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New Insights Into the Growth Mechanism of Ultrathin Au Nanowires from Combined In-Situ EXAFS and SAXS Studies
摘要： The synthesis at room temperature of Au nanowires (NWs) in hexane solution of HAuCl4.3H2O, oleylamine and triisopropylsilane, was “in-situ” monitored by means of X-ray Absorption Fine Structure Spectroscopies and Small Angle X-Ray Scattering to determine, under identical synthesis conditions, both the changes of the oxidation state of gold atoms and the evolution of the size and shape of the objects involved in the formation of Au NWs. We propose a multi-stage process for the formation of the NWs: first, Au(III) atoms form a planar-square geometry complex that is continuously reduced to give Au(I) disc-like structures with diameters bigger than that of the final NWs. In a second stage, characteristic length/thickness ratio of these disc-like objects increases to form cylinders, presumably by aurophilic interactions between Au(I) centers and stacking of the discs. When most of the Au atoms have been reduced to Au(I), the reduction to Au(0) begins (third stage) and the NWs grow forming an hexagonal arrangement, separated by a bilayer of oleylamine molecules (fourth stage). Finally, a slow reduction leads the reaction to the final product, formed by bundles of long, ultrathin Au NWs.
关键词： triisopropylsilane,in-situ EXAFS,growth mechanism,SAXS,Au nanowires,oleylamine
更新于2025-09-23 15:21:21
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Evolution of Size and Optical Properties of Upconverting Nanoparticles during High Temperature Synthesis
摘要： We investigated the growth of β-phase NaYF4:Yb3+,Er3+ upconversion nanoparticles synthesized by the thermal decomposition method using a combination of in situ and offline analytical methods for determining the application-relevant optical properties, size, crystal phase, and chemical composition. This included in situ steady state luminescence in combination with offline time-resolved luminescence spectroscopy, as well as small-angle X-ray scattering (SAXS) transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), and inductively coupled plasma optical emission spectrometry (ICP-OES). For assessing the suitability of our optical monitoring approach, the in situ collected spectroscopic data, that reveal the luminescence evolution during nanocrystal synthesis, were compared to measurements done after cooling of the reaction mixture of the as-synthesized particles. The excellent correlation of the in situ and time-resolved upconversion luminescence with the nanoparticle sizes determined during the course of the reaction provides important insights into the various stages of nanoparticle growth. This study highlights the capability of in situ luminescence monitoring to control the efficiency of UCNP synthesis, particularly the reaction times at elevated temperatures and the particle quality in terms of size, shape and crystall structure, as well as luminescence lifetime and upconversion quantum yield.
关键词： thermal decomposition,XRD,ICP-OES,TEM,in situ luminescence,SAXS,upconversion nanoparticles
更新于2025-09-23 15:21:01
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Isothermal crystallization of poly(glycolic acid) studied by terahertz and infrared spectroscopy and SAXS/WAXD simultaneous measurements
摘要： Isothermal crystallization of poly(glycolic acid) (PGA) has been studied using terahertz (THz) and infrared (IR) spectroscopy and simultaneous small-angle X-ray scattering (SAXS)/wide-angle X-ray diffraction (WAXD) measurements. Changes in the intermolecular interactions in PGA during the isothermal crystallization were monitored using THz spectroscopy, which is an efficient technique for analyzing the higher-order structure of polymers. In the THz spectra, the temporal difference in the intensity observed in the isothermal crystallization is due to the difference in the vibrational origins of two bands at 192 and 65 cm?1. The band at 192 cm?1 primarily originates from the intramolecular vibrational mode (twisting of the local structure of the PGA molecular chain). Furthermore, the band at 65 cm?1 exists due to the intermolecular vibration mode (C = O···H-C hydrogen bonds between polymer chains). In addition, these THz bands appeared after the appearance of the SAXS and WAXD peaks. When a lamellar structure is formed and the molecular chains are oriented, the THz band originating from the intermolecular vibration is observed. It is highly possible that the intermolecular vibration appearing in the THz spectra requires the molecular chains to be oriented.
关键词： Terahertz spectroscopy,Intermolecular interactions,Infrared spectroscopy,Isothermal crystallization,SAXS/WAXD,Poly(glycolic acid)
更新于2025-09-10 09:29:36
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Thermal behavior of poly(VDF-ter-TrFE-ter-CTFE) copolymers: Influence of CTFE termonomer on the crystal-crystal transitions
摘要： Depending on their CTFE content (from 0 to 10 mol %), poly (VDF-ter-TrFE-ter-CTFE), poly(vinylidene fluoride-ter-trifluoroethylene-ter-chlorotrifluoroethylene) copolymers exhibit ferroelectric (FE) or relaxor ferroelectric (RFE) properties at low temperature whereas they all present paraelectric (PE) behavior at high temperature. This thermal evolution of their electro-active properties is related to reversible crystal-crystal transitions. We studied these structural transitions for three different copolymers with various amount of CTFE (0, 4.4 and 9.7 mol %) using simultaneous SAXS-WAXS experiments along thermal cycles. We identified two types of crystalline phase at low temperature with their proper crystal-crystal transition: the first one containing all-trans conformations (orthorhombic FE phase) has a discontinuous transition towards the hexagonal PE phase, the second one which incorporates gauche disordered conformations (orthorhombic DFE (Defective Ferroelectric) or RFE) transits continuously towards the same hexagonal PE phase. For the intermediate composition (4.4 mol % CTFE), we observe the coexistence of these two simultaneous phase transitions, one discontinuous (FE to PE) and one continuous (RFE to PE), whereas only the continuous one exists in the higher CTFE composition (9.7 mol %). Relaxor ferroelectric properties are precisely observed in the temperature range of the structural RFE to PE transition [0 °C, 40 °C], highlighting the importance of this crystal-crystal transition. By coupling electric displacement?electric field (D?E) loop measurements, thermo-mechanical experiments (DSC and DMA) and dielectric spectroscopy, we propose a model to explain this RFE-PE continuous crystal-crystal transition in terpolymers.
关键词： Structural transition,Electro-active terpolymer,SAXS-WAXS
更新于2025-09-10 09:29:36
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Irradiation Effects on Polymer-Grafted Gold Nanoparticles for Cancer Therapy
摘要： In the context of cancer treatment, gold nanoparticles (AuNPs) are considered as very promising radiosensitizers. Here, well-defined polymer-grafted AuNPs were synthesized and studied under gamma irradiation to better understand the involved radiosensitizing mechanisms. First, various water-soluble and well-defined thiol-functionalized homopolymers and copolymers were obtained through Atom Transfer Radical Polymerization. They were then used as ligands in the one-step synthesis of AuNPs, resulting in stable hybrid metal-polymer nanoparticles. Second, these nano-objects were irradiated in solution by gamma rays at different doses. Structures were fully characterized through SEC, SAXS and SANS measurements, prior and after irradiation. We were thus able to quantify and to localize radiation impacts onto the grafted polymers, revealing the production sites of reactive species around AuNPs. Both external and near-surface scissions were observed. Interestingly, the ratio between these two effects was found to vary according to the nature of polymer ligands. Medium-range and long-distance dose enhancements could not be identified from the calculated scission yields, but several mechanisms were considered to explain high yields found for near-surface scissions. Then, cytotoxicity was shown to be equivalent for both non-irradiated and irradiated polymer-grafted NPs, suggesting that released polymer fragments were non-toxic. Finally, the potential to add bioactive molecules such as anticancer drugs has been explored by grafting doxorubicin (DOX) onto the polymer corona. This may lead to nano-objects combining both radiosensitization and chemotherapy effects. This work is the first one to study in details the impact of radiation on radiosensitizing nano-objects combining physical, chemical and biological analyses.
关键词： irradiation,Polymer-grafted AuNPs,radiosensitization,doxorubicin,cytotoxicity,SAXS,SANS
更新于2025-09-09 09:28:46
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X-ray study of anisotropically shaped metal halide perovskite nanoparticles in tubular pores
摘要： Recently, we have reported that metal halide perovskite nanoparticles formed in nanoporous alumina and silicon thin films exhibit blue shifted photoluminescence due to spatial confinement, thus allowing for color tuning of the emission by varying the pore size. While perovskite nanoparticles grown in nanoporous alumina films have been integrated into LEDs, similar approaches have failed with silicon. Here, we report the results of investigating the structure of the alumina pore system and the perovskite crystallites forming within. We use two x-ray diffraction techniques, namely, small-angle x-ray scattering (SAXS) and high-energy microbeam wide-angle x-ray scattering (WAXS). SAXS reveals that the alumina pore system diffracts like regularly arranged tubes with the average diameter and nearest neighbor distance of 12 nm and 20 nm, respectively. High-energy microbeam WAXS shows that perovskite nanoparticles within the nanoporous alumina have a distinctly anisotropic shape with the average particle length along and perpendicular to the pore axis of 26 nm and 13 nm, respectively. In contrast, no shape anisotropy has been detected for nanoparticles inside the silicon pores in a previous study. This suggests that utilizing nanoporous alumina has a twofold advantage. First, the tubular alumina pores, spanning the entire insulating film, offer percolated paths for the perovskite to fill. Second, the elongation of the nanoparticles in the tubular alumina pores can be expected to aid device performance as the length of the nanoparticles approaches the active layer thickness (ca. 40 nm) of LEDs, while the small diameter of the crystallites accounts for the observed blue shifted emission.
关键词： LEDs,anisotropic shape,nanoporous alumina,SAXS,WAXS,nanoparticles,metal halide perovskite
更新于2025-09-04 15:30:14