Halima Alem

Aqueous synthesis of highly luminescent glutathione-capped Mn2 +-doped ZnS quantum dots

In this paper, an aqueous-based route has been developed to prepare highly luminescent glutathione (GSH)-capped Mn-doped ZnS quantum dots (QDs). The dots obtained have an average diameter of 4.3 nm and exhibit the Mn(2+)-related orange luminescence with very low surface defect density. The highest photoluminescence was observed for a Mn(2+) to Zn(2+) molar ratio of 3%. Consecutive overcoating of the Mn:ZnS@GSH QDs by a ZnS shell was done, and the core/shell structured QDs exhibit a PL quantum yield of 23%. Transmission electron microscopy, X-ray powder diffraction, electron spin resonance, X-ray photoelectron spectroscopy, UV-visible spectroscopy and spectrofluorometry have been used to characterize the crystal structure, the doping status, and the optical properties of the doped-QDs. Our systematic investigation shows that Mn:ZnS/ZnS@GSH QDs are highly promising fluorescent labels in biological applications.

Functional responsive superparamagnetic core/shell nanoparticles and their drug release properties

The preparation of responsive superparamagnetic iron oxide (SPIO) nanoparticles (NPs), able to carry the anticancer drug doxorubicin (DOX) and to release it in physiological media at the physiological temperature, is one of the major challenges in nanomedicine. In this work, two families of NPs were synthesized. The first one consists of superparamagnetic Fe3O4 NPs functionalized via covalent grafting by a biocompatible responsive copolymer based on 2-(2-methoxy)ethyl methacrylate (MEO2MA) and oligo(ethylene glycol) methacrylate (OEGMA). The second one consists of the same core/shell NPs but folic acid, a biological cancer targeting molecule, was grafted at the polymer chain end. The core/shell NPs were fully characterized by the combination of spectroscopic and microscopic techniques. The influence of the polymer chain structure in water and in physiological media was studied. We demonstrate that the magnetic properties of the NPs were only influenced by the amount of the grafted polymer and no influence of NP aggregation was evidenced. Indeed, the derived nanostructured materials displayed a combination of the physical properties of the core and the macromolecular behavior of the shell. The drug release experiments confirmed that DOX was largely released above the co-polymer LCST due to the presence of DOX. The nanomaterials developed in this work have high potential as multi-modal cancer therapy tools.

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.

ZnO nanoparticles sensitized by CuInZnxS2+x quantum dots as highly efficient solar light driven photocatalysts

Alloyed CuInZnxS2+ 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.

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.

Growth and toxic gas sensing properties of poly(urethaneimide) thin films

In this work we present a study on the growth and the gas sensing properties of poly(urethane imide) thin films. We first deeply characterized by atomic force microscopy (AFM) the nanostructuration of the poly(urethane imide) holding different amine groups. We further studied the interaction between highly toxic gases such as hexamethyleneimine (HMI) and pyridine and the polymer by using an unconventional method based on Quartz Crystal Microbalance (QCM) measurement. We showed for the first time that weak interactions, i.e. hydrogen bonding between the gas molecules and the polymer film allow the diffusion of the gas molecule deep in the polymeric film and the recovery of the film once the gas molecules leave the sensor. This first work paves a new way for the design of a completely recoverable sensor able to detect highly toxic gases for environmental concern.

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.

A Facile Approach for the 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.