalytic behavior. The samples appeared organized in a hierarchical needle-like structure, with different morphologies depending on the Ti content and preparation method, with homogeneously distributed Au nanoparticles decorating the Ce–Ti mixed oxides. The morphology influences the preferential photooxidation of CO to CO2 in excess of H2 under simulated solar light irradiation at room temperature and atmospheric pressure. The Au/CeO2–TiO2 systems exhibit much higher activity compared to a benchmark sample with a non-organized structure. The most efficient sample exhibited CO conversions of 52.9 and 80.2%, and CO2 selectivities equal to 95.3 and 59.4%, in the dark and under simulated sunlight, respectively. A clear morphology–functionality correlation was found in our systematic analysis, with CO conversion maximized for a TiO2 content equal to 15 wt %. The outcomes of this study are significant advancements toward the development of an effective strategy for exploitation of hydrogen as a viable clean fuel in stationary, automotive, and portable power generators.
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| 8. |
- Marin, Riccardo, et al.
(författare)
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Mercaptosilane-Passivated CuInS2 Quantum Dots for Luminescence Thermometry and Luminescent Labels
- 2019
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Ingår i: ACS Applied Nano Materials. - : American Chemical Society (ACS). - 2574-0970. ; 2:4, s. 2426-2436
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Tidskriftsartikel (refereegranskat)abstract
- Bright and nontoxic quantum dots (QDs) are highly desirable in a variety of applications, from solid-state devices to luminescent probes in assays. However, the processability of these species is often curbed by their surface chemistry, which limits their dispersibility in selected solvents. This renders a surface modification step often mandatory to make the QDs compatible with the solvent of interest. Here, we present a new synthetic approach to produce CuInS2 QDs compatible with organic polar solvents and readily usable for the preparation of composite materials. 3-Mercaptopropyl trimethoxysilane (MPTS) was used simultaneously as solvent, sulfur source, and capping agent for the QD synthesis. The synthesized QDs possessed a maximum photoluminescence quantum yield around 6%, reaching approximately 55% after growing a ZnS shell. The partial condensation of MPTS molecules on the surface of QDs was probed by solid-state nuclear magnetic resonance, whose results were used to interpret the interaction of the QDs with different solvents. To prove the versatility of the developed QDs, imparted by the thiolated silane molecules, we prepared via straightforward procedures two nanocomposites of practical interest: (i) silica nanoparticles decorated with QDs and (ii) an inexpensive polymeric film with embedded QDs. We further demonstrate the potential of this composite film as a luminescence thermometer operational over a broad temperature interval, with relative thermal sensitivity above 1% K–1 in the range of biological interest.
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| 9. |
- Salvestrini, Viola, et al.
(författare)
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Safety profile of trastuzumab-emtansine (T-DM1) with concurrent radiation therapy : A systematic review and meta-analysis
- 2023
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Ingår i: Radiotherapy and Oncology. - : ELSEVIER IRELAND LTD. - 0167-8140 .- 1879-0887. ; 186
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Forskningsöversikt (refereegranskat)abstract
- Background and Purpose: In recent years, the treatment landscape for breast cancer has undergone significant advancements, with the introduction of several new anticancer agents. One such agent is trastuzumab emtansine (T-DM1), an antibody drug conjugate that has shown improved outcomes in both early and advanced breast cancer. However, there is currently a lack of comprehensive evidence regarding the safety profile of combining T-DM1 with radiation therapy (RT). In this study, we aim to provide a summary of the available data on the safety of combining RT with T-DM1 in both early and metastatic breast cancer settings. Materials and Methods: This systematic review and meta-analysis project is part of the consensus recommendations by the European Society for Radiotherapy and Oncology (ESTRO) Guidelines Committee on integrating RT with targeted treatments for breast cancer. A thorough literature search was conducted using the PUBMED/MedLine, Embase, and Cochrane databases to identify original studies focusing on the safety profile of combining T-DM1 with RT. Results: After applying eligibility criteria, nine articles were included in the meta-analysis. Pooled data from these studies revealed a high incidence of grade 3 + radionecrosis (17%), while the rates of grade 3 + radiation-related pneumonitis (<1%) and skin toxicity (1%) were found to be very low. Conclusion: Although there is some concern regarding a slight increase in pneumonitis when combining T-DM1 with postoperative RT, the safety profile of this combination was deemed acceptable for locoregional treatment in non-metastatic breast cancer. However, caution is advised when irradiating intracranial sites concurrently with T-DM1. There is a pressing need for international consensus guidelines regarding the safety considerations of combining T-DM1 and RT for breast cancer.
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| 10. |
- Xia, Zhenyuan, 1983, et al.
(författare)
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Dispersion Stability and Surface Morphology Study of Electrochemically Exfoliated Bilayer Graphene Oxide
- 2019
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 123:24, s. 15122-15130
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Tidskriftsartikel (refereegranskat)abstract
- During the last decade, electrochemical exfoliation of graphite has aroused great interest from both academia and industry for mass production of graphene sheets. Electrochemically exfoliated graphene oxide (EGO) features a much better tunability than chemically EGO, or even than graphene obtained with ultrasonic exfoliation. Chemical and electrical properties of EGO can be modified extensively, thanks to its step-controllable oxidation process, varying the electrolytes and/or the applied potential. It is thus possible, using tunable electrochemical oxidation, to produce low-defect EGO sheets, featuring both good electric conductivity and good dispersibility in common solvents (e.g., acetonitrile or isopropanol). This greatly facilitates its application in several fields, for example, in flexible electronics. In this work, we correlate the dispersion behavior of EGO with its chemical properties using the relative Hansen solubility parameter, zeta potential values, X-ray photoemission spectroscopy, and Raman analysis. A surface morphology study by atomic force microscopy and transmission electron microscopy analyses also reveals that EGO sheets are multiple structures of (partially oxidized) graphene bilayers. Conductive EGO films could be easily prepared by vacuum filtration on different substrates, obtaining electrical conductivity values of up to ∼104 S/m with no need for further reduction procedures.
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