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This study investigates the impacts of structure and composition on the optical and electronic properties of a series of pyridinium-based bismuth iodide complexes. Organic substrates with various functional groups, such as 4-aminopyridine (4-Ampy), 4-methylpyridine (4-Mepy), 4-dimethylaminopyridine (4-Dmapy), and 4-pyridinecarbonitrile (4-CNpy) with different electron-donating and electron-withdrawing groups at the para position of the pyridine ring were employed. Crystallographic analysis reveals various bismuth iodide structures, including 1D chains and discrete 0D motifs. The optical band gap of these materials, identified via diffuse reflectance spectroscopy (DRS) and verified with density functional theory (DFT) calculations, is influenced by the crystal packing and stabilising interactions. Through a comprehensive analysis, including Hirshfeld surface (HS) and void assessment, the study underscores the influence of noncovalent intermolecular interactions on crystal packing. Spectroscopic evaluations provide insights into electronic interactions, elucidating the role of electron donor and acceptor substituents within the lattice. Thermogravimetric differential thermal analysis (TG–DTA) indicates structural stability up to 250 °C. Linear sweep voltammetry (LSV) reveals significant conductivity in the range of 10–20 mS per pixel at 298.15 K. X-ray absorption spectroscopy (XAS) at the Bi L3 edge indicates a similar oxidation state and electronic environment across all samples, underscoring the role of bismuth centres surrounded by iodides. [ABSTRACT FROM AUTHOR]

Phase formation by pulsed laser irradiation of suspended nanoparticles has recently been introduced as a promising synthesis technique for heterostructures. The main challenge still lingers regarding the exact mechanism of particle formation due to the non‐equilibrium kinetic by‐products resulting from the localized alternative, fast, high‐temperature nature of the process. Here, the authors analyze the bond breaking/formation of copper or copper (II) interfaces with ethanol during the absorption of pulses for Cu‐CuO‐Cu2O formation applicable as an electrocatalyst in ethanol oxidation fuel cells. This study includes but is not limited to, a comprehensive discussion of the interaction between nano‐laser pulses and suspension for practical control of the synthesis process. The observed exponential and logarithmic changes in the content of heterostructures for the CuO‐ethanol and Cu‐ethanol samples irradiated with different fluences are interpreted as the dominant role of physical and chemical reactions, respectively, during the pulsed laser irradiation of suspensions synthesis. It is also shown that the local interface between dissociated ethanol and the molten sphere is responsible for the oxidative/reductive interactions resulting in the formation of catalytic‐augmented Cu3+ by‐product, thanks to the reactive bond force field molecular dynamics studies confirmed by ab‐initio calculations and experimental observations. [ABSTRACT FROM AUTHOR]

Synthetic opals, a composition of homogeneous silica spheres in the mesoscale size range, have attracted the attention of scientists due to their favorable chemical and physical properties. Their chemical inertness and stability, biocompatibility, homogeneity, elevated specific surface area, and ease of functionalization of their surfaces make them a versatile nanotool. In the present study, the Stöber process was used to investigate the effect of parameters, such as reagent concentration and synthesis temperature, on the resulting silica particle size and structure. The optimal conditions for successfully obtaining homogeneous particles in the mesoscale range with high reproducibility were investigated. Several synthesis procedures and their dependence on the reaction temperature were presented to allow the selection of the assumed diameter of silica spheres. The numerous samples obtained were examined for size, homogeneity, structure, and specific surface area. On the basis of specific surface area measurements and nuclear magnetic resonance studies, the internal hierarchical structure of the spherical silica was confirmed as consisting of a solid core and layers of secondary spheres covered by a solid shell. Structural studies (X-ray Spectroscopy, X-ray Absorption Near-Edge Structure, and nuclear magnetic resonance), together with infrared vibrational spectroscopy, showed no dependence of the structure of the obtained mesospheres on the concentration of reagents and the size of the obtained particles. [ABSTRACT FROM AUTHOR]

In this study we investigate the effect of the nanoporous anodic titanium oxide substrate on the morphology and uniformity of hydrothermally precipitated hydroxyapatite coatings. Nanotubular TiO 2 substrates were synthesized on a titanium plate by anodic oxidation and subsequently annealed at 500 °C or 600 °C to create the crystalline anatase and/or rutile forms of TiO 2 . The substrates were further used for HAp growth under hydrothermal conditions. The samples were then characterized with the XRD, Raman and SEM techniques. The results show that hydrothermal synthesis leads to formation of needle-like coating layer of HAp particles. The diameter and length of HAp crystals decrease with increasing annealing temperature of TiO 2 nanotubular arrays. Furthermore, we demonstrate that nanostructured surface of titanium oxide has beneficial influence on the HAp nucleation and coverage. [ABSTRACT FROM AUTHOR]

The novel iron-oxide nanoparticles (NPs) stabilized with triethanolammonium oleate were produced. The specimens were divided into two groups: the top NPs (extracted from the supernatant) and the bottom NPs (nanoparticles sedimented at the bottom of the flask during centrifugation), respectively. The XRD and Mössbauer studies revealed a presence of the Fe3O4 phase in both types of nanoparticles. Furthermore, the formation of maghemite layer on the surface of nanoparticles was observed. Average particle sizes determined from TEM and XRD studies were lower than the superparamagnetic limit for the magnetite NPs. For glycerol dispersions of both types of NPs, when exposed to 100 kHz external magnetic field, a significant heat release was observed. Furthermore, the contrasts of T1- and T2-weighted MR images were significantly dependent on the concentration of NPs in their water solutions. Additionally, the reductions of the relaxation times were different for the top and the bottom NPs. The viability studies of the colon cancer cells have shown low cytotoxicity of both types of NPs due to their coating with triethanolammonium oleate, which confirm the possibility to apply the NPs for MRI-guided hyperthermia. Moreover, the presence of NPs did not cause greatest increase of the number of apoptotic cells in the human dermal fibroblasts' culture and has stimulated proliferation of those cells, revealing great potential of the NPs in regenerative medicine. [ABSTRACT FROM AUTHOR]

A new X-ray absorption spectroscopy (XAS) beamline is currently under construction at a bending magnet of the National Synchrotron Radiation Centre SOLARIS. The front end of this beamline was installed in April 2020. This beamline has a few outstanding characteristic features: The monochromator is a fixed exit beam Lemmonier type monochromator allowing to cover the pursued energy range (1 keV to ~15 keV) with 3 sets of crystals: KAP (100) + multilayer, InSb (111) and Ge (220). The monochromator is a high vacuum system allowing the change of crystals in less than an hour. In order to minimize absorption of photons no windows will be installed in the beamline down to the monochromator, and just one thin polypropylene window will be used for separating the vacuum of the monochromator from the ionization chambers and the sample chamber. A special differential ion pump will be installed to maintain the pressure difference of four orders of magnitude between the storage ring and the monochromator. As SOLARIS is a low energy machine, the beamline can be built without any radiation safety hutches without exceeding the strict low radiation safety levels. The straightforward design of the beamline without additional optical elements, its compact overall dimensions and an easy to handle monochromator make this beamline especially user friendly. In combination with the characteristics of the 1.5 GeV SOLARIS storage ring this beamline will be specifically attractive for the tender X-ray range, i.e. the K-edges of important elements such as P, S, Si, Al and Mg. [ABSTRACT FROM AUTHOR]

Herein, we propose newly designed and synthesized gold nanopeanuts (Au NPes) as supports for cisplatin (cPt) immobilization, dedicated to combined glioblastoma nano-chemo-radiotherapy. Au NPes offer a large active surface, which can be used for drugs immobilization. Transmission electron microscopy (TEM) revealed that the size of the synthesized Au NPes along the longitudinal axis is ~60 nm, while along the transverse axis ~20 nm. Raman, thermogravimetric analysis (TGA) and differential scanning calorimetry (DCS) measurements showed, that the created nanosystem is stable up to a temperature of 110 °C. MTT assay revealed, that the highest cell mortality was observed for cell lines subjected to nano-chemo-radiotherapy (20–55%). Hence, Au NPes with immobilized cPt (cPt@AuNPes) are a promising nanosystem to improve the therapeutic efficiency of combined nano-chemo-radiotherapy. [ABSTRACT FROM AUTHOR]

Gold nanostars (AuS NPs) are a very attractive nanomaterial, which is characterized by high effective transduction of the electromagnetic radiation into heat energy. Therefore, AuS NPs can be used as photosensitizers in photothermal therapy (PTT). However, understanding the photothermal conversion efficiency in nanostars is very important to select the most appropriate shape and size of AuS NPs. Therefore, in this article, the synthesis of AuS NPs with different lengths of star arms for potential application in PTT was investigated. Moreover, the formation mechanism of these AuS NPs depending on the reducer concentration is proposed. Transmission electron microscopy (TEM) with selected area diffraction (SEAD) and X-ray diffraction (X-Ray) showed that all the obtained AuS NPs are crystalline and have cores with similar values of the diagonal (parameter d), from 140 nm to 146 nm. However, the widths of the star arm edges (parameter c) and the lengths of the arms (parameter a) vary between 3.75 nm and 193 nm for AuS1 NPs to 6.25 nm and 356 nm for AuS4 NPs. Ultraviolet-visible (UV-Vis) spectra revealed that, with increasing edge widths and lengths of the star arms, the surface plasmon resonance (SPR) peak is shifted to the higher wavelengths, from 640 nm for AuS1 NPs to 770 nm for AuS4 NPs. Moreover, the increase of temperature in the AuS NPs solutions as well as the values of calculated photothermal efficiency grew with the elongation of the star arms. The potential application of AuS NPs in the PTT showed that the highest decrease of viability, around 75%, of cells cultured with AuS NPs and irradiated by lasers was noticed for AuS4 NPs with the longest arms, while the smallest changes were visible for gold nanostars with the shortest arms. The present study shows that photothermal properties of AuS NPs depend on edge widths and lengths of the star arms and the values of photothermal efficiency are higher with the increase of the arm lengths, which is correlated with the reducer concentration. [ABSTRACT FROM AUTHOR]

Alternative Local Melting-Solidification of Suspended Nanoparticles for Heterostructure Formation Enabled by Pulsed Laser Irradiation (Adv. Funct. Ab-initio calculations, heterostructures, laser-suspension interactions, phase formation, reactive bond molecular dynamics The synthesized submicron Cu-CuO-Cu SB 2 sb O heterostructures containing Cu SB 2 sb O SB 3 sb phase are thoroughly investigated for application in ethanol oxidation fuel cells. [Extracted from the article]

Pulsed Laser Irradiation In article number 2304359, Mohammad Sadegh Shakeri and co‐workers propose a mechanism for phase formation and particle growth in pulsed laser irradiation of suspensions (PLIS). PLIS is proposed as a suitable method for the synthesis of submicron heterostructures. They use mathematical modeling, reactive bond molecular dynamics, and density functional theory to validate experimental observations. The synthesized submicron Cu‐CuO‐Cu2O heterostructures containing Cu2O3 phase are thoroughly investigated for application in ethanol oxidation fuel cells. [ABSTRACT FROM AUTHOR]

[Display omitted] • Atomically dispersed Cu on TiO2 nanoparticles synthesized by the wet impregnation method; • 100% Selectivity to hydrogen in the methanol photoreforming has been achieved; • Cu2+ Oxidation state bypassed to prevent CO 2 generation; • Cu+→Cu0 → Cu+ Redox cycle identified under the reaction conditions; • An apparent quantum efficiency of 10% at λ = 365 nm and the 0.45 W LED source. Hydrogen generation by photoreforming of methanol is being one of the most intensely investigated photochemical transformations in pursuing a sustainable, zero waste circular economy. This transformation usually produces a significant amount of gaseous carbon in the form of CO 2 and CO that disqualifies many active photocatalysts as being fully sustainable. Here, we demonstrate the atomically dispersed Cu on TiO 2 composite nanoparticles synthesized by the wet impregnation method that are highly active and selective in hydrogen production by photoreforming of methanol solution. Our photocatalyst exhibits an apparent quantum efficiency of 10% at 365 nm wavelength and the low power 0.45 W light emitting diode (LED) source. The only gaseous product found is molecular hydrogen, whereas all carbon is trapped in the downstream liquid mixture of formaldehyde and formic acid, making the process fully sustainable and clean. We used various experimental techniques and density functional theory calculations (DFT) to characterize our photocatalysts and provide an insight into the exceptional behavior of the Cu/TiO 2 system. A combination of ab initio DFT and X–ray photoelectron spectroscopy (XPS) measurements allowed us to identify the Cu+–Cu0–Cu+ redox cycle under the reaction conditions. Bypassing the Cu2+ oxidation state is crucial to keep the oxidation potential of photogenerated holes low enough to prevent CO 2 generation and keeping all carbon in the liquid phase. This work paves the way toward an efficient and clean generation of hydrogen by photoreforming of methanol over well–established and cheap Cu/TiO 2 photocatalyst. [ABSTRACT FROM AUTHOR]

We studied the magnetic properties of Co nanowires electrodeposited in polycarbonate membranes as a function of the electrodeposition and template parameters. We showed the response of the current as a function of time, for nanowires prepared in various conditions. X-ray diffraction measurements indicate that nanowires have polycrystalline hcp structure with small addition of fcc phase. Magnetic properties analyzed by SQUID measurements suggest that easy axis of magnetization follows the nanowire axis with coercivity increasing with a decrease of nanowire diameter and length. The largest coercivity, equal to 850 Oe, was obtained for nanowires with the diameter of 30 nm and the length of 1.5 μm. We find the coercivity to be insensitive to pH value. Low electrodeposition temperature, low cathodic potential, and medium pH are the synthesis parameters most beneficial for large coercivity and/or magnetic anisotropy with easy axis along nanowires. [ABSTRACT FROM AUTHOR]

Self-ordered arrays of Ni, Ni(50)Pd(50), and Ni(78)Pd(22) nanowires were synthesized by simultaneous electrochemical deposition of Ni and Pd components into porous templates of anodic aluminum oxide using alternating current. This paper is focused on the interplay of structure and chemical composition of Ni and Ni–Pd bicomponent nanowires arrays and the peculiarities of its magnetic anisotropy. [ABSTRACT FROM AUTHOR]