Magnetron sputtering onto nonionic surfactant for 1-step preparation of metal nanoparticles without additional chemical reagents.

Plasma-based sputtering onto liquids (SoL) is a straightforward approach for synthesizing small metal nanoparticles (NPs) without additional stabilizing reagents. In this work, nonionic surfactant Triton X-100 was used for the first time as a host liquid for the SoL process and the production of colloidal solutions of gold, silver and copper NPs was demonstrated. The average diameter of spherical Au NPs lies in the range from 2.6 to 5.5 nm depending on the conditions. The approach presented here opens the pathway to the production of concentrated dispersions of metal NPs of high purity that can be dispersed in water for future usage, therefore extending further the reach of this synthesis pathway.

A Coculture Based, 3D Bioprinted Ovarian Tumor Model Combining Cancer Cells and Cancer Associated Fibroblasts.

Ovarian cancer remains a major public health issue due to its poor prognosis. To develop more effective therapies, it is crucial to set-up reliable models that closely mimic the complexity of the ovarian tumor's microenvironment. 3D bioprinting is currently a promising approach to build heterogenous and reproducible cancer models with controlled shape and architecture. However, this technology is still poorly investigated to model ovarian tumors. In this study, a 3D bioprinted ovarian tumor model combining cancer cells (SKOV-3) and cancer associated fibroblasts (CAFs) are described. The resulting tumor models show their ability to maintain cell viability and proliferation. Cells are observed to self-assemble in heterotypic aggregates. Moreover, CAFs are observed to be recruited and to circle cancer cells reproducing an in vivo process taking place in the tumor microenvironment. Interestingly, this approach also shows its ability to rapidly generate a high number of reproducible tumor models that can be subjected to usual characterizations (cell viability and metabolic activity; histology and immunological studies; and real-time imaging). Therefore, these ovarian tumor models can be an interesting tool for high throughput drug screening applications.

Hybrid Mineral/Organic Material Induces Bone Bridging and Bone Volume Augmentation in Rat Calvarial Critical Size Defects.

In craniofacial bone defects, the promotion of bone volume augmentation remains a challenge. Finding strategies for bone regeneration such as combining resorbable minerals with organic polymers would contribute to solving the bone volume roadblock. Here, dicalcium phosphate dihydrate, chitosan and hyaluronic acid were used to functionalize a bone-side collagen membrane. Despite an increase in the release of inflammatory mediators by human circulating monocytes, the in vivo implantation of the functionalized membrane allowed the repair of a critical-sized defect in a calvaria rat model with de novo bone exhibiting physiological matrix composition and structural organization. Microtomography, histological and Raman analysis combined with nanoindentation testing revealed an increase in bone volume in the presence of the functionalized membrane and the formation of woven bone after eight weeks of implantation; these data showed the potential of dicalcium phosphate dihydrate, chitosan and hyaluronic acid to induce an efficient repair of critical-sized bone defects and establish the importance of thorough multi-scale characterization in assessing biomaterial outcomes in animal models.

Mn-Doped Quinary Ag-In-Ga-Zn-S Quantum Dots for Dual-Modal Imaging.

Doping of transition metals within a semiconductor quantum dot (QD) has a high impact on the optical and magnetic properties of the QD. In this study, we report the synthesis of Mn2+-doped Ag-In-Ga-Zn-S (Mn:AIGZS) QDs via thermolysis of a dithiocarbamate complex of Ag+, In3+, Ga3+, and Zn2+ and of Mn(stearate)2 in oleylamine. The influence of the Mn2+ loading on the photoluminescence (PL) and magnetic properties of the dots are investigated. Mn:AIGZS QDs exhibit a diameter of ca. 2 nm, a high PL quantum yield (up to 41.3% for a 2.5% doping in Mn2+), and robust photo- and colloidal stabilities. The optical properties of Mn:AIGZS QDs are preserved upon transfer into water using the glutathione tetramethylammonium ligand. At the same time, Mn:AIGZS QDs exhibit high relaxivity (r 1 = 0.15 mM-1 s-1 and r 2 = 0.57 mM-1 s-1 at 298 K and 2.34 T), which shows their potential applicability for bimodal PL/magnetic resonance imaging (MRI) probes.

An Alkaline Based Method for Generating Crystalline, Strong, and Shape Memory Polyvinyl Alcohol Biomaterials.

Strong, stretchable, and durable biomaterials with shape memory properties can be useful in different biomedical devices, tissue engineering, and soft robotics. However, it is challenging to combine these features. Semi-crystalline polyvinyl alcohol (PVA) has been used to make hydrogels by conventional methods such as freeze-thaw and chemical crosslinking, but it is formidable to produce strong materials with adjustable properties. Herein, a method to induce crystallinity and produce physically crosslinked PVA hydrogels via applying high-concentration sodium hydroxide into dense PVA polymer is introduced. Such a strategy enables the production of physically crosslinked PVA biomaterial with high mechanical properties, low water content, resistance to injury, and shape memory properties. It is also found that the developed PVA hydrogel can recover 90% of plastic deformation due to extension upon supplying water, providing a strong contraction force sufficiently to lift objects 1100 times more than their weight. Cytocompatibility, antifouling property, hemocompatibility, and biocompatibility are also demonstrated in vitro and in vivo. The fabrication methods of PVA-based catheters, injectable electronics, and microfluidic devices are demonstrated. This gelation approach enables both layer-by-layer and 3D printing fabrications.

Microengineered poly(HEMA) hydrogels for wearable contact lens biosensing.

Microchannels in hydrogels play an essential role in enabling a smart contact lens. However, microchannels have rarely been created in commercial hydrogel contact lenses due to their sensitivity to conventional microfabrication techniques. Here, we report the fabrication of microchannels in poly(2-hydroxyethyl methacrylate) (poly(HEMA)) hydrogels that are used in commercial contact lenses with a three-dimensional (3D) printed mold. We investigated the corresponding capillary flow behaviors in these microchannels. We observed different capillary flow regimes in these microchannels, depending on their hydration level. In particular, we found that a peristaltic pressure could reinstate flow in a dehydrated channel, indicating that the motion of eye-blinking may help tears flow in a microchannel-containing contact lens. Colorimetric pH and electrochemical Na+ sensing capabilities were demonstrated in these microchannels. This work paves the way for the development of microengineered poly(HEMA) hydrogels for various biomedical applications such as eye-care and wearable biosensing.

Biopolymers-calcium phosphate antibacterial coating reduces the pathogenicity of internalized bacteria by mesenchymal stromal cells.

A multifunctional material system that kills bacteria and drives bone healing is urgently sought to improve bone prosthesis. Herein, the osteoinductive coating made of calcium phosphate/chitosan/hyaluronic acid, named Hybrid, was proposed as an antibacterial substrate for stromal cell adhesion. This Hybrid coating possesses a contact-killing effect reducing by 90% the viability of Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Pseudomonas aeruginosa (P. aeruginosa) strains after 48 h of contact. In addition to the production of immunomodulatory mediators, Wharton's jelly (WJ-SCs), dental pulp (DPSCs) and bone marrow (BM-MSCs) derived stromal cells were able to release antibacterial and antibiofilm agents effective against S. aureus and P. aeruginosa strains, respectively. Studying the effect of the Hybrid coating on the internalization of S. aureus by the stromal cells, in acute-mimicking bone infection, highlighted an increase in the bacteria internalization by DPSCs and BM-MSCs when cultured on the Hybrid coating versus uncoated glass. Despite the internalization, Hybrid coating showed a beneficial effect by reducing the pathogenicity of the internalized bacteria. The formation of biofilm was reduced by at least 50% in comparison to internalized bacteria by stromal cells on uncoated glass. This work opens the route for the development of innovative antibacterial coatings by taking into account the internalization of bacteria by stromal cells.

3D Bioprinting of Oxygenated Cell-Laden Gelatin Methacryloyl Constructs.

Cell survival during the early stages of transplantation and before new blood vessels formation is a major challenge in translational applications of 3D bioprinted tissues. Supplementing oxygen (O2 ) to transplanted cells via an O2 generating source such as calcium peroxide (CPO) is an attractive approach to ensure cell viability. Calcium peroxide also produces calcium hydroxide that reduces the viscosity of bioinks, which is a limiting factor for bioprinting. Therefore, adapting this solution into 3D bioprinting is of significant importance. In this study, a gelatin methacryloyl (GelMA) bioink that is optimized in terms of pH and viscosity is developed. The improved rheological properties lead to the production of a robust bioink suitable for 3D bioprinting and controlled O2 release. In addition, O2 release, bioprinting conditions, and mechanical performance of hydrogels having different CPO concentrations are characterized. As a proof of concept study, fibroblasts and cardiomyocytes are bioprinted using CPO containing GelMA bioink. Viability and metabolic activity of printed cells are checked after 7 days of culture under hypoxic condition. The results show that the addition of CPO improves the metabolic activity and viability of cells in bioprinted constructs under hypoxic condition.

Synthesis of ordered microporous/macroporous MOF-808 through modulator-induced defect-formation, and surfactant self-assembly strategies.

Ordered materials with interconnected porosity allow the diffusion of molecules within their inner porous structure to access the active sites located in the microporous core. As a follow-up of our work on engineering of MOF-808, in this contribution, we study the synthesis of defective MOF-808 using two different strategies: the use of modulators and the surfactant-assisted synthesis to obtain materials with ordered and interconnected pores. The results of the study indicated that (i) the use of modulators of different chain length led to the formation of microporous/mesoporous MOFs through the formation of missing linker defects. However, the use of the acetic acid contributes to the formation of MOFs with larger mesoporous size distributions compared to materials synthesized with formic and propionic acids as modulators, and (ii) the self-assembly of CTAB surfactant produced an ordered microporous/macroporous network which enhanced crystallinity. However, the surface properties of the materials seem to be unaffected by the use of surfactants during synthesis. These results contribute to the development of ordered materials with a broad range of pore size distributions and give rise to new opportunities to extend the applications of MOF-808.

Layer-by-Layer Self-Assembly of Polyelectrolytes on Superparamagnetic Nanoparticle Surfaces.

Designing and manufacturing multifunctional nanoparticles (NPs) are of considerable interest for both academic and industrial research. Among NPs used in this field, iron oxide NPs show low toxicity compared to metallic ones and are thus of high interest for biomedical applications. In this work, superparamagnetic Fe3-δO4-based core/shell NPs were successfully prepared and characterized by the combination of different techniques, and their physical properties were investigated. We demonstrate the efficiency of the layer-by-layer process to graft polyelectrolytes on the surface of iron oxide NPs. The influence of the polyelectrolyte chain configuration on the magnetic properties of the Fe3-δO4/polymer core/shell NPs was enlightened. The simple and fast process described in this work is efficient for the grafting of polyelectrolytes from surfaces, and thus, derived Fe3-δO4 NPs display both the physical properties of the core and of the macromolecular shell. Finally, the cytotoxicity toward the human THP-1 monocytic cell line of the core/shell NPs was assessed. The results showed that the polymer-capped Fe3-δO4 NPs exhibited almost no toxicity after 24 h of exposure at concentrations up to 25 µg mL-1. Our results show that these smart superparamagnetic nanocarriers with stealth properties are promising for applications in multimodal cancer therapy, including drug delivery.

Chemical Functionalization of the Zinc Selenide Surface and Its Impact on Lactobacillus rhamnosus GG Biofilms.

Bacteria grow on surfaces and form communities called biofilms. Bacterial adhesion and properties of the derived biofilms depend on, among others, the nature of the supporting substrate. Here, we report how the surface properties of the substrate affect the biofilm growth of probiotic Lactobacillus rhamnosus GG (LGG). Hydrophilic (OH), hydrophobic (CH3), and positively charged (NH3+) surfaces were obtained by the functionalization of a ZnSe crystal with alkanethiol self-assembled monolayers (SAM). The self-assembly of alkanethiols onto ZnSe was studied in situ using infrared spectroscopy in attenuated total reflection mode (ATR-FTIR). The organization of grafted SAMs was analyzed based on the results of ATR-FTIR, high-energy elastic backscattering spectrometry, and contact angle measurements. The kinetics and adhesion strength of LGG initial attachment as well as its physiological state on surfaces terminated by the different functional groups were assessed by the combination of ATR-FTIR, force measurements based on atomic force microscopy, and fluorescent staining of bacteria. The strength of interactions between LGG and the surface was strongly affected by the terminal group of the alkanethiol chain. The -NH3+ groups displayed the highest affinity with LGG at the first stage of interaction. The surface properties also played an important role when LGG biofilms were further grown in a nutritive medium for 24 h under flow conditions. Notably, the analysis of the infrared spectra recorded during the biofilm cultivation revealed differences in the kinetics of growth and in the polysaccharide features of the biofilm depending on the substrate functionality. LGG biofilm was stable only on the positively charged surface upon rinsing. Findings of this work clearly show that the adhesion features and the growth of LGG biofilms are substrate-dependent.

Doxorubicin-Loaded Thermoresponsive Superparamagnetic Nanocarriers for Controlled Drug Delivery and Magnetic Hyperthermia Applications.

This study reports on the development of thermoresponsive core/shell magnetic nanoparticles (MNPs) based on an iron oxide core and a thermoresponsive copolymer shell composed of 2-(2-methoxy)ethyl methacrylate (MEO2MA) and oligo(ethylene glycol)methacrylate (OEGMA) moieties. These smart nano-objects combine the magnetic properties of the core and the drug carrier properties of the polymeric shell. Loading the anticancer drug doxorubicin (DOX) in the thermoresponsive MNPs via supramolecular interactions provides advanced features to the delivery of DOX with spatial and temporal controls. The so coated iron oxide MNPs exhibit superparamagnetic behavior with a saturation magnetization of around 30 emu g-1. Drug release experiments confirmed that only a small amount of DOX was released at room temperature, while almost 100% drug release was achieved after 52 h at 42 °C with Fe3-δO4@P(MEO2MA60OEGMA40), which grafted polymer chains displaying a low critical solution temperature of 41 °C. Moreover, the MNPs exhibit magnetic hyperthermia properties as shown by specific absorption rate measurements. Finally, the cytotoxicity of the core/shell MNPs toward human ovary cancer SKOV-3 cells was tested. The results showed that the polymer-capped MNPs exhibited almost no toxicity at concentrations up to 12 µg mL-1, whereas when loaded with DOX, an increase in cytotoxicity and a decrease of SKOV-3 cell viability were observed. From these results, we conclude that these smart superparamagnetic nanocarriers with stealth properties are able to deliver drugs to tumor and are promising for applications in multimodal cancer therapy.

Boosting mesenchymal stem cells regenerative activities on biopolymers-calcium phosphate functionalized collagen membrane.

The regeneration of bone-soft tissue interface, using functional membranes, remains challenging and can be promoted by improving mesenchymal stem cells (MSCs) paracrine function. Herein, a collagen membrane, used as guided bone regeneration membrane, was functionalized by calcium phosphate, chitosan and hyaluronic acid hybrid coating by simultaneous spray of interacting species process. Composed of brushite, octacalcium phosphate and hydroxyapatite, the hybrid coating increased the membrane stiffness by 50%. After 7 days of MSCs culture on the hybrid coated polymeric membrane, biological studies were marked by a lack of osteoblastic commitment. However, MSCs showed an enhanced proliferation along with the secretion of cytokines and growth factors that could block bone resorption and favour endothelial cell recruitment without exacerbating polynuclear neutrophils infiltration. These data shed light on the great potential of inorganic/organic coated collagen membranes as an alternative bioactive factor-like platform to improve MSCs regenerative capacity, in particular to support bone tissue vascularization and to modulate inflammatory infiltrates.

ZnO Nanorods with High Photocatalytic and Antibacterial Activity under Solar Light Irradiation.

ZnO nanorods (NRs) with an average length and diameter of 186 and 20 nm, respectively, were prepared through a mild solvothermal route and used as photocatalysts either as dispersed powder or immobilized on glass slides. The ZnO NRs were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). Dispersed ZnO NRs and, to a lesser extent, immobilized ZnO NRs were demonstrated to exhibit high photocatalytic activity under simulated sunlight of low intensity (5.5 mW/cm²) both for the degradation of the Orange II dye and for Escherichia coli bacterial decontamination (2.5-fold survival decrease after 180 min irradiation for immobilized NRs). SEM, atomic force microscopy (AFM), fluorescence spectroscopy, and epifluorescence microscopy demonstrate that cell surface damages are responsible of bacterial inactivation. The immobilized ZnO NRs could be reused up to five times for bacterial decontamination at comparable efficiency and therefore have great potential for real environmental applications.

A Facile Approach for Doxorubicine Delivery in Cancer Cells by Responsive and Fluorescent Core/Shell Quantum Dots.

Biocompatible thermoresponsive copolymers based on 2-(2-methoxyethoxy) ethyl methacrylate (MEO2MA) and oligo (ethylene glycol) methacrylate (OEGMA) were grown from the surface of ZnO quantum dots (QDs) by surface initiated atom transfer radical polymerization with activators regenerated by electron transfer (SI-ARGET ATRP) in order to design smart and fluorescent core/shell nanosystems to be used toward cancer cells. Tunable lower critical solution temperature (LCST) values were obtained and studied in water and in culture medium. The complete efficiency of the process was demonstrated by the combination of spectroscopic and microscopic studies. The colloidal behavior of the ZnO/copolymer core/shell QDs in water and in physiological media with temperature was assessed. Finally, the cytotoxicity toward human colon cancer HT29 cells of the core/shell QDs was tested. The results showed that the polymer-capped QDs exhibited almost no toxicity at concentrations up to 12.5 µg.mL-1, while when loaded with doxorubicin hydrochloride (DOX), a higher cytotoxicity and a decreased HT29 cancer cell viability in a short time were observed.

Thermo-responsive magnetic Fe3O4@P(MEO2MAX-OEGMA100-X) NPs and their applications as drug delivery systems.

The unique physical properties of the superparamagnetic nanoparticles (SPIONs) have made them candidates of choice in nanomedicine especially for diagnostic imaging, therapeutic applications and drug delivery based systems. In this study, superparamagnetic Fe3O4 NPs were synthesized and functionalized with a biocompatible thermoresponsive copolymer to obtain temperature responsive core/shell NPs. The ultimate goal of this work is to build a drug delivery system able to release anticancer drugs in the physiological temperatures range. The core/shell NPs were first synthesized and their chemical, physical, magnetic and thermo-responsive properties where fully characterized in a second step. The lower critical solution temperature (LCST) of the core/shell NPs was tuned in physiological media in order to release the cancer drug at a controlled temperature slightly above the body temperature to avoid any premature release of the drug. The core/shell NPs exhibiting the targeted LCST were then loaded with Doxurubicin (DOX) and the drug release properties were then studied with the temperature. Moreover the cytotoxicity tests have shown that the core/shell NPs had a very limited cytotoxicity up to concentration of 25µg/mL. This investigation showed that the significant release occurred at the targeted temperature in the physiological media making those nano-systems very promising for further use in drug delivery platform.

ZnO nanoparticles sensitized by CuInZn x S2+x quantum dots as highly efficient solar light driven photocatalysts.

Alloyed CuInZn x S2+x (ZCIS) quantum dots (QDs) were successfully associated to ZnO nanoparticles by a thermal treatment at 400 °C for 15 min. The ZnO/ZCIS composite was characterized by TEM, SEM, XRD, XPS and UV-vis absorption spectroscopy. ZCIS QDs, with an average diameter of ≈4.5 nm, were found to be homogeneously distributed at the surface of ZnO nanoparticles. ZCIS-sensitized ZnO nanoparticles exhibit a high photocatalytic activity under simulated solar light irradiation for the degradation of Orange II dye (>95% degradation after 180 min of irradiation at an intensity of 5 mW/cm2). The heterojunction built between the ZnO nanoparticle and ZCIS QDs not only extends the light adsorption range by the photocatalyst but also acts to decrease electron/hole recombination. Interestingly, the ZnO/ZCIS composite was found to produce increased amounts of H2O2 and singlet oxygen 1O2 compared to ZnO, suggesting that these reactive oxygen species play a key role in the photodegradation mechanism. The activity of the ZnO/ZCIS composite is retained at over 90% of its original value after ten successive photocatalytic runs, indicating its high stability and its potential for practical photocatalytic applications.

Efficient synthetic access to thermo-responsive core/shell nanoparticles.

Core/shell nanostructures based on silica, fluorescent ZnO quantum dots (QDs) and superparamagnetic Fe3O4 nanoparticles (NPs) were prepared and fully characterized by the combination of different techniques and the physical properties of the nanostructures were studied. We demonstrate the efficiency of the atom transfer radical polymerization with activators regenerated by electron transfer process to graft (co-)polymers of different structures and polarity at the surface of metal oxide NPs. The influence of the polymer chain configuration on the optical properties of the ZnO/polymer core/shell QDs was enlightened. Concerning the magnetic properties of the Fe3O4/polymer nanostructures, only the amount of the grafted polymer plays a role on the saturation magnetization of the NPs and no influence of the aggregation was evidenced. The simple and fast process described in this work is efficient for the grafting of copolymers from surfaces and the derived NPs display the combination of the physical properties of the core and the macromolecular behavior of the shell.

CdSe nanorod/TiO2 nanoparticle heterojunctions with enhanced solar- and visible-light photocatalytic activity.

CdSe nanorods (NRs) with an average length of ≈120 nm were prepared by a solvothermal process and associated to TiO2 nanoparticles (Aeroxide® P25) by annealing at 300 °C for 1 h. The content of CdSe NRs in CdSe/TiO2 composites was varied from 0.5 to 5 wt %. The CdSe/TiO2 heterostructured materials were characterized by XRD, TEM, SEM, XPS, UV-visible spectroscopy and Raman spectroscopy. TEM images and XRD patterns show that CdSe NRs with wurtzite structure are associated to TiO2 particles. The UV-visible spectra demonstrate that the narrow bandgap of CdSe NRs serves to increase the photoresponse of CdSe/TiO2 composites until ≈725 nm. The CdSe (2 wt %)/TiO2 composite exhibits the highest photocatalytic activity for the degradation of rhodamine B in aqueous solution under simulated sunlight or visible light irradiation. The enhancement in photocatalytic activity likely originates from CdSe sensitization of TiO2 and the heterojunction between these materials which facilitates electron transfer from CdSe to TiO2. Due to its high stability (up to ten reuses without any significant loss in activity), the CdSe/TiO2 heterostructured catalysts show high potential for real water decontamination.

Synthesis of Core/Shell ZnO/rGO Nanoparticles by Calcination of ZIF-8/rGO Composites and Their Photocatalytic Activity.

A facile two-step method was developed to prepare core/shell ZnO/rGO particles from ZIF-8/rGO composites. ZIF-8 particles were first grown at the surface of rGO sheets. Next, ZIF-8 particles were transformed into ZnO particles by thermal decomposition under air at 500 °C. All materials were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, thermogravimetric analysis, and Brunauer-Emmett-Teller analyses. Results obtained show that ZIF-8 particles strongly associate with rGO sheets and that the calcination of this material produces porous core/shell ZnO/rGO particles with an average diameter of ca. 40 nm. The wt % of rGO associated with ZIF-8 particles was varied from 5 to 20%. The ZnO/rGO (10%) particles exhibit the highest photocatalytic activity for the degradation of the Orange II dye under simulated solar light irradiation of weak intensity (5 mW/cm2). This high photocatalytic activity was demonstrated to originate from superoxide O2 •- radicals due to the efficient trapping of photogenerated electrons in ZnO by rGO.