Search Results (62)

A classical molecular dynamics simulation of cation diffusion in isolated crystals (U_xPu_yTh_1−x−y)O₂ bounded by a free surface was performed. It was shown that in the bulk of the same model crystallite, the diffusion coefficients of cations of all types were practically identical. At the same time, the cation diffusion coefficients changed with the melting temperature of nanocrystals, which increased with increasing thorium content. At a given temperature, the diffusion coefficients were the higher, the lower were the melting points of the (U_xPu_yTh_1−x−y)O₂ crystallites. The temperature dependences of the diffusion coefficients in crystallites of different compositions converged when using coordinates normalized to the melting points. Full article

In this work, we studied Cu-doped and (Cu,Y)-codoped ZrO₂ nanopowders produced through a coprecipitation approach to identify the nature of Cu-related bulk and surface paramagnetic centers. We conducted EPR, NMR, and Raman scattering studies on Cu- and (Cu,Y)-doped ZrO₂ powders calcined at different temperatures. At low calcination temperatures (400 °C) and low Cu loading (0.1–1.0 mol.% of CuO), the EPR signal was found to be attributed to surface-related Cu-H₂O complexes. For powders with higher Cu content (up to 8.0 mol.% of CuO), the superparamagnetic signal associated with the formation of copper clusters was observed. At higher calcination temperatures, the destruction of Cu-related surface complexes promotes the incorporation of Cu²⁺ ions into the bulk of ZrO₂ nanocrystals at Zr positions. Co-doping ZrO₂ with Cu and Y was observed to facilitate the incorporation of Cu²⁺ ions into cation sites at lower calcination temperatures when compared with Cu-doped ZrO₂. Full article

The interactions between cellulose nanocrystals and six different polymers (three anionic, two non-ionic, and one cationic) were investigated using rheological measurements of aqueous solutions of nanocrystals and polymers. The experimental viscosity data could be described adequately by a power-law model. The variations in power-law parameters (consistency index and flow behavior index) with concentrations of nanocrystals and polymers were determined for different combinations of nanocrystals and polymers. The interactions between nanocrystals and the following polymers: anionic sodium carboxymethyl cellulose and non-ionic guar gum, were found to be strong in that the consistency index increased substantially with the addition of nanocrystals to polymer solutions. The interaction between nanocrystals and non-ionic polymer polyethylene oxide was moderate. Depending on the concentrations of nanocrystals and polymer, the consistency index both increased and decreased upon the addition of nanocrystals to polymer solution. The interactions between nanocrystals and the following polymers: anionic xanthan gum, anionic polyacrylamide, and cationic quaternary ammonium salt of hydroxyethyl cellulose, were found to be weak. The changes in rheological properties with nanocrystal addition to these polymer solutions were found to be small or negligible. Full article

Bio-based eco-friendly cellulose nanocrystals (CNCs) gain an increasing interest for diverse applications. We report the results of an investigation of hydrogels spontaneously formed by the self-assembly of carboxylated CNCs in the presence of CaCl₂ using several complementary techniques: rheometry, isothermal titration calorimetry, FTIR-spectroscopy, cryo-electron microscopy, cryo-electron tomography, and polarized optical microscopy. Increasing CaCl₂ concentration was shown to induce a strong increase in the storage modulus of CNC hydrogels accompanied by the growth of CNC aggregates included in the network. Comparison of the rheological data at the same ionic strength provided by NaCl and CaCl₂ shows much higher dynamic moduli in the presence of CaCl₂, which implies that calcium cations not only screen the repulsion between similarly charged nanocrystals favoring their self-assembly, but also crosslink the polyanionic nanocrystals. Crosslinking is endothermic and driven by increasing entropy, which is most likely due to the release of water molecules surrounding the interacting COO⁻ and Ca²⁺ ions. The hydrogels can be easily destroyed by increasing the shear rate because of the alignment of rodlike nanocrystals along the direction of flow and then quickly recover up to 90% of their viscosity in 15 s, when the shear rate is decreased. Full article

The rapid expansion of medical nanotechnology has significantly broadened the potential applications of cellulose nanocrystals (CNCs). While CNCs were initially developed for drug delivery, they are now being investigated for a range of advanced biomedical applications. As these applications evolve, it becomes crucial to understand the physicochemical behavior of CNCs in biologically relevant media to optimize their design and ensure biocompatibility. Functionalized CNCs can adsorb biomolecules, forming a “protein corona” that can impact their physicochemical properties, including alterations in particle size, zeta potential, and overall functionality. In this study, CNCs were coated with low (8500 Da)- and high (400,000–500,000 Da)-molecular-weight cationic polymer (poly(diallyldimethylammonium chloride—(PDDA) via non-covalent grafting, and their physicochemical characteristics, as well as their biological effects, were assessed in physiologically relevant media after sterilization. Our findings show that autoclaving significantly alters the physicochemical properties of CNC-PDDA, particularly when coated with low-molecular-weight (LMW) polymer. Furthermore, we observed that CNC-PDDA of a high molecular weight (HMW) has a greater impact on cell viability and blood biocompatibility than its LMW counterpart. Moreover, cellular immune responses to both CNC-PDDA LMW and HMW vary in the presence or absence of serum, implying that protein adsorption influences cell-nanomaterial recognition and their biological activity. This study provides valuable insights for optimizing CNC-based nanomaterials for therapeutic applications. Full article

Fluorescent materials for sensing have gained attention for the visual detection of different substances as metals and pesticides for environmental monitoring. This work presents fluorescent nanocomposites in solution, film, and paper obtained without capping and stabilizing agents, coming from quantum dots of cadmium sulfide (CdS QDs) and anionic–cationic polymer matrices. Fluorescent films were formed by casting and fluorescent paper by impregnation from the solutions. The optical properties of CdS QDs in solution showed absorption between 418 and 430 nm and a maximum emission at 460 nm. TEM analysis evidenced particle size between 3 and 6 nm and diffraction patterns characteristic of CdS nanocrystals. Infrared spectra evidenced changes in the wavenumber in the fluorescent films. The band gap values (2.95–2.82 eV) suggested an application for visible transmitting film. Fluorescent solutions by UV-vis and fluorescence evidenced a chemical interaction with glyphosate standard between 1 and 100 µg/mL concentrations. The analysis of red, green, and blue color codes (RGB) evidenced a color response of the fluorescent paper at 10 and 100 µg/mL, but the fluorescent films did not show change. Nanocomposites of chitosan and pectin, in solution and on paper, exhibited a behavior “turn-on” sensor, while carboxymethylcellulose had a “turn-off” sensor. This methodology presents three fluorescent materials with potential applications in visual sensing. Full article

Curcumin, a naturally occurring poorly water-soluble polyphenol with a broad spectrum, is a typical BCS IV drug. The objective of this study was to develop curcumin nanocrystals liposomes with the aim of improving bioavailability. In this study, we prepared cationic curcumin nanocrystals with a particle size of only 29.42 nm; such a phenomenal range of particle sizes is very rare. Moreover, we summarized and evaluated the parameters of the nanocrystal preparation process, including methods, formulations, etc., and the rules we concluded can be generalized to other nanocrystal preparation processes. To counteract the instability of the nanocrystals in the digestive tract, cationic curcumin nanocrystals were loaded into negatively charged liposomes through gravitational force between different charges. Unexpectedly, chitosan oligosaccharide was found to promote the self-assembly process of curcumin nanocrystal liposomes. In vitro and in vivo experiments demonstrated that chitosan-modified curcumin nanocrystal liposomes exhibited enhanced resistance to enzyme barriers, mucus barriers, and cellular barriers, resulting in a 5.4-fold increase in bioavailability compared to crude powder formulations. It can be concluded that cationic nanocrystals liposomes represent an appropriate novel strategy for improving the dissolution rate and bioavailability of poorly soluble natural products such as curcumin. Full article

Alginate, categorized as a natural-based biodegradable polymer, stands out for its inherently exclusive properties. Although this unique polymer is widely processed using film, coating, and membrane technologies for different usage areas, textile applications are still limited. This study aims to compile promising approaches that will pave the way for the use of wet-spun alginate filaments in textile applications. In this regard, this study provides information about the molecular structure of alginate, the gel formation mechanism, and cross-linking using different techniques. Our literature review categorizes parameters affecting the mechanical properties of wet-spun alginate filaments, such as the effect of ion source and spinning dope concentration, needle diameter, temperature, and coagulants. Following this, a detailed and comprehensive literature review of the various approaches, such as use of additives, preparation of blended filaments, and grafted nanocrystal addition, developed by researchers to produce composite alginate filaments is presented. Additionally, studies concerning the use of different cations in the coagulation phase are reported. Moreover, studies about the functionalism of wet-spun alginate filaments have been offered. Full article

The tailoring of the surface properties of cellulose nanocrystals (CNCs) to meet various requirements in environmental, food, and material areas has always been of great interest. In this study, the surface chemistry of CNCs was noncovalently modified by cetyltrimethylammonium bromide (CTAB), followed by characterizations and an investigation into its application as a coating material for interfacial interaction over various substrates. Due to the CTAB modification, the surface charge of the CNCs was neutralized, resulting in an increased size of each nanocrystal at the aqueous status and the aggregated microfibers when dried up. The CTAB modification not only decreased the crystallinity of the samples from 48.57% to 9.12%, but also reasonably hydrophobized the CNCs and decreased their total surface energy. Finally, the adsorption behavior of the CNCs and CTAB-CNCs over nonionic, anionic, and cationic polymers was investigated by ellipsometry. Based on the thickness of the CNC and CTAB-CNC layers over 2-Hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), and polyethyleneimine (PEI), we proposed that the adsorption behavior was overall influenced by electrostatic interaction, hydrogen bonding, and van der Waals forces, and the thickness of the adsorbed layers could be impacted by both the surface charge and the size of the crystals. Full article

This work aims to demonstrate that the Fe₂O₃ nanocrystals’ adsorptive and photocatalytic properties can be adjusted by exposing the crystal facets that are functionalized. To this end, cube- and disc-like structures were synthesized using a metal ion-mediated hydrothermal route. Thereafter, some of the samples were annealed at 500 °C for 3 h. Our paper combines the experimental part with theoretical calculations of the obtained materials’ band edge positions. The results reveal that—aside from hematite—the as-synthesized discs also contain γ-FeOOH and β-Fe₂O₃ phases, which transform into α-Fe₂O₃ during annealing. The hydrodynamic diameter, zeta potential, and adsorption kinetics measurements show that the cube-like samples exhibit the highest affinity for cationic, whereas the discs have an affinity for anionic dye. Measurements of the wall zeta potential also reveal that annealing the discs modifies their surface state and ability to adsorb molecules. Photocatalytic tests show that the as-synthesized powders have better photocatalytic performance toward methylene blue decomposition than the annealed ones. The observed small changes in the concentration of the MO during illumination result from the energy band structure of the cube-like crystal orientation. Full article

Until now, the comprehensive structural analysis of single crystals of zeolite ECR-1, an aluminosilicate with the EON topology, has been hindered owing to the submicron dimensions of the obtained crystals. Additionally, this zeolite, which is characterized by a topology comprising alternating periodic building units of MAZ and MOR layers, exhibits stacking faults that impede accurate refinement through the Rietveld method. In this report, we present, for the first time, the structure of ECR-1 elucidated by studying a nanocrystal with a significantly reduced number of stacking faults. The sample used was synthesized hydrothermally using trioxane as the organic structure-directing agent. The structure determination was conducted using precession electron diffraction (PED) at 103 K. Partial dehydration occurred owing to the high vacuum conditions in the TEM sample chamber. From the dynamical refinement (R_obs = 0.097), 8.16 Na⁺ compensating cations were localized on six distinct crystallographic sites, along with approximately four water molecules per unit cell. Furthermore, a canonical Monte Carlo computational study was conducted to compare the experimental cationic distribution and location of water molecules with the simulation. Full article

In this paper, we report on the solvothermal preparation and detailed characterization of pristine and intentionally doped zirconium dioxide (ZrO₂) nanocrystals (NCs, ~5 nm) with Eu³⁺ or Ti⁴⁺/Eu³⁺ ions using alkoxide precursors. The results indicated that the ZrO₂ NCs were dominantly of a tetragonal phase (t-ZrO₂) with a small proportion of monoclinic ZrO₂ (m-ZrO₂). The high purity of t-ZrO₂ NCs could be synthesized with more Eu³⁺ doping. It was found that the as-obtained ZrO₂ NCs contain some naturally present Ti⁴⁺ ions originating from precursors, but were being overlooked commonly, and some carbon impurities produced during synthesis. These species showed distinct photoluminescence (PL) properties. At least two types of Eu³⁺, located at low- and high-symmetry sites (probably sevenfold and eightfold oxygen coordination), respectively, were demonstrated to build into the lattice structure of t-ZrO₂ NCs together. The cationic dopants were illustrated to be distributed non-randomly over the sites normally occupied by Zr, while Ti impurities preferentially occupied the sites near the low-symmetry site of Eu³⁺, yielding efficient energy transfer from the titanate groups to the neighboring Eu³⁺. Luminescence nanothermometry could measure temperature in a non-contact and remote way and could find great potentials in micro/nano-electronics, integrated photonics, and biomedicine. On the basis of the dual-emitting combination strategy involving the white broadband CT (Ti³⁺→O⁻) emissions of the titanate groups and red sharp Eu³⁺ emissions, t-ZrO₂:Eu³⁺ nanophosphors were demonstrated to be ratiometric self-referencing optical thermometric materials, with a working range of 130–230 K and a maxima of relative sensitivity of ~1.9% K⁻¹ at 230 K. Full article

Per- and poly-fluoroalkyl substances (PFAS) are concerning contaminants due to their ubiquity, persistence, and toxicity. Conventional PFAS water treatments such as granular activated carbon are limited by low adsorption rates and capacities. Carbon-based nano-adsorbents with enhanced surface areas address these limitations but are hindered by their high cost and toxicity. Cellulose nanocrystals (CNC) are promising PFAS adsorbents due to sustainable sourcing, large surface areas, and amenable surface properties. In this study, CNC was synthesized from the agro-food waste, apple pomace (APCNC), and coated with Moringa oleifera cationic protein (MOCP) aqueous extract to produce MOCP/APCNC for the removal of perfluorooctanoic acid (PFOA) from water. APCNC and MOCP/APCNC were manufactured, characterized, and utilized in PFOA batch adsorption kinetics and equilibrium trials. APCNC was successfully produced from apple pomace (AP) and determined through characterization and comparison to commercial CNC (CCNC). APCNC and MOCP/APCNC exhibited rapid PFOA adsorption, approaching equilibrium within 15 min. MOCP coatings inverted the MOCP/CNC surface charge to cationic (−15.07 to 7.38 mV) and enhanced the PFOA adsorption rate (2.65 × 10⁻³ to 5.05 × 10⁻³ g/mg/s), capacity (47.1 to 61.1 mg/g), and robustness across varied water qualities. The sustainable sourcing of APCNC combined with a green surface coating to produce MOCP/CNC provides a highly promising environmentally friendly approach to PFAS remediation. Full article

Even with significant developments in nanoscience, relatively little is known about the interactions of nanocrystal semiconducting materials with bio-macromolecules. To investigate the interfacial phenomena of cadmium selenide quantum dot (CdSe QD) nanocrystals with proteins extracted from Moringa oleifera seeds, different concentrations of cadmium selenide quantum dots–Moringa oleifera seed protein (CdSe–MSP) complexes were prepared. Respective CdSe QDs with hexagonal phase and crystalline size in the range of 4–7 nm were synthesized and labelled with the purified mesoporous MSP having a surface area of 8.4 m²/g. The interaction mechanism between CdSe QDs and MSP was studied using UV–Vis absorption, fluorescence emission and Fourier Transform Infrared spectroscopies. The UV–Vis absorption spectra showed absorption bands of CdSe–MSP complexes at 546.5 nm. The fluorescence intensity of CdSe QDs was found to decrease with increasing concentration of MSP. The thermodynamic potentials $∆H^{\theta }$ (−321.3 $\times {10}^3$ Jmol⁻¹);$∆S^{\theta }$ (156.0 JK⁻¹mol⁻¹) and $∆G^{\theta }$ (−46.6 $\times {10}^3$ Jmol⁻¹) were also calculated. The stability of the complex found is strongly influenced by electrostatics interaction and surface-bound complexation equilibrium attraction. This information can help to elucidate the surface characteristics of MSP and its potential interactions with other molecules or nanoparticles. Full article

Perovskites have been recognized as a class of promising materials for optoelectronic devices. We intentionally include excessive Cs⁺ cations in precursors in the synthesis of perovskite CsPbBr₃ nanocrystals and investigate how the Cs⁺ cations influence the lattice strain in these perovskite nanocrystals. Upon light illumination, the lattice strain due to the addition of alkali metal Cs⁺ cations can be compensated by light–induced lattice expansion. When the Cs⁺ cation in precursors is about 10% excessive, the electron–phonon coupling strength can be reduced by about 70%, and the carrier cooling can be slowed down about 3.5 times in lead halide perovskite CsPbBr₃ nanocrystals. This work reveals a new understanding of the role of Cs⁺ cations, which take the A–site in ABX₃ perovskite and provide a new way to improve the performance of perovskites and their practical devices further. Full article