Encapsulation of short-chain bioactive peptides (BAPs) for gastrointestinal delivery: a review.

The majority of known peptides with high bioactivity (BAPs) such as antihypertensive, antidiabetic, antioxidant, hypocholesterolemic, anti-inflammatory and antimicrobial actions, are short-chain sequences of less than ten amino acids. These short-chain BAPs of varying natural and synthetic origin must be bioaccessible to be capable of being adsorbed systemically upon oral administration to show their full range of bioactivity. However, in general, in vitro and in vivo studies have shown that gastrointestinal digestion reduces BAPs bioactivity unless they are protected from degradation by encapsulation. This review gives a critical analysis of short-chain BAP encapsulation and performance with regard to the oral delivery route. In particular, it focuses on short-chain BAPs with antihypertensive and antidiabetic activity and encapsulation methods via nanoparticles and microparticles. Also addressed are the different wall materials used to form these particles and their associated payloads and release kinetics, along with the current challenges and a perspective of the future applications of these systems.

From angular to round: in depth interfacial analysis of binary phosphatidylethanolamine mixtures in the inverse hexagonal phase.

Packing stress in the lipidic inverse hexagonal HII phase arises from the necessity of the ideally cylinder-shaped micelles to fill out the hexagonally-shaped Wigner-Seitz unit cell. Thus, hydrocarbon chains stretch towards the corners and compress in the direction of the flat side of the hexagonal unit cell. Additionally, the lipid/water interface deviates from being perfectly circular. To study this packing frustration in greater detail, we have doped 1-palmitoyl-2-oleoyl-sn-phosphatidylethanolamine (POPE) with increasing molar concentrations of 1,2-palmitoyl-sn-phosphatidylethanolamine (DPPE: 0 to 15 mol%). Due to its effectively longer hydrophobic tails, DPPE tends to aggregate in the corner regions of the unit cell, and thus, increases the circularity of the lipid/water interface. From small angle X-ray diffraction (SAXD) we determined electron density maps. Using those, we analysed the size, shape and homogeneity of the lipid/water interface as well as that of the methyl trough region. At 6 and 9 mol% DPPE the nanotubular water core most closely resembles a circle; further to this, in comparison to its neighbouring concentrations, the 9 mol% DPPE sample has the smallest water core area and smallest number of lipids per circumference, best alleviating the packing stress. Finally, a three-water layer model was applied, discerning headgroup, perturbed and free water, demonstrating that the hexagonal phase is most stable in the direction of the flat faces (compression zones) and least stable towards the vertices of the unit cell (decompression zones).

γ-Cyclodextrin Metal-Organic Frameworks: Do Solvents Make a Difference?

Conventionally, methanol is the solvent of choice in the synthesis of gamma-cyclodextrin metal-organic frameworks (γ-CD-MOFs), but using ethanol as a replacement could allow for a more food-grade synthesis condition. Therefore, the aim of the study was to compare the γ-CD-MOFs synthesised with both methanol and ethanol. The γ-CD-MOFs were characterised by scanning electron microscopy (SEM), surface area and pore measurement, Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction (PXRD). The encapsulation efficiency (EE) and loading capacity (LC) of the γ-CD-MOFs were also determined for curcumin, using methanol, ethanol and a mixture of the two as encapsulation solvent. It was found that γ-CD-MOFs synthesised by methanol and ethanol do not differ greatly, the most significant difference being the larger crystal size of γ-CD-MOFs crystallised from ethanol. However, the change in solvent significantly influenced the EE and LC of the crystals. The higher solubility of curcumin in ethanol reduced interactions with the γ-CD-MOFs and resulted in lowered EE and LC. This suggests that different solvents should be used to deliberately manipulate the EE and LC of target compounds for better use of γ-CD-MOFs as their encapsulating and delivery agents.

Correction: Planar confined water organisation in lipid bilayer stacks of phosphatidylcholine and phosphatidylethanolamine.

Correction for 'Planar confined water organisation in lipid bilayer stacks of phosphatidylcholine and phosphatidylethanolamine' by Gerome Vancuylenberg et al., Soft Matter, 2023, https://doi.org/10.1039/D3SM00387F.

Planar confined water organisation in lipid bilayer stacks of phosphatidylcholine and phosphatidylethanolamine.

Phospholipid-based liposomes are abundantly studied in biomembrane research and used in numerous medical and biotechnological applications. Despite current extensive knowledge on membrane nanostructure and its mechanical properties under various environmental conditions, there is still a lack of understanding on interfacial lipid-water interactions. In this work, the nature of the confined water layer for L-α-phosphatidylcholine (egg-PC), 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), 1,2-dimyristoyl-sn-glycerol-3-phosphocholine (DMPC) and 1,2-dimyristoyl-sn-glycero-3-phosphoethanolamine (DMPE) in the fluid lamellar phase of multilamellar vesicles was investigated. A new model for describing three different water regions is proposed, which have been characterised using a combination of small angle X-ray scattering (SAXS) and densitometry. The three regions concern (i) 'the headgroup water', (ii) 'perturbed water' near the membrane/water interface and (iii) a core layer of 'free water' (unperturbed water). The behaviour of all three layers is discussed as a function of temperature, concerning influences of chain saturation and headgroup type. While the overall water layer and perturbed water layer thickness increase with temperature, the free water layer displays the opposite trend for PCs, and in PEs is completely absent. Furthermore, an estimate of the temperature dependent headgroup orientation is given for both, PCs and PEs. The newly presented structural data deduced from the three-water region model will be useful for future refined molecular dynamics simulations and allow a better theoretical understanding of the attractive van der Waals force between adjacent membranes.

High Resolution Membrane Structures within Hybrid Lipid-Polymer Vesicles Revealed by Combining X-Ray Scattering and Electron Microscopy.

Hybrid vesicles consisting of phospholipids and block-copolymers are increasingly finding applications in science and technology. Herein, small angle X-ray scattering (SAXS) and cryo-electron tomography (cryo-ET) are used to obtain detailed structural information about hybrid vesicles with different ratios of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and poly(1,2-butadiene-block-ethylene oxide) (PBd22 -PEO14 , Ms  = 1800 g mol-1 ). Using single particle analysis (SPA) the authors are able to further interpret the information gained from SAXS and cryo-ET experiments, showing that increasing PBd22 -PEO14 mole fraction increases the membrane thickness from 52 Å for a pure lipid system to 97 Å for pure PBd22 -PEO14 vesicles. Two vesicle populations with different membrane thicknesses in hybrid vesicle samples are found. As these lipids and polymers are reported to homogeneously mix, bistability is inferred between weak and strong interdigitation regimes of PBd22 -PEO14 within the hybrid membranes. It is hypothesized that membranes of intermediate structure are not energetically favorable. Therefore, each vesicle exists in one of these two membrane structures, which are assumed to have comparable free energies. The authors conclude that, by combining biophysical methods, accurate determination of the influence of composition on the structural properties of hybrid membranes is achieved, revealing that two distinct membranes structures can coexist in homogeneously mixed lipid-polymer hybrid vesicles.

Structuring supramolecular hyaluronan hydrogels via peptide self-assembly for modulating the cell microenvironment.

The use of synthetic extracellular matrices (ECMs) in fundamental in vitro cell culture studies has been instrumental for investigating the interplay between cells and matrix components. To provide cells with a more native environment in vitro, it is desirable to design matrices that are biomimetic and emulate compositional and structural features of natural ECMs. Here, the supramolecular fabrication of peptide-hyaluronan (HA) hydrogels is presented as potential ECM surrogates, combining native HA and rationally designed cationic amphipatic peptides [(KI)nK, lysine (K), isoleucine (I), n â€‹= â€‹2-6] whose mechanical properties and microstructure are tunable by the peptide sequence. (KI)nK peptides adopt ß-sheet configuration and self-assemble into filamentous nanostructures triggered by pH or ionic strength. The self-assembly propensity of (KI)nK peptides increases with the sequence length, forming single phase hydrogels (shorter peptides) or with phase separation (longer peptides) in presence of the anionic polyelectrolyte HA through electrostatic complexations. The gel phase formed in (KI)nK-HA complexes exhibits viscoelastic behavior and triggers the formation of human mesenchymal stem cell (MSC) spheroids which disassemble over the time. It is anticipated that these (KI)nK-HA hydrogels with tunable physical and biochemical properties offer a promising platform for in vitro applications and in stem cell therapy.

Polymorphism of a Highly Asymmetrical Triacylglycerol in Milk Fat: 1-Butyryl 2-Stearoyl 3-Palmitoyl-glycerol.

Milk fat has more than 200 triacylglycerols (TAGs), which play a pivotal role in its crystallization behavior. Asymmetrical TAGs containing short butyryl chains contribute to a significant portion of milk fat TAGs. This work aims to elucidate the crystallization behavior of asymmetrical milk fat TAGs by employing the pure compound of 1-butyryl 2-stearoyl 3-palmitoyl-glycerol (BuSP). The structural evolution of BuSP after being cooled down to 20 °C from the melt is evaluated by small- and wide-angle X-ray scattering (SAXS and WAXS) and differential scanning calorimetry (DSC). The temporal structural observation shows that BuSP crystallizes into the α-form with short and long spacings of 4.10 and 56.9 Å, respectively, during the first hour of isothermal hold at 20 °C. The polymorphic transformation of the α to ß' phase occurred after 4 h of isothermal hold, and the ß'- to α-form fraction ratio was about 70:30 at the end of the isothermal experiment (18 h). Pure ß'-form X-ray patterns are obtained from the BuSP powder with short spacings of 4.33, 4.14, and 3.80 Å, while the long spacing of 51.2 Å depicts a three-chain-length lamellar structure with a tilt angle of 32°. Corresponding DSC measurements display that BuSP crystallizes from the melt at 29.1 °C, whereas the melting of α- and ß'-forms was recorded at 30.3 and 47.8 °C, respectively. In the absence of the ß-form, the ß'-polymorph is the most stable observed form in BuSP. This work exemplarily explains the crystallization behavior of asymmetrical milk fat TAGs and thus provides new insights into their role in overall milk fat crystallization.

Structure and Dynamics of Dioleoyl-Phosphatidylcholine Bilayers under the Influence of Quercetin and Rutin.

Quercetin and rutin, two widely studied flavonoids with applications foreseen in the sectors of pharmaceutical and cosmetic industries, have been chosen as model compounds for a detailed structural and dynamical investigation onto their influence on fluid lipid bilayers. Combining global small angle X-ray scattering analysis with molecular dynamics, various changes in the properties of dioleoyl-phosphatidylcholine (DOPC) bilayers have been determined. The solubility of quercetin in DOPC membranes is assured up to 12 mol %, whereas rutin, with additional glucose and rhamnose groups, are fully soluble only up to 6 mol %. Both flavonoids induce an increase in membrane undulations and thin the bilayers slightly (<1 Å) in a concentration dependent manner, wherein quercetin shows a stronger effect. Concomitantly, in the order of 2-4%, the adjacent bilayer distance increases with the flavonoid's concentration. Partial molecular areas of quercetin and rutin are determined to be 26 and 51 Å2, respectively. Simulated averaged areas per molecule confirm these estimates. A 60° tilted orientation of quercetin is observed with respect to the bilayer normal, whereas the flavonoid moiety of rutin is oriented more perpendicular (α-angle 30°) to the membrane surface. Both flavonoid moieties are located at a depth of 12 and 16 Å for quercetin and rutin, respectively, while their anionic forms display a location closer to the polar interface. Finally, at both simulated concentrations (1.5 and 12 mol %), DOPC-rutin systems induce a stronger packing of the pure DOPC lipid bilayer, mainly due to stronger attractive electrostatic interactions in the polar lipid head region.

Responsive Nanofibers with Embedded Hierarchical Lipid Self-Assemblies.

We introduce the design and study of a hybrid electrospun membrane with a dedicated nanoscale structural hierarchy for controlled functions in the biomedical domain. The hybrid system comprises submicrometer-sized internally self-assembled lipid nanoparticles (ISAsomes or mesosomes) embedded into the electrospun membrane with a nanofibrous polymer network. The internal structure of ISAsomes, studied by small-angle X-ray scattering (SAXS) and electron microscopy, demonstrated a spontaneous response to variations in the environmental conditions as they undergo a bicontinuous inverse cubic phase (cubosomes) in solution to a crystalline lamellar phase in the polymer membrane; nevertheless, this phase reorganization is reversible. As revealed by in situ SAXS measurements, if the membrane was put in contact with aqueous media, the cubic phase reappeared and submicrometer-sized cubosomes were released upon dissolution of the nanofibers. Furthermore, the hybrid membranes exhibited a specific anisotropic feature and morphological response under an external strain. While nanofibers were aligned under external strain in the microscale, the semicrystalline domains from the polymer phase were positioned perpendicular to the lamellae of the lipid phase in the nanoscale. The fabricated membranes and their spontaneous responses offer new strategies for the development of structure-controlled functions in electrospun nanofibers for biomedical applications, such as drug delivery or controlled interactions with biointerfaces.

Solvents, CO2 and biopolymers: Structure formation in chitosan aerogel.

The functionality of biopolymer aerogels is inherently linked to its microstructure, which in turn depends on the synthesis protocol. Detailed investigations on the macroscopic size change and nanostructure formation during chitosan aerogel synthesis reveal a new aspect of biopolymer aerogels that increases process flexibility. Formaldehyde-cross-linked chitosan gels retain a significant fraction of their original volume after solvent exchange into methanol (50.3 %), ethanol (47.1 %) or isopropanol (26.7 %), but shrink dramatically during subsequent supercritical CO2 processing (down to 4.9 %, 3.5 % and 3.7 %, respectively). In contrast, chitosan gels shrink more strongly upon exchange into n-heptane (7.2 %), a low affinity solvent, and retain this volume during CO2 processing. Small-angle X-ray scattering confirms that the occurrence of the volumetric changes correlates with mesoporous network formation through physical coagulation in CO2 or n-heptane. The structure formation step can be controlled by solvent-polymer and polymer-drying interactions, which would be a new tool to tailor the aerogel structure.

Structurally Tunable pH-responsive Phosphine Oxide Based Gels by Facile Synthesis Strategy.

Design and synthesis of nanostructured responsive gels have attracted increasing attention, particularly in the biomedical domain. Polymer chain configurations and nanodomain sizes within the network can be used to steer their functions as drug carriers. Here, a catalyst-free facile one-step synthesis strategy is reported for the design of pH-responsive gels and controlled structures in nanoscale. Transparent and impurity free gels were directly synthesized from trivinylphosphine oxide (TVPO) and cyclic secondary diamine monomers via Michael addition polymerization under mild conditions. NMR analysis confirmed the consumption of all TVPO and the absence of side products, thereby eliminating post purification steps. The small-angle X-ray scattering (SAXS) elucidates the nanoscale structural features in gels, that is, it demonstrates the presence of collapsed nanodomains within gel networks and it was possible to tune the size of these domains by varying the amine monomers and the nature of the solvent. The fabricated gels demonstrate structure tunability via solvent-polymer interactions and pH specific drug release behavior. Three different anionic dyes (acid blue 80, acid blue 90, and fluorescein) of varying size and chemistry were incorporated into the hydrogel as model drugs and their release behavior was studied. Compared to acidic pH, a higher and faster release of acid blue 80 and fluorescein was observed at pH 10, possibly because of their increased solubility in alkaline pH. In addition, their release in phosphate buffered saline (PBS) and simulated body fluid (SBF) matrix was positively influenced by the ionic interaction with positively charged metal ions. In the case of hydrogel containing acid blue 90 a very low drug release (<1%) was observed, which is due to the reaction of its accessible free amino group with the vinyl groups of the TVPO. In vitro evaluation of the prepared hydrogel using human dermal fibroblasts indicates no cytotoxic effects, warranting further research for biomedical applications. Our strategy of such gel synthesis lays the basis for the design of other gel-based functional materials.

Excitonic channels from bio-inspired templated supramolecular assembly of J-aggregate nanowires.

Supramolecular assemblies with controlled morphology are of paramount importance for energy transport in organic semiconductors. Despite considerable freedom in molecular design, the preparation of dyes that form one dimensional J-aggregates is challenging. Here, we demonstrate a simple and effective route to functionalize dendronized polymers (DPs) with J-aggregates to construct tubular DP/J-aggregate nanowires. When J-aggregates are adsorbed onto DPs anchored to glass substrates, they assemble into microcrystalline domains typical for J-aggregates adsorbed on functionalized surfaces. Differently, the complexation between the dendronized polymer and J-aggregates in solution leads to dense packing of J-aggregate strands on the periphery of the DPs. Using a layer-by-layer (LBL) technique, DPs loaded with J-aggregates can also be adsorbed onto a DP monolayer. In this case, the thin film absorption spectra are narrower and indicate higher ratios of J-aggregate to monomer and dimer absorption than bare J-aggregates deposited similarly. The demonstration of J-aggregate adsorption on filamentous polymeric templates is a promising step toward artificial 1D light harvesting antennas, with potential applications in opto-electronic devices.

Structural insights into semicrystalline states of electrospun nanofibers: a multiscale analytical approach.

A dedicated nanofiber design for applications in the biomedical domain is based on the understanding of nanofiber structures. The structure of electrospun nanofibers strongly influences their properties and functionalities. In polymeric nanofibers X-ray scattering and diffraction methods, i.e. SAXS and WAXD, are capable of decoding their structural insights from about 100 nm down to the Angström scale. Here, we present a comprehensive X-ray scattering and diffraction based study and introduce new data analysis approaches to unveil detailed structural features in electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVDFhfp) nanofiber membranes. Particular emphasis was placed on anisotropic morphologies being developed during the nanofiber fabrication process. Global analysis was performed on SAXS data to derive the nanofibrillar structure of repeating lamella crystalline domains with average dimensions of 12.5 nm thickness and 7.8 nm spacing along with associated tie-molecules. The varying surface roughness of the nanofiber was evaluated by extracting the Porod exponent in parallel and perpendicular direction to the nanofiber axis, which was further validated by Atomic Force Microscopy. Additionally, the presence of a mixture of the monoclinic alpha and the orthorhombic beta PVDFhfp phases both exhibiting about 6% larger unit cells compared to the corresponding pure PVDF phases was derived from WAXD. The current study shows a generic approach in detailed understanding of internal structures and surface morphology for nanofibers. This forms the basis for targeted structure and morphology steering and the respective controlling during the fabrication process with the aim to engineer nanofibers for different biomedical applications with specific requirements.

Formation of Nanofibrous Structure in Biopolymer Aerogel during Supercritical CO2 Processing: The Case of Chitosan Aerogel.

Supercritical drying is widely considered as the gold standard to produce aerogels that preserve the microstructure of the gels, but we have found this is not always the case. Chitosan aerogel, one of the emerging biopolymer aerogels, was prepared by chemical cross-linking gelation, followed by solvent exchange with methanol and supercritical drying using CO2. Small-angle X-ray scattering analysis shows that the structure of the wet gel, which consists of Gaussian chains of individual molecular strands, converts into a nanofibrous network during CO2 processing. In situ observation reveals a drastic shrinkage of the gel in CO2, demonstrating that physical coagulation caused by the low affinity between chitosan and CO2 is the main structure-forming step. These results challenge the common perception of supercritical drying: it is no longer an inactive drying method, but rather an active nanostructure forming a tool to produce porous biopolymer materials with tailored structure and properties.

Gold nanoparticle distribution in advanced in vitro and ex vivo human placental barrier models.

BACKGROUND: Gold nanoparticles (AuNPs) are promising candidates to design the next generation NP-based drug formulations specifically treating maternal, fetal or placental complications with reduced side effects. Profound knowledge on AuNP distribution and effects at the human placental barrier in dependence on the particle properties and surface modifications, however, is currently lacking. Moreover, the predictive value of human placental transfer models for NP translocation studies is not yet clearly understood, in particular with regards to differences between static and dynamic exposures. To understand if small (3-4 nm) AuNPs with different surface modifications (PEGylated versus carboxylated) are taken up and cross the human placental barrier, we performed translocation studies in a static human in vitro co-culture placenta model and the dynamic human ex vivo placental perfusion model. The samples were analysed using ICP-MS, laser ablation-ICP-MS and TEM analysis for sensitive, label-free detection of AuNPs. RESULTS: After 24 h of exposure, both AuNP types crossed the human placental barrier in vitro, although in low amounts. Even though cellular uptake was higher for carboxylated AuNPs, translocation was slightly increased for PEGylated AuNPs. After 6 h of perfusion, only PEGylated AuNPs were observed in the fetal circulation and tissue accumulation was similar for both AuNP types. While PEGylated AuNPs were highly stable in the biological media and provided consistent results among the two placenta models, carboxylated AuNPs agglomerated and adhered to the perfusion device, resulting in different cellular doses under static and dynamic exposure conditions. CONCLUSIONS: Gold nanoparticles cross the human placental barrier in limited amounts and accumulate in placental tissue, depending on their size- and/or surface modification. However, it is challenging to identify the contribution of individual characteristics since they often affect colloidal particle stability, resulting in different biological interaction in particular under static versus dynamic conditions. This study highlights that human ex vivo and in vitro placenta models can provide valuable mechanistic insights on NP uptake and translocation if accounting for NP stability and non-specific interactions with the test system.

Bile Salts Caught in the Act: From Emulsification to Nanostructural Reorganization of Lipid Self-Assemblies.

Bile salts (BSs) are important for the digestion and absorption of fats and fat-soluble vitamins in the small intestine. In this work, we scrutinized, with small-angle X-ray scattering (SAXS), the crucial functions of bile salts beyond their capacity for the interfacial stabilization of submicrometer-sized lipid particles. By studying a wide compositional range of BS-lipid dispersions using two widely applied lipids for drug-delivery systems (one a monoglyceride being stabilizer-sensitive and the other an aliphatic alcohol being relatively stabilizer-insensitive), we identified the necessary BS to lipid ratios to guarantee full emulsification. A novel ad hoc developed global small-angle-X-ray scattering analysis method revealed that the addition of BS hardly changes the bilayer thicknesses in bicontinuous phases, while significant membrane thinning is observed in the coexisting fluid lamellar phase. Furthermore, we show that a BS strongly decreases the average critical packing parameter. At increasing BS concentration, the order of phases formed is (i) the bicontinuous diamond cubic ( Pn3 m), (ii) the bicontinuous primitive cubic ( Im3 m), and (iii) the fluid lamellar phase ( Lα). These distinctive findings on BS-driven "emulsification" and "membrane curvature reduction" provide new molecular-scale insights for the understanding of the interfacial action of bile salts on lipid assemblies.

Global Small-Angle X-ray Scattering Data Analysis of Triacylglycerols in the α-Phase (Part II).

The early-stage crystallization behavior in a triacylglycerol mixture has been investigated on the nanoscale with a novel global small-angle X-ray scattering analysis technique. This method has been tailored for the determination of the electron density profiles (EDPs) replicating both (i) the nanostructural texture of molten triacylglycerols (TAGs) (refer to "Global Small-Angle X-ray Scattering Data Analysis of Triacylglycerols in the Molten State (Part I)" of this publication series) and (ii) the lamellar structure of the metastable α-polymorph. In a first stage, the α-phase scattering contribution alone was examined by classical Fourier analysis as well as by globally fitting the data, leading to practically identical EDPs. On the basis of these findings, we extended our analysis to the entire X-ray scattering contribution arising from molten TAGs and the solid α-phase fraction. Remarkably, the experimental and theoretical data agree very well, providing for the first time a detailed nanostructural understanding about the coexisting molecular assemblies. This, in turn, also allowed us to quantitatively determine the solid fat content (SFC) with X-ray scattering data. Our new theoretical approach for measurement of SFC is based on the global analysis of small-angle scattering/diffraction patterns, and the SFC results are in good agreement with values obtained from other techniques such as NMR spectroscopy.

Global Small-Angle X-ray Scattering Data Analysis of Triacylglycerols in the Molten State (Part I).

The study of triacylglycerols (TAGs) in their molten state is of fundamental importance for a deeper understanding of the TAG crystallization processes, being highly relevant for both manufacturing and medical applications. Although different models have been proposed to explain the nanostructured nature of the fluid state of TAGs, none of them are fully satisfactory. In this paper, we propose a new model consisting of positionally uncorrelated lamellar TAG assemblies embedded in an isotropic medium that assist as prenucleating structures. This model was validated by applying a novel global fitting method, resulting in an excellent agreement with the small-angle X-ray scattering data. A deeper analysis of the scattering patterns at different temperatures, both in cooling and heating directions, allowed us further to detect the crystalline traces of TAGs even after heating to 40 °C and record, on cooling, the onset of crystallization at 30-25 °C. The application of the presented novel model not only explains the outstandingly structured fluid of molten TAGs, but also lays the basis for analyzing first the crystallization steps in greater detail, which is outlined in our follow-up paper "Global Small-Angle X-ray Scattering Data Analysis of Triacylglycerols in the α-Phase (Part II)".

Intracellular ROS Induction by Ag@ZnO Core-Shell Nanoparticles: Frontiers of Permanent Optically Active Holes in Breast Cancer Theranostic.

In this study, we investigated whether ZnO coating on Ag nanoparticles (NPs) tunes electron flux and hole figuration at the metal-semiconductor interface under UV radiation. This effect triggers the photoactivity and generation of reactive oxygen species from Ag@ZnO NPs, which results in enhanced cytotoxic effects and apoptotic cell death in human breast cancer cells (MDA-MB231). In this context, upregulation of apoptotic cascade proteins (i.e., Bax/Bcl2 association, p53, cytochrome c, and caspase-3) along with activation of oxidative stress proteins suggested the occurrence of apoptosis by Ag@ZnO NPs in cancer cells through the mitochondrial pathway. Also, preincubation of breast cancer cells with Ag@ZnO NPs in dark conditions muted NP-related toxic effects and consequent apoptotic fate, highlighting biocompatible properties of unexcited Ag@ZnO NPs. Furthermore, the diagnostic efficacy of Ag@ZnO NPs as computed tomography (CT)/optical nanoprobes was investigated. Results confirmed the efficacy of the photoactivated system in obtaining desirable outcomes from CT/optical imaging, which represents novel theranostic NPs for simultaneous imaging and treatment of cancer.