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Spherical nanoparticles and anisotropic magnetic nanochains were synthesized, and the impact of their shape anisotropy on cellular uptake was studied. Our findings reveal significant differences in the extent of their intracellular accumulation.

To improve the physical stability of nanoparticle dispersions, several methods for their transformation into stable and easily dispersible dry products have been investigated thus far. Recently, electrospinning was shown to be a novel nanoparticle dispersion drying method, which addresses the crucial challenges of the current drying methods. It is a relatively simple method, but it is affected by various ambient, process, and dispersion parameters, which impact the properties of the electrospun product. The aim of this study was, thus, to investigate the influence of the most important dispersion parameter, namely the total polymer concentration, on the drying method efficiency and the properties of the electrospun product. The formulation was based on a mixture of hydrophilic polymers poloxamer 188 and polyethylene oxide in the weight ratio of 1:1, which is acceptable for potential parenteral application. We showed that the total polymer concentration of prior-drying samples is closely related to their viscosity and conductivity, also affecting the morphology of the electrospun product. However, the change in morphology of the electrospun product does not affect the efficiency of SPION reconstitution from the electrospun product. Regardless of the morphology, the electrospun product is not in powder form and is therefore safer to handle compared to powder nanoformulations. The optimal total polymer concentration in the prior-drying SPION dispersion, which enables the formation of an easily dispersible electrospun product with high SPION-loading (65% (w/w)) and fibrillar morphology, was shown to be 4.2% (w/v).

Controlled spatial arrangements of superparamagnetic iron oxide nanoparticles (SPIONs) in complex nanostructures determine fine tuning of physico-chemical properties which, in turn, may lead to new practical applications. We report here on newly observed properties of hierarchical SPIONs nanostructure with bundle-like morphology, also known as nanobundles. Colloidal chemical processes and sol-gel synthesis were used for the synthesis of nanobundles, i.e. i) self-assembly of SPIONs into magnetic nanoparticle clusters, ii) their magnetic assembly to the nanochains, and finally iii) formation of bundle-like hierarchical nanostructure. An XRPD measurements show spinel crystal structure of maghemite/magnetite nanoparticles, EDS analysis reveals Fe, Si and O as main elements whereas SEM/TEM analysis show silica-coated magnetic nanoclusters (∼100 nm) and their hierarchical assemblies with bundle-like morphology of ∼8 μm length and ∼1 μm width. TEM analysis revealed core-shell nature of iron oxide nanoparticle clusters with their size of around 80 nm that were coated by an amorphous silica shell with thickness of ∼15 nm. The nanoclusters in the core are constructed of maghemite/magnetite nanoparticle assembly with primary iron oxide nanoparticle size about 10 nm. The magnetization M data as a function of an applied external magnetic field H were successfully fitted by the Langevin function, whence the magnetic moment μp = 19256 μB, and the diameter d = 9.6 nm of nanoparticles were determined. Microsized bundle-like particles are superparamagnetic, magnetically guidable and possess high transverse relaxivity of r2 = 397.8 mM−1s−1. Magnetic properties and such high value of transverse relaxivity holds promise for nanobundles application in MRI imaging (MRI contrast agent), as nanobundles may enhance the magnetic field in their surroundings and enhance proton relaxation processes. Our nanobundles can open new opportunities in the biomedical applications, magnetic separation, photonic crystals and magnetic liquid manipulation and can be inspiration for synthesizing novel self-assembled nanoparticle structures. © 2022 Elsevier Ltd and Techna Group S.r.l.

The conjugation of photoactive benzophenone with diphenylalanine yielded a self-assembling photocatalyst that was probed in the E → Z photoisomerisation of stilbene derivatives.

Nanocomposite hydrogels have attracted researchers’ attention in recent years to achieve superior performances in a variety of materials applications. In this work, we describe the outcome of three different strategies to combine a self-assembling tripeptide and carbon nano-onions (CNOs), through covalent and non-covalent approaches, into supramolecular and nanostructured hydrogels. Importantly, the tripeptide coated the nano-onions and extended their aqueous dispersions’ stability by several hours. Furthermore, CNOs could be loaded in the tripeptide hydrogels at the highest level ever reported for nanocarbons, indicating high compatibility between the components. The materials were formed in phosphate-buffered solutions, thus paving the way for biological applications, and were characterized by several spectroscopic, microscopic, thermogravimetric, and rheological techniques. In vitro experiments demonstrated excellent cytocompatibility.

We studied inflammatory and oxidative stress-related parameters and cytotoxic response of human umbilical vein endothelial cells (HUVEC) to a 24 h treatment with milled particles simulating debris involved in sandblasting of orthopedic implants (OI). We used different abrasives (corundum—(Al2O3), used corundum retrieved from removed OI (u. Al2O3), and zirconia/silica composite (ZrO2/SiO2)). Morphological changes were observed by scanning electron microscopy (SEM). Concentration of Interleukins IL-6 and IL-1β and Tumor Necrosis Factor α (TNF)-α was assessed by enzyme-linked immunosorbent assay (ELISA). Activity of Cholinesterase (ChE) and Glutathione S-transferase (GST) was measured by spectrophotometry. Reactive oxygen species (ROS), lipid droplets (LD) and apoptosis were measured by flow cytometry (FCM). Detachment of the cells from glass and budding of the cell membrane did not differ in the treated and untreated control cells. Increased concentration of IL-1β and of IL-6 was found after treatment with all tested particle types, indicating inflammatory response of the treated cells. Increased ChE activity was found after treatment with u. Al2O3 and ZrO2/SiO2. Increased GST activity was found after treatment with ZrO2/SiO2. Increased LD quantity but not ROS quantity was found after treatment with u. Al2O3. No cytotoxicity was detected after treatment with u. Al2O3. The tested materials in concentrations added to in vitro cell lines were found non-toxic but bioactive and therefore prone to induce a response of the human body to OI.

FLO-1 cell line represents an important tool in esophageal adenocarcinoma (EAC) research as a verified and authentic cell line to study the disease pathophysiology and antitumor drug screenings. Since in vitro characteristics of cells depend on the microenvironment and culturing conditions, we performed a thorough characterization of the FLO-1 cell line under different culturing conditions with the aim of (1) examining the effect of serum-free growth medium and air–liquid interface (A–L) culturing, which better reflect physiological conditions in vivo and (2) investigating the differentiation potential of FLO-1 cells to mimic the properties of the in vivo esophageal epithelium. Our study shows that the composition of the media influenced the morphological, ultrastructural and molecular characteristics of FLO-1 cells, such as the expression of junctional proteins. Importantly, FLO-1 cells formed spheres at the A–L interface, recapitulating key elements of tumors in the esophageal tube, i.e., direct contact with the gas phase and three-dimensional architecture. On the other hand, FLO-1 models exhibited high permeability to model drugs and zero permeability markers, and low transepithelial resistance, and therefore poorly mimicked normal esophageal epithelium. In conclusion, the identified effect of culture conditions on the characteristics of FLO-1 cells should be considered for standardization, data reproducibility and validity of the in vitro EAC model. Moreover, the sphere-forming ability of FLO-1 cells at the A–L interface should be considered in EAC tumor biology and anticancer drug studies as a reliable and straightforward model with the potential to increase the predictive efficiency of the current in vitro approaches.

Anisotropic magnetic nanoparticles with a mesoporous silica shell have the combined merits of a magnetic core and a robust shell. Preparation of magnetically guidable core–shell nanostructures with a robust silica shell that contains well-defined, large, radially aligned silica pores is challenging, and hence this has rarely been described in detail. Herein, a dynamic soft-templating strategy is developed to controllably synthesize hierarchical, dual-mesoporous silica shells on diverse core nanoparticles, in terms of nanoparticle shape (i.e., spherical, chainlike, and disclike), magnetic properties (i.e., hard magnetic and superparamagnetic), and dimensions (i.e., from 3 nm to submicrometers). The developed interfacial coassembly method allows easy design of applicable silica shells containing tunable pore geometries with pore sizes ranging from below 5 nm to above 40 nm, with a specific surface area of 577 m2 g–1 and pore volume of 1.817 cm3 g–1. These are the highest values reported for magnetically guidable anisotropic nanoparticles. The versatility of the method is shown by transfer of the coating procedure to core particles as diverse as spherical superparamagnetic nanoparticles and their clusters as well as by ferromagnetic 3 nm thick hexaferrite nanoplatelets. This method can serve as a general approach for the fabrication of well-designed mesoporous silica coatings on a wide variety of core nanoparticles.

Superparamagnetic iron oxide nanoparticles (SPIONs) have great potential for use in medicine, but they may cause side effects due to oxidative stress. In our study, we investigated the effects of silica-coated SPIONs on endothelial cells and whether oleic acid (OA) can protect the cells from their harmful effects. We used viability assays, flow cytometry, infrared spectroscopy, fluorescence microscopy, and transmission electron microscopy. Our results show that silica-coated SPIONs are internalized by endothelial cells, where they increase the amount of reactive oxygen species (ROS) and cause cell death. Exposure to silica-coated SPIONs induced accumulation of lipid droplets (LD) that was not dependent on diacylglycerol acyltransferase (DGAT)-mediated LD biogenesis, suggesting that silica-coated SPIONs suppress LD degradation. Addition of exogenous OA promoted LD biogenesis and reduced SPION-dependent increases in oxidative stress and cell death. However, exogenous OA protected cells from SPION-induced cell damage even in the presence of DGAT inhibitors, implying that LDs are not required for the protective effect of exogenous OA. The molecular phenotype of the cells determined by Fourier transform infrared spectroscopy confirmed the destructive effect of silica-coated SPIONs and the ameliorative role of OA in the case of oxidative stress. Thus, exogenous OA protects endothelial cells from SPION-induced oxidative stress and cell death independent of its incorporation into triglycerides.

Diphenylalanine is an amyloidogenic building block that can form a versatile array of supramolecular materials. Its shortcomings, however, include the uncontrolled hierarchical assembly into microtubes of heterogeneous size distribution and well-known cytotoxicity. This study rationalized heterochirality as a successful strategy to address both of these pitfalls and it provided an unprotected heterochiral dipeptide that self-organized into a homogeneous and optically clear hydrogel with excellent ability to sustain fibroblast cell proliferation and viability. Substitution of one l-amino acid with its d-enantiomer preserved the ability of the dipeptide to self-organize into nanotubes, as shown by single-crystal XRD analysis, whereby the pattern of electrostatic and hydrogen bonding interactions of the backbone was unaltered. The effect of heterochirality was manifested in subtle changes in the positioning of the aromatic side chains, which resulted in weaker intermolecular interactions between nanotubes. As a result, d-Phe-l-Phe self-organized into homogeneous nanofibrils with a diameter of 4 nm, corresponding to two layers of peptides around a water channel, and yielded a transparent hydrogel. In contrast with homochiral Phe-Phe stereoisomer, it formed stable hydrogels thermoreversibly. d-Phe-l-Phe displayed no amyloid toxicity in cell cultures with fibroblast cells proliferating in high numbers and viability on this biomaterial, marking it as a preferred substrate over tissue-culture plastic. Halogenation also enabled the tailoring of d-Phe-l-Phe self-organization. Fluorination allowed analogous supramolecular packing as confirmed by XRD, thus nanotube formation, and gave intermediate levels of bundling. In contrast, iodination was the most effective strategy to augment the stability of the resulting hydrogel, although at the expense of optical transparency and biocompatibility. Interestingly, iodine presence hindered the supramolecular packing into nanotubes, resulting instead into amphipathic layers of stacked peptides without the occurrence of halogen bonding. By unravelling fine details to control these materials at the meso- and macro-scale, this study significantly advanced our understanding of these systems.

Sustainability is becoming a key driver for product differentiation, and corporations around the world are setting specific sustainability metrics on new products. Greenhouse gas emissions (GHG), l...

A metastable ε-polymorph of iron(III) oxide (ε-Fe2O3) is a very attractive material from the technological, engineering, and scientific points of view. In comparison with other iron oxides, it is characterized by unusual magnetic properties and a giant coercivity of ~20 kOe, which is the largest value among metal oxides. The routine method of ε-Fe2O3 formation is based on the thermal annealing of maghemite (γ-Fe2O3) nanoparticles confined in a silica matrix where the ε-Fe2O3 appears as an intermediate phase between the maghemite and an α-polymorph (α-Fe2O3) hematite (γ→ε→α pathway). In this study, it is demonstrated that the ε→α transformation can be reversed when hematite nanoparticles with an anisotropic hollow morphology are annealed above 600 °C. The observed reversal of the phase stability is explained in terms of an increased nanoparticle surface area and surface energy related to the hollow structure. This study demonstrates the applicability of surface-induced phase transformation to stabilize and control ε-Fe2O3 nanostructures with anisotropic shape and high coercivity ~1600 kA/m that is one of the key properties of functional magnetic materials for information processing and storage. The understanding of ε-Fe2O3 formation mechanism can provide a new viewpoint and guidance for designing metastable polymorphs and applicative properties. © 2020 Acta Materialia Inc.

N-(4-Nitrobenzoyl)-Phe self-assembled into a transparent supramolecular hydrogel, which displayed high fibroblast and keratinocyte cell viability. The compound showed a mild antimicrobial activity against E. coli both as a hydrogel and in solution. Single-crystal XRD data revealed packing details, including protonation of the C-terminus due to an apparent pK(a) shift, as confirmed by pH titrations. MicroRaman analysis revealed almost identical features between the gel and crystal states, although more disorder in the former. The hydrogel is thermoreversible and disassembles within a range of temperatures that can be fine-tuned by experimental conditions, such as gelator concentration. At the minimum gelling concentration of 0.63 wt %, the hydrogel disassembles in a physiological temperature range of 39-42 degrees C, thus opening the way to its potential use as a biomaterial.

Dipeptides are popular building blocks for supramolecular gels that do not persist in the environment and may find various applications. In this work, we show that a simple substitution on the aromatic side-chain of phenylalanine with either fluorine or iodine enables supramolecular diversity upon self-assembly at neutral pH, leading to hydrogels or crystals. Each building block is characterized by H-1- and C-13-NMR spectroscopy, LC-MS, circular dichroism, and molecular models. The supramolecular behaviour is monitored with a variety of techniques, including circular dichroism, oscillatory rheology, transmission electron microscopy, attenuated total reflectance Fourier-transformed infrared spectroscopy, visible Raman spectroscopy, synchrotron-radiation single-crystal X-ray diffraction and UV Resonance Raman spectroscopy, allowing key differences to be pinpointed amongst the halogenated analogues.

Dipeptides are convenient building blocks for supramolecular gel biomaterials that can be produced on a large scale at low cost and do not persist in the environment. In the case of unprotected sequences, hydrophobicity is a key requirement to enable gelation, with Phe-Phe standing out for its self-assembling ability. Conversely, more hydrophilic sequences such as homochiral dipeptides Phe-Val and Val-Phe neither fibrillate nor gel aqueous buffers and their crystal structures reveal amphipathic layers. In this work, we test emerging rules for the design of self-assembling dipeptides using heterochiral Phe-Val and Val-Phe. Each dipeptide is characterized by H-1- and C-13-NMR, LC-MS, circular dichroism, infrared and Raman spectroscopies, rheology, electron microscopy, and single-crystal X-ray diffraction. In particular, d-Phe-l-Val is the first heterochiral dipeptide to self-assemble into supramolecular water-channels whose cavity is defined by four peptide molecules arranged head-to-tail. This minimalistic sequence is devoid of amyloid character as probed by thioflavin T fluorescence and it displays excellent biocompatibility in vitro. The dataset provided, through comparison with the literature, significantly advances the definition of molecular design rules for minimalistic unprotected dipeptides that self-assemble into water-channels and biocompatible gels, to assist with the future development of supramolecular biomaterials with fine control over nanomorphological features for a variety of applications.

Unprotected dipeptides are attractive building blocks for environmentally friendly hydrogel biomaterials by virtue of their low-cost and ease of preparation. This work investigates the self-assembling behaviour of the distinct stereoisomers of Ile-Phe and Phe-Ile in phosphate buffered saline (PBS) to form hydrogels, using transmission electron microscopy (TEM), attenuated total reflectance infrared spectroscopy (ATR-IR), circular dichroism (CD), and oscillatory rheometry. Each peptide purity and identity was also confirmed by 1 H- and 13 C-NMR spectroscopy and HPLC-MS. Finally, single-crystal XRD data allowed the key interactions responsible for the supramolecular packing into amphipathic layers or water-channels to be revealed. The presence of the latter in the crystal structure is a distinctive feature of the only gelator of this work that self-organizes into stable hydrogels, with fast kinetics and the highest elastic modulus amongst its structural isomers and stereoisomers.

One of the key technological challenges in the development of iron-oxide-based magnetic nanoparticles (MNPs) is their long-term physical stability in colloidal dispersions. This can be improved by their transformation into a dry form. Here, we introduce electrospinning as a drying method for ethanol-based and water-based MNP dispersions, which enables the preparation of high-loaded dry MNP products. The obtained easily dispersible electrospun product contained up to 50 % (w/w) of MNPs, homogeneously distributed in the fibrillar structure, which is much more compared to the products of currently available methods for drying MNP dispersions. The polymers used as building blocks of nanofibers, namely poloxamer 188 and polyethylene oxide, improved the tolerance of MNPs to high ionic strength dispersion medium and thus enhanced the short-term physical stability of MNP dispersions after reconstitution. The dry product was stable for up to 1 month at room temperature and relative humidity up to 70 %. It was in the form of a nanofiber mat, which prevented the aerosolization of MNPs and their unintentional ambient exposure. Therefore, the electrospun product with MNPs is expected to be a safer dry formulation of MNPs than the nanoparticulate powders, which are usually the final products of the conventional drying methods.

The increasing interest in upconverting nanoparticles (UCNPs) in biodiagnostics and therapy fuels the development of biocompatible UCNPs platforms. UCNPs are typically nanocrystallites of rare-earth fluorides codoped with Yb

In this paper we present a major advance in the colloidal stabilization of nanoparticles in complex biological media that is one of the ongoing challenges for the usage of nanoparticles in biomedicine. A very common solution is to coat the nanoparticles surfaces with dextran via an electrostatic or coordinative attachment. The dextran molecules can be subsequently crosslinked to form a biocompatible coating. However, these procedures are not suitable for nanoparticles with an extreme tendency for agglomeration that often occurs during the coating steps. The novel functionalisation strategy ensures the colloidal stability of the system in all the steps of the coating process. In addition to this, the robustness of the dextran coating, obtained by the covalent attachment of the dextran molecules via the 3-glycidyloxypropyl-trimethoxysilane linker to the surfaces of the silica-coated nanoparticles, ensures the colloidal stability of nanoparticles in complex biological media. As a case study we selected permanently magnetic barium hexaferrite nanoplatelets that are extremely prone to agglomeration due to the magnetic dipole-dipole interaction and their plate-like shape. At the same time barium hexaferrite nanoplatelets are receiving an increasing attention for its use in biomedical applications. The multistep formation of the coating was followed with transmission electron microscopy, nuclear magnetic resonance and electro-kinetic measurements, while the colloidal stability in different complex biological buffer media was inspected visually and with dynamic laser scattering.

Investigation and synthesis of anisotropic magnetic nanostructures, such as wires, rods, fibers, tubes and chains, is an important field of research due to the beneficial properties and great potential for practical applications ranging from magnetic data storage to biomedicine. Silica coated iron oxide nanochains of length up to 1 μm and diameter ∼80–100 nm have been synthesized by the simultaneous magnetic assembly of superparamagnetic iron oxide nanoparticle clusters (SNCs) as links (viz. maghemite, γ-Fe2O3) and the fixation of the assembled SNCs with an additional layer of deposited silica. We reveal that is possible to achieve either superparamagnetic or ferromagnetic behavior with the nanochains depending only on their physical orientation. The superparamagnetic behavior is observed for random orientation of nanochains whereas ferromagnetic properties (HC ≈ 100 Oe) come to the fore when the orientation is mainly parallel. These peculiar magnetic properties can be related to: (1) the specific size, which is ∼9 nm, of primary building blocks of the nanochains, i.e. of maghemite nanoparticles; (2) to the anisotropic chain-like shape of the particles; and (3) to inter-particle interactions. Large pore volume and pore size of silica shell as well as good colloidal stability and magnetic responsiveness of such nanochains enable applications in biomedicine. © 2019 Elsevier B.V.

Magneli phase titanium suboxides (Magneli TiOx) are novel conductive materials with great industrial potential. This is the first comprehensive investigation to provide an extensive dataset for hazard characterisation of Magneli TiOx using six standardised test organisms and two human cell lines. Three Magneli TiOx particles and three anatase crystalline phase TiO2 nanomaterials with different primary powder sizes, but similar hydrodynamic diameters in biological media, were investigated. All Magneli TiOx and TiO2 nanomaterials induced negligible biological responses in Tetrahymena thermophila, Lemna minor, Artemia franciscana and Danio rerio. Adverse effects were found only at 100 mg L−1 where approximately 50% endpoint inhibition was recorded in the cases of Daphnia magna exposed to two Magneli TiOx, Pseudokirchneriella subcapitata exposed to all three Magneli TiOx and HepG2 cells exposed to one type of Magneli TiOx. This study provides the first evidence that the tested Magneli TiOx are not acutely hazardous according to existing EU classification for conventional chemicals.

Self-assembling peptides are being applied both in the biomedical area and as building blocks in nanotechnology. Their applications are closely linked to their modes of self-assembly, which determine the functional nanostructures that they form. This work brings together two structural elements that direct nanoscale self-association in divergent directions: proline as a β-breaker and the β-structure-associated diphenylalanine motif, into a single tripeptide sequence. Amino acid chirality was found to resolve the tension inherent to these conflicting self-assembly instructions. Stereoconfiguration determined the ability of each of the eight possible Pro-Phe-Phe stereoisomers to self-associate into diverse nanostructures, including nanoparticles, nanotapes, or fibrils, which yielded hydrogels with gel-to-sol transition at a physiologically relevant temperature. Three single-crystal structures and all-atom molecular dynamics simulations elucidated the ability of each peptide to establish key interactions to form long-range assemblies (i,e., stacks leading to gelling fibrils), medium-range assemblies (i.e., stacks yielding nanotapes), or short-range assemblies (i.e., dimers or trimers that further associated into nanoparticles). Importantly, diphenylalanine is known to serve as a binding site for pathological amyloids, potentially allowing these heterochiral systems to influence the fibrillization of other biologically relevant peptides. To probe this hypothesis, all eight Pro-Phe-Phe stereoisomers were tested in vitro on the Alzheimer's disease-associated Aβ(1-42) peptide. Indeed, one nonfibril-forming stereoisomer effectively inhibited Aβ fibrillization through multivalent binding between diphenylalanine motifs. This work thus defined heterochirality as a useful feature to strategically develop future therapeutics to interfere with pathological processes, with the additional value of resistance to protease-mediated degradation and biocompatibility.

A porous hematite/alumina nanocomposite is produced by sol-gel combustion synthesis. The XRPD, Raman and FTIR methods show the presence of α-Fe2O3 phase while SEM, TEM, EDS and BET techniques further reveal the formation of porous ellipsoid-like nanostructure of hematite nanoparticles coated by amorphous alumina. Hematite nanoparticles have a size of ~40 nm whereas the porous hematite/alumina nanocomposite particles are ~100 nm in size with characteristic pores of ~7 nm. The M(H) at 300 K exhibits coercivity HC = 293 Oe and magnetization MS = 2.71 emu/g and at 5 K HC = 1150 Oe and MS = 9.25 emu/g. The M(T) under H = 100 Oe shows a bifurcation between ZFC/FC magnetization curves at all measurement temperatures Tirr>350 K (irreversibility temperature) and blocking temperature at TB ~ 305 K. Unexpectedly, the M(T) measurements under H = 10 kOe reveal the suppressed Morin transition at TM = 225 K. The analysis of the results and data from the literature reveal that the porous surface structure of hematite induces the atypical magnetic properties. A magnetic resonance imaging (MRI) properties show the transverse relaxivity rate (r2) of 0.44 mM−1s−1 at 7 T and 1.06 mM−1s−1 at 15.2 T. The investigated nanocomposite particles could be useful in biomedical applications due to their low cytotoxicity and porous nanostructure.

The feasibility of a peroxidase–aldolase cascade reaction for the synthesis of therapeutically- valuable iminocyclitols is discussed herein. A two-enzyme system consisting of chloroperoxidase (CPO) and D-fructose-6-phosphate aldolase (FSA) was evaluated for the synthesis of a precursor of D-fagomine from a β-amino alcohol (N-Cbz-3- aminopropanol). Both the oxidation and aldol addition reactions were investigated to elucidate the reaction mechanism, prepare suitable stabilized biocatalysts, and find the optimal conditions for its application. Also, the inactivation of both enzymes and many other side reactions (the oxidation of the intermediate amino aldehyde, an aldehyde-peroxide reaction, etc.), are discussed and analyzed in detail. An in-depth, systematic, step-by-step kinetic modeling of all the reactions was proposed as an approach for a better understanding of the system, and a possible strategy to optimize it. The model was able to accurately describe the system and predict the outcome at different experimental conditions. The inactivation of FSA caused by CPO-catalyzed reactions was identified as the many bottleneck in the reaction. A two- step reaction approach and the use of immobilized enzymes derivatives on magnetic nanoparticle clusters and functionalized agarose carriers increased the stability of FSA, and thus a higher product yield was obtained with a 577-fold higher preFagomine formation per mol of enzyme.

Fructose-6-phosphate aldolase (FSA) is an important enzyme for the C-C bond-forming reactions in organic synthesis. The present work is focused on the synthesis of a precursor of D-fagomine catalyzed by a mutant FSA. The biocatalyst has been immobilized onto several supports: magnetic nanoparticle clusters (mNC), cobalt-chelated agarose (Co-IDA), amino-functionalized agarose (MANA-agarose) and glyoxal-agarose, obtaining a 29.0%, 93.8%, 89.7% and 53.9% of retained activity, respectively. Glyoxal-agarose FSA derivative stood up as the best option for the synthesis of the precursor of D-fagomine due to the high reaction rate, conversion, yield and operational stability achieved. FSA immobilized in glyoxal-agarose could be reused up to 6 reaction cycles reaching a 4-fold improvement in biocatalyst yield compared to the non-immobilized enzyme., This work was supported by the Spanish MINECO (project No. CTQ2014-53114R), co-financed by European Regional Development Fund. The Department of Chemical, Biological and Environmental Engineering of UAB constitutes the Biochemical Engineering Unit of the Reference Network in Biotechnology, and the research group 2017-SGR-1462, Generalitat de Catalunya. Financial support from Spanish MINECO for the PhD scholarship of Luis Miguel Vázquez and Gerard Masdeu were also received. The authors received also financial support from the Slovenian Research Agency (ARRS) for research core funding No. (P2-0089) and projects No. (J1-7302, J3-7494, and J2-8166).

International audience; Superparamagnetic iron oxide nanoparticles (SPIONs) have a recognized potential for magnetic hyperthermia, and they are also being increasingly proposed as agents for photothermal treatment (photothermia), a biomedical modality where nanoparticles are excited by light to generate local hyperthermia. While it is known that endosomal internalization of SPIONs negatively affects magnetic hyperthermia, photothermia is not decreased. In an attempt to mimic nanoparticles clustering in endosomes, we herein investigate the effects of silica encapsulation and SPION clustering on both magnetic hyperthermia and photothermia.

Self-assembling peptides are attracting wide interest as biodegradable building blocks to achieve functional nanomaterials that do not persist in the environment. Amongst the many applications, biocatalysis is gaining momentum, although a clear structure-to-activity relationship is still lacking. This work applied emerging design rules to the heterochiral octapeptide sequence His&ndash, Leu&ndash, DLeu&ndash, Ile&ndash, His&ndash, Ile for self-assembly into nanofibrils that, at higher concentration, give rise to a supramolecular hydrogel for the mimicry of esterase-like activity. The peptide was synthesized by solid-phase and purified by HPLC, while its identity was confirmed by 1H-NMR and electrospray ionization (ESI)-MS. The hydrogel formed by this peptide was studied with oscillatory rheometry, and the supramolecular behavior of the peptide was investigated with transmission electron microscopy (TEM) analysis, circular dichroism (CD) spectroscopy, thioflavin T amyloid fluorescence assay, and attenuated total reflectance (ATR) Fourier-transform infrared (FT-IR) spectroscopy. The biocatalytic activity was studied by monitoring the hydrolysis of p-nitrophenyl acetate (pNPA) at neutral pH, and the reaction kinetics followed an apparent Michaelis&ndash, Menten model, for which a Lineweaver&ndash, Burk plot was produced to determine its enzymatic parameters for a comparison with the literature. Finally, LC&ndash, MS analysis was conducted on a series of experiments to evaluate the extent of, if any, undesired peptide acetylation at the N-terminus. In conclusion, we provide new insights that allow gaining a clearer picture of self-assembling peptide design rules for biocatalysis.

Ferrous core-shell nanoparticles consisting of a magnetic γ-Fe2O3 multi-nanoparticle core and an outer silica shell have been synthesized and covalently functionalized with Rhodamine B (RhB) fluorescent molecules (γ-Fe2O3/SiO2/RhB NPs). The resulting γ-Fe2O3/SiO2/RhB NPs were integrated with a renewable and naturally-abundant cellulose derivative (i.e. cellulose acetate, CA) that was processed in the form of electrospun fibers to yield multifunctional fluorescent fibrous nanocomposites. The encapsulation of the nanoparticles within the fibers and the covalent anchoring of the RhB fluorophore onto the nanoparticle surfaces prevented the fluorophore’s leakage from the fibrous mat, enabling thus stable fluorescence-based operation of the developed materials. These materials were further evaluated as dual fluorescent sensors (i.e. ammonia gas and pH sensors), demonstrating consistent response for very high ammonia concentrations (up to 12000 ppm) and fast and linear response in both alkaline and acidic environments. The superparamagnetic nature of embedded nanoparticles provides means of electrospun fibers morphology control by magnetic field-assisted processes and additional means of electromagnetic-based manipulation making possible their use in a wide range of sensing applications.

Amino acid stereoconfiguration has been shown to play a key role in the self-assembly of unprotected tripeptides into hydrogels under physiological conditions. Dramatic changes were noted for hydrophobic sequences based on the diphenylalanine motif from the formation of amorphous aggregates in the case of homochiral peptides to nanostructured and stable hydrogels in the case of heterochiral stereoisomers. Herein, we report that by further shortening the sequence to a dipeptide, the overall differences between isomers are less marked, with both homo- and hetero-chiral dipeptides forming gels, although with different stability over time. The soft materials are studied by a number of spectroscopic and microcopic techniques, and single-crystal X-ray diffraction to unveil the supramolecular interactions of these hydrogel building blocks.

Due to advances in electron microscopy and to the development of novel nanoparticle structures with different morphologies and the dependence of physical properties on the nanoparticle morphology, there is a need for a more precise analysis of nanoparticle structure and morphology. That should provide a simple and unambiguous comparison of nanoparticles‘ shapes and of material properties that depend on the shape, which has been lacking thus far. Here we study nanochains consisting of silica-coated iron oxide (maghemite, γ-Fe2O3) nanoparticle clusters covered by an additional layer of silica (core-shell structure). We have developed an algorithm for image segmentation and a quantitative analysis of nanochain shape from real TEM images. To that end we used two distinct measures of circularity and elongation measure (the aspect ratio measure). We show that the relative position and the area of the links, as well as the links‘ shape lead to significant differences in the measured aspect ratio of the entire nanochain (substantially influence the elongation of nanochains). We have also analyzed the core-shell structures in nanochains, and computed the shell's share in the overall area of observed nanochains. A Matlab code was developed and used for the computation of the elongation measure of shapes appearing in electron microscopy images. Here we have investigated magnetic properties of synthetic nanochains, that revealed superparamagnetic behavior at room temperature (SPION) with the possibility of tuning the magnetization values (approx. from 19 to 46 emu/g). We have compared of magnetization M(H) curves of the anisotropic nanochains and of isotropic nanoparticle (nanochain links), with the conclusion that the nanochains have a higher magnetic susceptibility, which fact can be understood as a consequence of their anisotropic shapes. The nanochains may be applied in biomedicine and magnetic separation, due to their morphology and magnetic properties.

The increasing interest in upconverting nanoparticles (UCNPs) in biodiagnostics and therapy fuels the development of biocompatible UCNPs platforms. UCNPs are typically nanocrystallites of rare-earth fluorides codoped with Yb3+ and Er3+ or Tm3+. The most studied UCNPs are based on NaYF4 but are not chemically stable in water. They dissolve significantly in the presence of phosphates. To prevent any adverse effects on the UCNPs induced by cellular phosphates, the surfaces of UCNPs must be made chemically inert and stable by suitable coatings. We studied the effect of various phosphonate coatings on chemical stability and in vitro cytotoxicity of the Yb3+,Er3+-codoped NaYF4 UCNPs in human endothelial cells obtained from cellular line Ea.hy926. Cell viability of endothelial cells was determined using the resazurin-based assay after the short-term (15 min), and long-term (24 h and 48 h) incubations with UCNPs dispersed in cell-culture medium. The coatings were obtained from tertaphosphonic acid (EDTMP), sodium alendronate and poly(ethylene glycol)-neridronate. Regardless of the coating conditions, 1 − 2 nm-thick amorphous surface layers were observed on the UCNPs with transmission electron microscopy. The upconversion fluorescence was measured in the dispersions of all UCNPs. Surafce quenching in aqueous suspensions of the UCNPs was reduced by the coatings. The dissolution degree of the UCNPs was determined from the concentration of dissolved fluoride measured with ion-selective electrode after the ageing of UCNPs in water, physiological buffer (i.e., phosphate-buffered saline—PBS) and cell-culture medium. The phosphonate coatings prepared at 80 °C significantly suppressed the dissolution of UCNPs in PBS while only minor dissolution of bare and coated UCNPs was measured in water and cell-culture medium. The viability of human endothelial cells was significantly reduced when incubated with UCNPs, but it increased with the improved chemical stability of UCNPs by the phosphonate coatings with negligible cytotoxicity when coated with EDTMP at 80 °C.

The combination of different components such as carbon nanostructures and organic gelators into composite nanostructured hydrogels is attracting wide interest for a variety of applications, including sensing and biomaterials. In particular, both supramolecular hydrogels that are formed from unprotected D,L-tripeptides bearing the Phe-Phe motif and nitrogen-doped carbon nanodots (NCNDs) are promising materials for biological use. In this work, they were combined to obtain luminescent, supramolecular hydrogels at physiological conditions. The self-assembly of a tripeptide upon application of a pH trigger was studied in the presence of NCNDs to evaluate effects at the supramolecular level. Luminescent hydrogels were obtained whereby NCND addition allowed the rheological properties to be fine-tuned and led to an overall more homogeneous system composed of thinner fibrils with narrower diameter distribution.

BACKGROUND Hybrid enzyme-nanoparticle complexes, obtained by enzyme immobilization onto superparamagnetic particles, display unique properties for use as biocatalysts. A novel methodology for the immobilization of chloroperoxidase (CPO) onto magnetic nanoparticle clusters (mNC) is presented. Chloroperoxidase catalyzes alcohol oxidations using peroxides, and it has been recently shown to recognize β-amino alcohols as substrates, although high required peroxide concentration led to poor CPO stability. RESULTS mNC retains the superparamagnetic properties of the single nanoparticle plus an increased magnetic moment, necessary for effective magnetic recovery. Different functional groups have been introduced on the silica layer that covers mNC . The linkage enzyme–support has been intended through different reactive groups on the CPO surface. The selected biocatalyst (95% yield, 63% retained activity), obtained by prior enzyme oxidation followed by coupling to the amino groups on the mNC surface, has been compared to soluble CPO in the model reaction (N-Cbz-3-aminopropanol oxidation) with significantly higher substrate conversion due to 4-fold increased enzyme stability. CONCLUSIONS Functionalized mNC has demonstrated to be efficient for the preparation of hybrid enzyme-mNC biocatalysts. The systematic study of chloroperoxidase immobilization onto mNC led to several useful biocatalysts. The described methodology could easily be extended to many other enzymes in the preparation of efficient and reusable biocatalysts.

We report the first histidine-containing self-assembling tripeptide devoid of capping groups that forms a thermoreversible hydrogel under physiological conditions and catalyses hydrolysis of an ester, providing a minimalist building block for functional soft materials.

Upconverting nanoparticles (UCNPs) of β-NaYF4, co-doped with Yb3+ and Tm3+ and 21–36 nm large, were synthesized using a modified thermal decomposition method. The as-synthesized UCNPs were coated with oleic acid and dispersed in nonpolar media. Their morphology, size and crystal structure were analysed with transmission electron microscopy and X-ray diffraction. The UCNPs showed a fluorescence emission spectrum characteristic of Tm3+. Their dissolution in water (pH ∼ 4–5) and phosphate buffered saline (PBS, pH = 7.4) was determined from the fraction of dissolved fluoride ions using a fluoride-ion-selective electrode. The dissolution of bare UCNPs was much more prominent in PBS than in water. Two amphiphilic coatings, poly(maleic anhydride-alt-1-octadecene)−bis(hexamethylene)triamine (PMAO–BHMT) and D-α-tocopheryl polyethylene glycol succinate (TPGS) were tested for their effects on the dissolution of the UCNPs. The coatings were formed directly on the as-synthesized UCNPs as was confirmed with electrokinetic measurements, infrared spectroscopy and thermogravimetric analyses. Both coatings enabled the dispersion of UCNPs in water, and improved the fluorescence emission intensity with respect to the bare UCNPs. However, only the PMAO–BHMT coating provided an effective protection against the dissolution of the UCNPs and long-term colloidal stability in PBS, and did not show cytotoxicity in EAhy926 endothelial cells.