Jonas G Croissant | University of New Mexico (original) (raw)

Papers by Jonas G Croissant

Research paper thumbnail of CHEMNANOMAT CHEMISTRY OF NANOMATERIALS FOR ENERGY, BIOLOGY AND MORE Gemcitabine Delivery and Photodynamic Therapy in Cancer Cells via Porphyrin-Ethylene-Based Periodic Mesoporous Organosilica Nanoparticles

Gemcitabine hydrochloride is an FDA-approved chemotherapeutic drug used in the treatment of vario... more Gemcitabine hydrochloride is an FDA-approved chemotherapeutic drug used in the treatment of various cancers. Several drawbacks of gemcitabine, including its short in vivo half-life of 8–17 min associated with ar apid excretion by the kidneys and its poor membrane permea-bility,h ave inspired research on an anodelivery approach. In this study,w er eport ethylene-based periodic mesopo-rous organosilica nanoparticles (PMOs) for photodynamic therapy and the autonomous delivery of gemcitabine in cancer cells. Porphyrins were used as photosensitizers and were localized in the walls of the PMOs while ah igh loading capacity of gemcitabine was observed in the porous structure. Depending on the nature of the photosensitizer, and its aggregation state, we were able to perform one or two-photon photodynamic therapy.T wo-photon excited photodynamic therapy combinedw ith gemcitabine delivery led to as ynergya nd av ery efficient cancer cell killing.

Research paper thumbnail of Chick chorioallantoic membrane assay as an in vivo model to study the effect of nanoparticle-based anticancer drugs in ovarian cancer OPEN

New therapy development is critically needed for ovarian cancer. We used the chicken egg CAM assa... more New therapy development is critically needed for ovarian cancer. We used the chicken egg CAM assay to evaluate efficacy of anticancer drug delivery using recently developed biodegradable PMO (periodic mesoporous organosilica) nanoparticles. Human ovarian cancer cells were transplanted onto the CAM membrane of fertilized eggs, resulting in rapid tumor formation. The tumor closely resembles cancer patient tumor and contains extracellular matrix as well as stromal cells and extensive vasculature. PMO nanoparticles loaded with doxorubicin were injected intravenously into the chicken egg resulting in elimination of the tumor. No significant damage to various organs in the chicken embryo occurred. In contrast, injection of free doxorubicin caused widespread organ damage, even when less amount was administered. The lack of toxic effect of nanoparticle loaded doxorubicin was associated with specific delivery of doxorubicin to the tumor. Furthermore, we observed excellent tumor accumulation of the nanoparticles. Lastly, a tumor could be established in the egg using tumor samples from ovarian cancer patients and that our nanoparticles were effective in eliminating the tumor. These results point to the remarkable efficacy of our nanoparticle based drug delivery system and suggests the value of the chicken egg tumor model for testing novel therapies for ovarian cancer. Annually, ovarian cancer accounts for an estimated 239,000 new cases and 152,000 deaths worldwide annually 1,2. This disease has both the highest morbidity and mortality rate among cancers of the reproductive system. Each year, at least 20,000 women in the United States are diagnosed with ovarian cancer 3. Recurrent epithelial ovarian cancer (EOC) is almost uniformly lethal. Tumor recurrence and metastasis are primarily responsible for the 70% five-year mortality of advanced EOC. Despite successful initial surgery and chemotherapy, over 70% of advanced EOC will recur, and only 15–30% of recurrent disease will respond to chemotherapy 3,4. Moreover, drug resistance causes treatment failure in over 90% of patients with the metastatic disease 5. Consequently, recurrent metastatic disease is a major clinical challenge that lacks effective therapy. Thus, there is a clear need to develop new therapies for this cancer. To initiate development of a novel therapy, it is necessary to employ a tumor model to evaluate its efficacy. In this paper, we discuss the chicken egg tumor model that possesses advantageous features as a tumor model. The chicken chorioallantoic membrane (CAM) system has been widely used for the study of human tumor growth 6–12 .

Research paper thumbnail of Ultra-thin enzymatic liquid membrane for CO 2 separation and capture

The limited flux and selectivities of current carbon dioxide membranes and the high costs associa... more The limited flux and selectivities of current carbon dioxide membranes and the high costs associated with conventional absorption-based CO 2 sequestration call for alternative CO 2 separation approaches. Here we describe an enzymatically active, ultra-thin, biomimetic membrane enabling CO 2 capture and separation under ambient pressure and temperature conditions. The membrane comprises a ~18-nm-thick close-packed array of 8 nm diameter hydrophilic pores that stabilize water by capillary condensation and precisely accommodate the metalloenzyme carbonic anhydrase (CA). CA catalyzes the rapid interconversion of CO 2 and water into carbonic acid. By minimizing diffusional constraints, stabilizing and concentrating CA within the nanopore array to a concentration 10× greater than achievable in solution, our enzymatic liquid membrane separates CO 2 at room temperature and atmospheric pressure at a rate of 2600 GPU with CO 2 /N 2 and CO 2 /H 2 selectivities as high as 788 and 1500, respectively, the highest combined flux and selectivity yet reported for ambient condition operation.

Research paper thumbnail of 2018, Adv Funct Mater, Porous Porphyrin-Based Organosilica NPs for NIR TPE-PDT & Gene Delivery in Zebrafish.pdf

The limited flux and selectivities of current carbon dioxide membranes and the high costs associa... more The limited flux and selectivities of current carbon dioxide membranes and the high costs associated with conventional absorption-based CO2 sequestration call for alternative CO2 separation approaches. Here we describe an enzymatically active, ultra-thin, biomimetic membrane enabling CO2 capture and separation under ambient pressure and temperature conditions. The membrane comprises a ~18-nm-thick close-packed array of 8 nm diameter hydrophilic pores that stabilize water by capillary condensation and precisely accommodate the metalloenzyme carbonic anhydrase (CA). CA catalyzes the rapid interconversion of CO2 and water into carbonic acid. By minimizing diffusional constraints, stabilizing and concentrating CA within the nanopore array to a concentration 10× greater than achievable in solution, our enzymatic liquid membrane separates CO2 at room temperature and atmospheric pressure at a rate of 2600 GPU with CO2/N2 and CO2/H2 selectivities as high as 788 and 1500, respectively, the highest combined flux and selectivity yet reported for ambient condition operation.

Research paper thumbnail of Two-Photon-Excited Silica and Organosilica Nanoparticles for Spatiotemporal Cancer Treatment

Coherent two-photon-excited (TPE) therapy in the near-infrared (NIR) provides safer cancer treatm... more Coherent two-photon-excited (TPE) therapy in the near-infrared (NIR) provides safer cancer treatments than current therapies lacking spatial and temporal selectivities because it is characterized by a 3D spatial resolution of 1 μm3 and very low scattering. In this review, the principle of TPE and its significance in combination with organosilica nanoparticles (NPs) are introduced and then studies involving the design of pioneering TPE-NIR organosilica nanomaterials are discussed for bioimaging, drug delivery, and photodynamic therapy. Organosilica nanoparticles and their rich and well-established chemistry, tunable composition, porosity, size, and morphology provide ideal platforms for minimal side-effect therapies via TPE-NIR. Mesoporous silica and organosilica nanoparticles endowed with high surface areas can be functionalized to carry hydrophobic and biologically unstable two-photon absorbers for drug delivery and diagnosis. Currently, most light-actuated clinical therapeutic applications with NPs involve photodynamic therapy by singlet oxygen generation, but low photosensitizing efficiencies, tumor resistance, and lack of spatial resolution limit their applicability. On the contrary, higher photosensitizing yields, versatile therapies, and a unique spatial resolution are available with engineered two-photon-sensitive organosilica particles that selectively impact tumors while healthy tissues remain untouched. Patients suffering pathologies such as retinoblastoma, breast, and skin cancers will greatly benefit from TPE-NIR ultrasensitive diagnosis and therapy.

Research paper thumbnail of Mesoporous Silica and Organosilica Nanoparticles: Physical Chemistry, Biosafety, Delivery Strategies, and Biomedical Applications

Predetermining the physico-chemical properties, biosafety, and stimuliresponsiveness of nanomater... more Predetermining the physico-chemical properties, biosafety, and stimuliresponsiveness of nanomaterials in biological environments is essential for safe and effective biomedical applications. At the forefront of biomedical research, mesoporous silica nanoparticles and mesoporous organosilica nanoparticles are increasingly investigated to predict their biological outcome by materials design. In this review, it is first chronicled that how the nanomaterial design of pure silica, partially hybridized organosilica, and fully hybridized organosilica (periodic mesoporous organosilicas) governs not only the physico-chemical properties but also the biosafety of the nanoparticles. The impact of the hybridization on the biocompatibility, protein corona, biodistribution, biodegradability, and clearance of the silica-based particles is described. Then, the influence of the surface engineering, the framework hybridization, as well as the morphology of the particles, on the ability to load and controllably deliver drugs under internal biological stimuli (e.g., pH, redox, enzymes) and external noninvasive stimuli (e.g., light, magnetic, ultrasound) are presented. To conclude, trends in the biomedical applications of silica and organosilica nanovectors are delineated, such as unconventional bioimaging techniques, large cargo delivery, combination therapy, gaseous molecule delivery, antimicrobial protection, and Alzheimer’s disease therapy.

Research paper thumbnail of Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles

Advanced Materials, 2017

The biorelated degradability and clearance of siliceous nanomaterials have been questioned world... more The biorelated degradability and clearance of siliceous nanomaterials have
been questioned worldwide, since they are crucial prerequisites for the
successful translation in clinics. Typically, the degradability and
biocompatibility of mesoporous silica nanoparticles (MSNs) have been an
ongoing discussion in research circles. The reason for such a concern is
that approved pharmaceutical products must not accumulate in the human
body, to prevent severe and unpredictable side-effects. Here, the biorelated
degradability and clearance of silicon and silica nanoparticles (NPs) are
comprehensively summarized. The influence of the size, morphology, surface
area, pore size, and surface functional groups, to name a few, on the
degradability of silicon and silica NPs is described. The noncovalent organic
doping of silica and the covalent incorporation of either hydrolytically stable
or redox- and enzymatically cleavable silsesquioxanes is then described for
organosilica, bridged silsesquioxane (BS), and periodic mesoporous organosilica
(PMO) NPs. Inorganically doped silica particles such as calcium-,
iron-, manganese-, and zirconium-doped NPs, also have radically different
hydrolytic stabilities. To conclude, the degradability and clearance timelines
of various siliceous nanomaterials are compared and it is highlighted that
researchers can select a specific nanomaterial in this large family according to
the targeted applications and the required clearance kinetics.

Research paper thumbnail of Cellular Internalization and Biocompatibility of Periodic Mesoporous Organosilica Nanoparticles with Tunable Morphologies: From Nanospheres to Nanowires

ChemPlusChem, 2017

This work describes the sol–gel syntheses of para-substituted phenylene-bridged periodic mesoporo... more This work describes the sol–gel syntheses of para-substituted phenylene-bridged periodic mesoporous organosilica (PMO) nanoparticles (NPs) with tunable morphologies ranging from nanowires to nanospheres. The findings show the key role of the addition of organic co-solvents in the aqueous templates on the final morphologies of PMO NPs. Other factors such as the temperature, the stirring speed, and the amount of organic solvents also influence the shape of PMO NPs. The tuning of the shape of the PMO nanomaterials made it possible to study the influence of the particle morphology on the cellular internalization and biocompatibility.

Research paper thumbnail of Engineering Hydrophobic Organosilica Doped Nanofibers for Enhanced and Fouling Resistant Membrane Distillation

Engineering and scaling-up new materials for better water desalination are imperative to find alt... more Engineering and scaling-up new materials for better water desalination are imperative to find alternative fresh water sources to meet future demands. Herein, the fabrication of hydrophobic poly(ether imide) composite nanofiber membranes doped with novel ethylene-pentafluorophenylene-based periodic mesoporous organosilica nanoparticles is reported for enhanced and fouling resistant membrane distillation. Novel organosilica nanoparticles were homogeneously incorporated into electrospun nanofiber membranes depicting a proportional increase of hydrophobicity to the particle contents. Direct contact membrane distillation experiments on the organosilica-doped membrane with only 5% doping showed an increase of flux of 140% compared to commercial membranes. The high porosity of organosilica nanoparticles was further utilized to load the eugenol antimicrobial agent which produced a dramatic enhancement of the antibiofouling properties of the membrane of 70% after 24 h.

Research paper thumbnail of Functional Nanoparticles: Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles (Adv. Mater. 9/2017

The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldw... more The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldwide, since they are crucial prerequisites for the successful translation in clinics. Typically, the degradability and biocompatibility of mesoporous silica nanoparticles (MSNs) have been an ongoing discussion in research circles. The reason for such a concern is that approved pharmaceutical products must not accumulate in the human body, to prevent severe and unpredictable side-effects. Here, the biorelated degradability and clearance of silicon and silica nanoparticles (NPs) are comprehensively summarized. The influence of the size, morphology, surface area, pore size, and surface functional groups, to name a few, on the degradability of silicon and silica NPs is described. The noncovalent organic doping of silica and the covalent incorporation of either hydrolytically stable or redox- and enzymatically cleavable silsesquioxanes is then described for organosilica, bridged silsesquioxane (BS), and periodic mesoporous organosilica (PMO) NPs. Inorganically doped silica particles such as calcium-, iron-, manganese-, and zirconium-doped NPs, also have radically different hydrolytic stabilities. To conclude, the degradability and clearance timelines of various siliceous nanomaterials are compared and it is highlighted that researchers can select a specific nanomaterial in this large family according to the targeted applications and the required clearance kinetics

Research paper thumbnail of 2017, Advanced Healthcare Materials, Cover

Healthcare-associated infections (HAIs) are the infections that patients get while receiving medi... more Healthcare-associated infections (HAIs) are the infections that patients get while receiving medical treatment in a medical facility with bacterial HAIs being the most common. Silver and gold nanoparticles (NPs) have been successfully employed as antibacterial motifs; however, NPs leaching in addition to poor dispersion and overall reproducibility are major hurdles to further product development. In this study, the authors design and fabricate a smart antibacterial mixed-matrix membrane coating comprising colloidal lysozyme-templated gold nanoclusters as nanofillers in poly(ethylene oxide)/poly(butylene terephthalate) amphiphilic polymer matrix. Mesoporous silica nanoparticles–lysozyme functionalized gold nanoclusters disperse homogenously within the polymer matrix with no phase separation and zero NPs leaching. This mixed-matrix coating can successfully sense and inhibit bacterial contamination via a controlled release mechanism that is only triggered by bacteria. The system is coated on a common radiographic dental imaging device (photostimulable phosphor plate) that is prone to oral bacteria contamination. Variation and eventually disappearance of the red fluorescence surface under UV light signals bacterial infection. Kanamycin, an antimicrobial agent, is controllably released to instantly inhibit bacterial growth. Interestingly, the quality of the images obtained with these coated surfaces is the same as uncoated surfaces and thus the safe application of such smart coatings can be expanded to include other medical devices without compromising their utility.

Research paper thumbnail of Fluorescent Periodic Mesoporous Organosilica Nanoparticles Dual-Functionalized via Click Chemistry for Two-Photon Photodynamic Therapy in Cells

The synthesis of ethenylene-based periodic mesoporous organosilica nanoparticles for two-photon i... more The synthesis of ethenylene-based periodic mesoporous organosilica nanoparticles for two-photon imaging and photodynamic therapy of breast cancer cells is described. A dedicated two-photon absorbing fluorophore possessing four triethoxysilyl groups and having large two-photon absorption in the near IR region, and azidopropyltriethoxysilane were incorporated into the structure. The mesoporous nanoparticles of 100 nm diameter were further functionalized by means of click chemistry with a propargylated fluorescent bromo-quinoline photosensitizer able to generate singlet oxygen. The photophysical properties and two-photon absorption properties of the nanoparticles were investigated evidencing complementary contribution of the two dyes. Both dyes contribute to the two-photon absorption response of the mesoporous nanoparticles while efficient FRET from the two-photon fluorophore to the quinoline sensitizer is observed. The dual-functionalized nanoparticles were incubated with MCF-7 breast cancer cells. Two-photon confocal imaging demonstrated the endocytosis of the nanoparticles within cancer cells. Moreover, brief two-photon irradiation (3 scans of 1.57 s) at 760 nm at high laser power (3 W) was shown to induce 40% of cancer cell death demonstrating the potential of the dual-functionalized mesoporous organosilica nanoparticles for two-photon photodynamic therapy.

Research paper thumbnail of Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles

The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldw... more The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldwide, since they are crucial prerequisites for the successful translation in clinics. Typically, the degradability and biocompatibility of mesoporous silica nanoparticles (MSNs) have been an ongoing discussion in research circles. The reason for such a concern is that approved pharmaceutical products must not accumulate in the human body, to prevent severe and unpredictable side-effects. Here, the biorelated degradability and clearance of silicon and silica nanoparticles (NPs) are comprehensively summarized. The influence of the size, morphology, surface area, pore size, and surface functional groups, to name a few, on the degradability of silicon and silica NPs is described. The noncovalent organic doping of silica and the covalent incorporation of either hydrolytically stable or redox- and enzymatically cleavable silsesquioxanes is then described for organosilica, bridged silsesquioxane (BS), and periodic mesoporous organosilica (PMO) NPs. Inorganically doped silica particles such as calcium-, iron-, manganese-, and zirconium-doped NPs, also have radically different hydrolytic stabilities. To conclude, the degradability and clearance timelines of various siliceous nanomaterials are compared and it is highlighted that researchers can select a specific nanomaterial in this large family according to the targeted applications and the required clearance kinetics.

Research paper thumbnail of Cellular Internalization and Biocompatibility of Periodic Mesoporous Organosilica Nanoparticles with Tunable Morphologies: from Nanospheres to Nanowires

This work describes the sol–gel syntheses of para-substituted phenylene-bridged periodic mesoporo... more This work describes the sol–gel syntheses of para-substituted phenylene-bridged periodic mesoporous organosilica (PMO) nanoparticles (NPs) with tunable morphologies ranging from nanowires to nanospheres. The findings show the key role of the addition of organic co-solvents in the aqueous templates on the final morphologies of PMO NPs. Other factors such as the temperature, the stirring speed, and the amount of organic solvents also influence the shape of PMO NPs. The tuning of the shape of the PMO nanomaterials made it possible to study the influence of the particle morphology on the cellular internalization and biocompatibility.

Research paper thumbnail of 2016, J Mater Chem B, C. Mauriello-Jimenez, Core-Shell Nanodiamonds-PMO NPs 2hv Imaging, PDT, Drug Delivery.pdf

In this article, we highlight the properties of nanodiamonds (ND), which were encapsulated in per... more In this article, we highlight the properties of nanodiamonds (ND), which were encapsulated in periodic mesoporous organosilica nanoparticles (PMO) and were able to generate reactive oxygen species for photodynamic applications upon two-photon excitation (TPE). The ND@PMO nanoparticles were characterized by various techniques and were then loaded with the anti-cancer drug doxorubicin. The release of the drug was pH sensitive and a synergistic cancer cell killing effect was observed when cancer cells were incubated with doxorubicin-loaded ND@PMO and irradiated with two-photon excitation at 800 nm.

Research paper thumbnail of Colloidal Gold Nanoclusters Spiked Silica Fillers in Mixed Matrix Coatings: Simultaneous Detection and Inhibition of Healthcare-Associated Infections

Healthcare-associated infections (HAIs) are the infections that patients get while receiving medi... more Healthcare-associated infections (HAIs) are the infections that patients get while receiving medical treatment in a medical facility with bacterial HAIs being the most common. Silver and gold nanoparticles (NPs) have been successfully employed as antibacterial motifs; however, NPs leaching in addition to poor dispersion and overall reproducibility are major hurdles to further product development. In this study, the authors design and fabricate a smart antibacterial mixed-matrix membrane coating comprising colloidal lysozyme-templated gold nanoclusters as nanofillers in poly(ethylene oxide)/ poly(butylene terephthalate) amphiphilic polymer matrix. Mesoporous silica nanoparticles–lysozyme functionalized gold nanoclusters disperse homogenously within the polymer matrix with no phase separation and zero NPs leaching. This mixed-matrix coating can successfully sense and inhibit bacterial contamination via a controlled release mechanism that is only triggered by bacteria. The system is coated on a common radiographic dental imaging device (photostimulable phosphor plate) that is prone to oral bacteria contamination. Variation and eventually disappearance of the red fluorescence surface under UV light signals bacterial infection. Kanamycin, an antimicrobial agent, is controllably released to instantly inhibit bacterial growth. Interestingly, the quality of the images obtained with these coated surfaces is the same as uncoated surfaces and thus the safe application of such smart coatings can be expanded to include other medical devices without compromising their utility.

Research paper thumbnail of Biodegradable Magnetic Silica@Iron Oxide Nanovectors with Ultra-Large Mesopores for High Protein Loading, Magnetothermal Release, and Delivery

The delivery of large cargos of diameter above 15 nm for biomedical applications has proved chall... more The delivery of large cargos of diameter above 15 nm for biomedical applications has proved challenging since it requires biocompatible, stably-loaded, and biodegradable nanomaterials. In this study, we describe the design of biodegradable silica-iron oxide hybrid nanovectors with large mesopores for large protein delivery in cancer cells. The mesopores of the nanomaterials spanned from 20 to 60 nm in diameter and post-functionalization allowed the electrostatic immobilization of large proteins (e.g. mTFP-Ferritin, ~534 kDa). Half of the content of the nanovectors was based with iron oxide nanophases which allowed the rapid biodegradation of the carrier in fetal bovine serum and a magnetic responsiveness. The nanovectors released large protein cargos in aqueous solution under acidic pH or magnetic stimuli. The delivery of large proteins was then autonomously achieved in cancer cells via the silica-iron oxide nanovectors, which is thus a promising for biomedical applications.

Research paper thumbnail of Organosilica hybrid nanomaterials with a high organic content: syntheses and applications of silsesquioxanes

Organic–inorganic hybrid materials garner properties from their organic and inorganic matrices as... more Organic–inorganic hybrid materials garner properties from their organic and inorganic matrices as well as synergistic features, and therefore have recently attracted much attention at the nanoscale. Non-porous organosilica hybrid nanomaterials with a high organic content such as silsesquioxanes (R-SiO 1.5 , with R organic groups) and bridged silsesquioxanes (O 1.5 SiR -SiO 1.5) are especially attractive hybrids since they provide 20 to 80 weight percent of organic functional groups in addition to the known chemistry and stability of silica. In the organosilica family, silsesquioxanes (R-SiO 1.5) stand between silicas (SiO 2) and sili-cones (R 2 SiO), and are variously called organosilicas, ormosil (organically-modified silica), polysilsesquiox-anes and silica hybrids. Herein, we comprehensively review non-porous silsesquioxane and bridged silses-quioxane nanomaterials and their applications in nanomedicine, electro-optics, and catalysis.

Research paper thumbnail of Periodic Mesoporous Organosilica Nanoparticles with Controlled Morphologies and High Drug/Dye Loadings for Multicargo Delivery in Cancer Cells

Despite the worldwide interest generated by periodic mesoporous organosilica (PMO) bulk materials... more Despite the worldwide interest generated by periodic mesoporous organosilica (PMO) bulk materials, the design of PMO nanomaterials with controlled morphology remains largely unexplored and their properties unknown. In this work, we describe the first study of PMO nanoparticles (NPs) based on meta-phenylene bridges, and we conducted a comparative structure–property relationship investigation with para-phenylene-bridged PMO NPs. Our findings indicate that the change of the isomer drastically affects the structure, morphology, size, porosity and thermal stability of PMO materials. We observed a much higher porosity and thermal stability of the para-based PMO which was likely due to a higher molecular periodicity. Additionally, the para isomer could generate multipodal NPs at very low stirring speed and upon this discovery we designed a phenylene– ethylene bridged PMO with a controlled Janus morphology. Unprecedentedly high payloads could be obtained from 40 to 110 wt % regardless of the organic bridge of PMOs. Finally, we demonstrate for the first time the co-delivery of two cargos by PMO NPs. Importantly, the cargo stability in PMOs did not require the capping of the pores, unlike pure silica, and the delivery could be autonomously triggered in cancer cells by acidic pH with nearly 70 % cell killing.

Research paper thumbnail of Biodegradable Oxamide-Phenylene-Based Mesoporous Organosilica Nano- particles with Unprecedented Drug Payloads for Delivery in Cells

We describe biodegradable mesoporous hybrid NPs in the presence of proteins, and its application ... more We describe biodegradable mesoporous hybrid NPs in the presence of proteins, and its application for drug delivery. We synthesized oxamide-phenylene-based mesoporous organosilica nanoparticles (MON) in the absence of silica source which had a remarkably high organic content with a high surface area. Oxamide functions provided biodegradability in the presence of trypsin model proteins. MON displayed exceptionally high payloads of hydrophilic and hydrophobic drugs (up to 84 wt%), and a unique zero premature leakage without the pore capping, unlike mesoporous silica. MON were biocompatible and internalized into cancer cells for drug delivery.

Research paper thumbnail of CHEMNANOMAT CHEMISTRY OF NANOMATERIALS FOR ENERGY, BIOLOGY AND MORE Gemcitabine Delivery and Photodynamic Therapy in Cancer Cells via Porphyrin-Ethylene-Based Periodic Mesoporous Organosilica Nanoparticles

Gemcitabine hydrochloride is an FDA-approved chemotherapeutic drug used in the treatment of vario... more Gemcitabine hydrochloride is an FDA-approved chemotherapeutic drug used in the treatment of various cancers. Several drawbacks of gemcitabine, including its short in vivo half-life of 8–17 min associated with ar apid excretion by the kidneys and its poor membrane permea-bility,h ave inspired research on an anodelivery approach. In this study,w er eport ethylene-based periodic mesopo-rous organosilica nanoparticles (PMOs) for photodynamic therapy and the autonomous delivery of gemcitabine in cancer cells. Porphyrins were used as photosensitizers and were localized in the walls of the PMOs while ah igh loading capacity of gemcitabine was observed in the porous structure. Depending on the nature of the photosensitizer, and its aggregation state, we were able to perform one or two-photon photodynamic therapy.T wo-photon excited photodynamic therapy combinedw ith gemcitabine delivery led to as ynergya nd av ery efficient cancer cell killing.

Research paper thumbnail of Chick chorioallantoic membrane assay as an in vivo model to study the effect of nanoparticle-based anticancer drugs in ovarian cancer OPEN

New therapy development is critically needed for ovarian cancer. We used the chicken egg CAM assa... more New therapy development is critically needed for ovarian cancer. We used the chicken egg CAM assay to evaluate efficacy of anticancer drug delivery using recently developed biodegradable PMO (periodic mesoporous organosilica) nanoparticles. Human ovarian cancer cells were transplanted onto the CAM membrane of fertilized eggs, resulting in rapid tumor formation. The tumor closely resembles cancer patient tumor and contains extracellular matrix as well as stromal cells and extensive vasculature. PMO nanoparticles loaded with doxorubicin were injected intravenously into the chicken egg resulting in elimination of the tumor. No significant damage to various organs in the chicken embryo occurred. In contrast, injection of free doxorubicin caused widespread organ damage, even when less amount was administered. The lack of toxic effect of nanoparticle loaded doxorubicin was associated with specific delivery of doxorubicin to the tumor. Furthermore, we observed excellent tumor accumulation of the nanoparticles. Lastly, a tumor could be established in the egg using tumor samples from ovarian cancer patients and that our nanoparticles were effective in eliminating the tumor. These results point to the remarkable efficacy of our nanoparticle based drug delivery system and suggests the value of the chicken egg tumor model for testing novel therapies for ovarian cancer. Annually, ovarian cancer accounts for an estimated 239,000 new cases and 152,000 deaths worldwide annually 1,2. This disease has both the highest morbidity and mortality rate among cancers of the reproductive system. Each year, at least 20,000 women in the United States are diagnosed with ovarian cancer 3. Recurrent epithelial ovarian cancer (EOC) is almost uniformly lethal. Tumor recurrence and metastasis are primarily responsible for the 70% five-year mortality of advanced EOC. Despite successful initial surgery and chemotherapy, over 70% of advanced EOC will recur, and only 15–30% of recurrent disease will respond to chemotherapy 3,4. Moreover, drug resistance causes treatment failure in over 90% of patients with the metastatic disease 5. Consequently, recurrent metastatic disease is a major clinical challenge that lacks effective therapy. Thus, there is a clear need to develop new therapies for this cancer. To initiate development of a novel therapy, it is necessary to employ a tumor model to evaluate its efficacy. In this paper, we discuss the chicken egg tumor model that possesses advantageous features as a tumor model. The chicken chorioallantoic membrane (CAM) system has been widely used for the study of human tumor growth 6–12 .

Research paper thumbnail of Ultra-thin enzymatic liquid membrane for CO 2 separation and capture

The limited flux and selectivities of current carbon dioxide membranes and the high costs associa... more The limited flux and selectivities of current carbon dioxide membranes and the high costs associated with conventional absorption-based CO 2 sequestration call for alternative CO 2 separation approaches. Here we describe an enzymatically active, ultra-thin, biomimetic membrane enabling CO 2 capture and separation under ambient pressure and temperature conditions. The membrane comprises a ~18-nm-thick close-packed array of 8 nm diameter hydrophilic pores that stabilize water by capillary condensation and precisely accommodate the metalloenzyme carbonic anhydrase (CA). CA catalyzes the rapid interconversion of CO 2 and water into carbonic acid. By minimizing diffusional constraints, stabilizing and concentrating CA within the nanopore array to a concentration 10× greater than achievable in solution, our enzymatic liquid membrane separates CO 2 at room temperature and atmospheric pressure at a rate of 2600 GPU with CO 2 /N 2 and CO 2 /H 2 selectivities as high as 788 and 1500, respectively, the highest combined flux and selectivity yet reported for ambient condition operation.

Research paper thumbnail of 2018, Adv Funct Mater, Porous Porphyrin-Based Organosilica NPs for NIR TPE-PDT & Gene Delivery in Zebrafish.pdf

The limited flux and selectivities of current carbon dioxide membranes and the high costs associa... more The limited flux and selectivities of current carbon dioxide membranes and the high costs associated with conventional absorption-based CO2 sequestration call for alternative CO2 separation approaches. Here we describe an enzymatically active, ultra-thin, biomimetic membrane enabling CO2 capture and separation under ambient pressure and temperature conditions. The membrane comprises a ~18-nm-thick close-packed array of 8 nm diameter hydrophilic pores that stabilize water by capillary condensation and precisely accommodate the metalloenzyme carbonic anhydrase (CA). CA catalyzes the rapid interconversion of CO2 and water into carbonic acid. By minimizing diffusional constraints, stabilizing and concentrating CA within the nanopore array to a concentration 10× greater than achievable in solution, our enzymatic liquid membrane separates CO2 at room temperature and atmospheric pressure at a rate of 2600 GPU with CO2/N2 and CO2/H2 selectivities as high as 788 and 1500, respectively, the highest combined flux and selectivity yet reported for ambient condition operation.

Research paper thumbnail of Two-Photon-Excited Silica and Organosilica Nanoparticles for Spatiotemporal Cancer Treatment

Coherent two-photon-excited (TPE) therapy in the near-infrared (NIR) provides safer cancer treatm... more Coherent two-photon-excited (TPE) therapy in the near-infrared (NIR) provides safer cancer treatments than current therapies lacking spatial and temporal selectivities because it is characterized by a 3D spatial resolution of 1 μm3 and very low scattering. In this review, the principle of TPE and its significance in combination with organosilica nanoparticles (NPs) are introduced and then studies involving the design of pioneering TPE-NIR organosilica nanomaterials are discussed for bioimaging, drug delivery, and photodynamic therapy. Organosilica nanoparticles and their rich and well-established chemistry, tunable composition, porosity, size, and morphology provide ideal platforms for minimal side-effect therapies via TPE-NIR. Mesoporous silica and organosilica nanoparticles endowed with high surface areas can be functionalized to carry hydrophobic and biologically unstable two-photon absorbers for drug delivery and diagnosis. Currently, most light-actuated clinical therapeutic applications with NPs involve photodynamic therapy by singlet oxygen generation, but low photosensitizing efficiencies, tumor resistance, and lack of spatial resolution limit their applicability. On the contrary, higher photosensitizing yields, versatile therapies, and a unique spatial resolution are available with engineered two-photon-sensitive organosilica particles that selectively impact tumors while healthy tissues remain untouched. Patients suffering pathologies such as retinoblastoma, breast, and skin cancers will greatly benefit from TPE-NIR ultrasensitive diagnosis and therapy.

Research paper thumbnail of Mesoporous Silica and Organosilica Nanoparticles: Physical Chemistry, Biosafety, Delivery Strategies, and Biomedical Applications

Predetermining the physico-chemical properties, biosafety, and stimuliresponsiveness of nanomater... more Predetermining the physico-chemical properties, biosafety, and stimuliresponsiveness of nanomaterials in biological environments is essential for safe and effective biomedical applications. At the forefront of biomedical research, mesoporous silica nanoparticles and mesoporous organosilica nanoparticles are increasingly investigated to predict their biological outcome by materials design. In this review, it is first chronicled that how the nanomaterial design of pure silica, partially hybridized organosilica, and fully hybridized organosilica (periodic mesoporous organosilicas) governs not only the physico-chemical properties but also the biosafety of the nanoparticles. The impact of the hybridization on the biocompatibility, protein corona, biodistribution, biodegradability, and clearance of the silica-based particles is described. Then, the influence of the surface engineering, the framework hybridization, as well as the morphology of the particles, on the ability to load and controllably deliver drugs under internal biological stimuli (e.g., pH, redox, enzymes) and external noninvasive stimuli (e.g., light, magnetic, ultrasound) are presented. To conclude, trends in the biomedical applications of silica and organosilica nanovectors are delineated, such as unconventional bioimaging techniques, large cargo delivery, combination therapy, gaseous molecule delivery, antimicrobial protection, and Alzheimer’s disease therapy.

Research paper thumbnail of Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles

Advanced Materials, 2017

The biorelated degradability and clearance of siliceous nanomaterials have been questioned world... more The biorelated degradability and clearance of siliceous nanomaterials have
been questioned worldwide, since they are crucial prerequisites for the
successful translation in clinics. Typically, the degradability and
biocompatibility of mesoporous silica nanoparticles (MSNs) have been an
ongoing discussion in research circles. The reason for such a concern is
that approved pharmaceutical products must not accumulate in the human
body, to prevent severe and unpredictable side-effects. Here, the biorelated
degradability and clearance of silicon and silica nanoparticles (NPs) are
comprehensively summarized. The influence of the size, morphology, surface
area, pore size, and surface functional groups, to name a few, on the
degradability of silicon and silica NPs is described. The noncovalent organic
doping of silica and the covalent incorporation of either hydrolytically stable
or redox- and enzymatically cleavable silsesquioxanes is then described for
organosilica, bridged silsesquioxane (BS), and periodic mesoporous organosilica
(PMO) NPs. Inorganically doped silica particles such as calcium-,
iron-, manganese-, and zirconium-doped NPs, also have radically different
hydrolytic stabilities. To conclude, the degradability and clearance timelines
of various siliceous nanomaterials are compared and it is highlighted that
researchers can select a specific nanomaterial in this large family according to
the targeted applications and the required clearance kinetics.

Research paper thumbnail of Cellular Internalization and Biocompatibility of Periodic Mesoporous Organosilica Nanoparticles with Tunable Morphologies: From Nanospheres to Nanowires

ChemPlusChem, 2017

This work describes the sol–gel syntheses of para-substituted phenylene-bridged periodic mesoporo... more This work describes the sol–gel syntheses of para-substituted phenylene-bridged periodic mesoporous organosilica (PMO) nanoparticles (NPs) with tunable morphologies ranging from nanowires to nanospheres. The findings show the key role of the addition of organic co-solvents in the aqueous templates on the final morphologies of PMO NPs. Other factors such as the temperature, the stirring speed, and the amount of organic solvents also influence the shape of PMO NPs. The tuning of the shape of the PMO nanomaterials made it possible to study the influence of the particle morphology on the cellular internalization and biocompatibility.

Research paper thumbnail of Engineering Hydrophobic Organosilica Doped Nanofibers for Enhanced and Fouling Resistant Membrane Distillation

Engineering and scaling-up new materials for better water desalination are imperative to find alt... more Engineering and scaling-up new materials for better water desalination are imperative to find alternative fresh water sources to meet future demands. Herein, the fabrication of hydrophobic poly(ether imide) composite nanofiber membranes doped with novel ethylene-pentafluorophenylene-based periodic mesoporous organosilica nanoparticles is reported for enhanced and fouling resistant membrane distillation. Novel organosilica nanoparticles were homogeneously incorporated into electrospun nanofiber membranes depicting a proportional increase of hydrophobicity to the particle contents. Direct contact membrane distillation experiments on the organosilica-doped membrane with only 5% doping showed an increase of flux of 140% compared to commercial membranes. The high porosity of organosilica nanoparticles was further utilized to load the eugenol antimicrobial agent which produced a dramatic enhancement of the antibiofouling properties of the membrane of 70% after 24 h.

Research paper thumbnail of Functional Nanoparticles: Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles (Adv. Mater. 9/2017

The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldw... more The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldwide, since they are crucial prerequisites for the successful translation in clinics. Typically, the degradability and biocompatibility of mesoporous silica nanoparticles (MSNs) have been an ongoing discussion in research circles. The reason for such a concern is that approved pharmaceutical products must not accumulate in the human body, to prevent severe and unpredictable side-effects. Here, the biorelated degradability and clearance of silicon and silica nanoparticles (NPs) are comprehensively summarized. The influence of the size, morphology, surface area, pore size, and surface functional groups, to name a few, on the degradability of silicon and silica NPs is described. The noncovalent organic doping of silica and the covalent incorporation of either hydrolytically stable or redox- and enzymatically cleavable silsesquioxanes is then described for organosilica, bridged silsesquioxane (BS), and periodic mesoporous organosilica (PMO) NPs. Inorganically doped silica particles such as calcium-, iron-, manganese-, and zirconium-doped NPs, also have radically different hydrolytic stabilities. To conclude, the degradability and clearance timelines of various siliceous nanomaterials are compared and it is highlighted that researchers can select a specific nanomaterial in this large family according to the targeted applications and the required clearance kinetics

Research paper thumbnail of 2017, Advanced Healthcare Materials, Cover

Healthcare-associated infections (HAIs) are the infections that patients get while receiving medi... more Healthcare-associated infections (HAIs) are the infections that patients get while receiving medical treatment in a medical facility with bacterial HAIs being the most common. Silver and gold nanoparticles (NPs) have been successfully employed as antibacterial motifs; however, NPs leaching in addition to poor dispersion and overall reproducibility are major hurdles to further product development. In this study, the authors design and fabricate a smart antibacterial mixed-matrix membrane coating comprising colloidal lysozyme-templated gold nanoclusters as nanofillers in poly(ethylene oxide)/poly(butylene terephthalate) amphiphilic polymer matrix. Mesoporous silica nanoparticles–lysozyme functionalized gold nanoclusters disperse homogenously within the polymer matrix with no phase separation and zero NPs leaching. This mixed-matrix coating can successfully sense and inhibit bacterial contamination via a controlled release mechanism that is only triggered by bacteria. The system is coated on a common radiographic dental imaging device (photostimulable phosphor plate) that is prone to oral bacteria contamination. Variation and eventually disappearance of the red fluorescence surface under UV light signals bacterial infection. Kanamycin, an antimicrobial agent, is controllably released to instantly inhibit bacterial growth. Interestingly, the quality of the images obtained with these coated surfaces is the same as uncoated surfaces and thus the safe application of such smart coatings can be expanded to include other medical devices without compromising their utility.

Research paper thumbnail of Fluorescent Periodic Mesoporous Organosilica Nanoparticles Dual-Functionalized via Click Chemistry for Two-Photon Photodynamic Therapy in Cells

The synthesis of ethenylene-based periodic mesoporous organosilica nanoparticles for two-photon i... more The synthesis of ethenylene-based periodic mesoporous organosilica nanoparticles for two-photon imaging and photodynamic therapy of breast cancer cells is described. A dedicated two-photon absorbing fluorophore possessing four triethoxysilyl groups and having large two-photon absorption in the near IR region, and azidopropyltriethoxysilane were incorporated into the structure. The mesoporous nanoparticles of 100 nm diameter were further functionalized by means of click chemistry with a propargylated fluorescent bromo-quinoline photosensitizer able to generate singlet oxygen. The photophysical properties and two-photon absorption properties of the nanoparticles were investigated evidencing complementary contribution of the two dyes. Both dyes contribute to the two-photon absorption response of the mesoporous nanoparticles while efficient FRET from the two-photon fluorophore to the quinoline sensitizer is observed. The dual-functionalized nanoparticles were incubated with MCF-7 breast cancer cells. Two-photon confocal imaging demonstrated the endocytosis of the nanoparticles within cancer cells. Moreover, brief two-photon irradiation (3 scans of 1.57 s) at 760 nm at high laser power (3 W) was shown to induce 40% of cancer cell death demonstrating the potential of the dual-functionalized mesoporous organosilica nanoparticles for two-photon photodynamic therapy.

Research paper thumbnail of Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles

The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldw... more The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldwide, since they are crucial prerequisites for the successful translation in clinics. Typically, the degradability and biocompatibility of mesoporous silica nanoparticles (MSNs) have been an ongoing discussion in research circles. The reason for such a concern is that approved pharmaceutical products must not accumulate in the human body, to prevent severe and unpredictable side-effects. Here, the biorelated degradability and clearance of silicon and silica nanoparticles (NPs) are comprehensively summarized. The influence of the size, morphology, surface area, pore size, and surface functional groups, to name a few, on the degradability of silicon and silica NPs is described. The noncovalent organic doping of silica and the covalent incorporation of either hydrolytically stable or redox- and enzymatically cleavable silsesquioxanes is then described for organosilica, bridged silsesquioxane (BS), and periodic mesoporous organosilica (PMO) NPs. Inorganically doped silica particles such as calcium-, iron-, manganese-, and zirconium-doped NPs, also have radically different hydrolytic stabilities. To conclude, the degradability and clearance timelines of various siliceous nanomaterials are compared and it is highlighted that researchers can select a specific nanomaterial in this large family according to the targeted applications and the required clearance kinetics.

Research paper thumbnail of Cellular Internalization and Biocompatibility of Periodic Mesoporous Organosilica Nanoparticles with Tunable Morphologies: from Nanospheres to Nanowires

This work describes the sol–gel syntheses of para-substituted phenylene-bridged periodic mesoporo... more This work describes the sol–gel syntheses of para-substituted phenylene-bridged periodic mesoporous organosilica (PMO) nanoparticles (NPs) with tunable morphologies ranging from nanowires to nanospheres. The findings show the key role of the addition of organic co-solvents in the aqueous templates on the final morphologies of PMO NPs. Other factors such as the temperature, the stirring speed, and the amount of organic solvents also influence the shape of PMO NPs. The tuning of the shape of the PMO nanomaterials made it possible to study the influence of the particle morphology on the cellular internalization and biocompatibility.

Research paper thumbnail of 2016, J Mater Chem B, C. Mauriello-Jimenez, Core-Shell Nanodiamonds-PMO NPs 2hv Imaging, PDT, Drug Delivery.pdf

In this article, we highlight the properties of nanodiamonds (ND), which were encapsulated in per... more In this article, we highlight the properties of nanodiamonds (ND), which were encapsulated in periodic mesoporous organosilica nanoparticles (PMO) and were able to generate reactive oxygen species for photodynamic applications upon two-photon excitation (TPE). The ND@PMO nanoparticles were characterized by various techniques and were then loaded with the anti-cancer drug doxorubicin. The release of the drug was pH sensitive and a synergistic cancer cell killing effect was observed when cancer cells were incubated with doxorubicin-loaded ND@PMO and irradiated with two-photon excitation at 800 nm.

Research paper thumbnail of Colloidal Gold Nanoclusters Spiked Silica Fillers in Mixed Matrix Coatings: Simultaneous Detection and Inhibition of Healthcare-Associated Infections

Healthcare-associated infections (HAIs) are the infections that patients get while receiving medi... more Healthcare-associated infections (HAIs) are the infections that patients get while receiving medical treatment in a medical facility with bacterial HAIs being the most common. Silver and gold nanoparticles (NPs) have been successfully employed as antibacterial motifs; however, NPs leaching in addition to poor dispersion and overall reproducibility are major hurdles to further product development. In this study, the authors design and fabricate a smart antibacterial mixed-matrix membrane coating comprising colloidal lysozyme-templated gold nanoclusters as nanofillers in poly(ethylene oxide)/ poly(butylene terephthalate) amphiphilic polymer matrix. Mesoporous silica nanoparticles–lysozyme functionalized gold nanoclusters disperse homogenously within the polymer matrix with no phase separation and zero NPs leaching. This mixed-matrix coating can successfully sense and inhibit bacterial contamination via a controlled release mechanism that is only triggered by bacteria. The system is coated on a common radiographic dental imaging device (photostimulable phosphor plate) that is prone to oral bacteria contamination. Variation and eventually disappearance of the red fluorescence surface under UV light signals bacterial infection. Kanamycin, an antimicrobial agent, is controllably released to instantly inhibit bacterial growth. Interestingly, the quality of the images obtained with these coated surfaces is the same as uncoated surfaces and thus the safe application of such smart coatings can be expanded to include other medical devices without compromising their utility.

Research paper thumbnail of Biodegradable Magnetic Silica@Iron Oxide Nanovectors with Ultra-Large Mesopores for High Protein Loading, Magnetothermal Release, and Delivery

The delivery of large cargos of diameter above 15 nm for biomedical applications has proved chall... more The delivery of large cargos of diameter above 15 nm for biomedical applications has proved challenging since it requires biocompatible, stably-loaded, and biodegradable nanomaterials. In this study, we describe the design of biodegradable silica-iron oxide hybrid nanovectors with large mesopores for large protein delivery in cancer cells. The mesopores of the nanomaterials spanned from 20 to 60 nm in diameter and post-functionalization allowed the electrostatic immobilization of large proteins (e.g. mTFP-Ferritin, ~534 kDa). Half of the content of the nanovectors was based with iron oxide nanophases which allowed the rapid biodegradation of the carrier in fetal bovine serum and a magnetic responsiveness. The nanovectors released large protein cargos in aqueous solution under acidic pH or magnetic stimuli. The delivery of large proteins was then autonomously achieved in cancer cells via the silica-iron oxide nanovectors, which is thus a promising for biomedical applications.

Research paper thumbnail of Organosilica hybrid nanomaterials with a high organic content: syntheses and applications of silsesquioxanes

Organic–inorganic hybrid materials garner properties from their organic and inorganic matrices as... more Organic–inorganic hybrid materials garner properties from their organic and inorganic matrices as well as synergistic features, and therefore have recently attracted much attention at the nanoscale. Non-porous organosilica hybrid nanomaterials with a high organic content such as silsesquioxanes (R-SiO 1.5 , with R organic groups) and bridged silsesquioxanes (O 1.5 SiR -SiO 1.5) are especially attractive hybrids since they provide 20 to 80 weight percent of organic functional groups in addition to the known chemistry and stability of silica. In the organosilica family, silsesquioxanes (R-SiO 1.5) stand between silicas (SiO 2) and sili-cones (R 2 SiO), and are variously called organosilicas, ormosil (organically-modified silica), polysilsesquiox-anes and silica hybrids. Herein, we comprehensively review non-porous silsesquioxane and bridged silses-quioxane nanomaterials and their applications in nanomedicine, electro-optics, and catalysis.

Research paper thumbnail of Periodic Mesoporous Organosilica Nanoparticles with Controlled Morphologies and High Drug/Dye Loadings for Multicargo Delivery in Cancer Cells

Despite the worldwide interest generated by periodic mesoporous organosilica (PMO) bulk materials... more Despite the worldwide interest generated by periodic mesoporous organosilica (PMO) bulk materials, the design of PMO nanomaterials with controlled morphology remains largely unexplored and their properties unknown. In this work, we describe the first study of PMO nanoparticles (NPs) based on meta-phenylene bridges, and we conducted a comparative structure–property relationship investigation with para-phenylene-bridged PMO NPs. Our findings indicate that the change of the isomer drastically affects the structure, morphology, size, porosity and thermal stability of PMO materials. We observed a much higher porosity and thermal stability of the para-based PMO which was likely due to a higher molecular periodicity. Additionally, the para isomer could generate multipodal NPs at very low stirring speed and upon this discovery we designed a phenylene– ethylene bridged PMO with a controlled Janus morphology. Unprecedentedly high payloads could be obtained from 40 to 110 wt % regardless of the organic bridge of PMOs. Finally, we demonstrate for the first time the co-delivery of two cargos by PMO NPs. Importantly, the cargo stability in PMOs did not require the capping of the pores, unlike pure silica, and the delivery could be autonomously triggered in cancer cells by acidic pH with nearly 70 % cell killing.

Research paper thumbnail of Biodegradable Oxamide-Phenylene-Based Mesoporous Organosilica Nano- particles with Unprecedented Drug Payloads for Delivery in Cells

We describe biodegradable mesoporous hybrid NPs in the presence of proteins, and its application ... more We describe biodegradable mesoporous hybrid NPs in the presence of proteins, and its application for drug delivery. We synthesized oxamide-phenylene-based mesoporous organosilica nanoparticles (MON) in the absence of silica source which had a remarkably high organic content with a high surface area. Oxamide functions provided biodegradability in the presence of trypsin model proteins. MON displayed exceptionally high payloads of hydrophilic and hydrophobic drugs (up to 84 wt%), and a unique zero premature leakage without the pore capping, unlike mesoporous silica. MON were biocompatible and internalized into cancer cells for drug delivery.

Research paper thumbnail of Recent Developments in Advanced Membranes and Porous Materials for Energy, Environment and Water Applications

Title: Light-Responsive Organosilica Composite Nanocarriers for Biomedical Applications Abstrac... more Title: Light-Responsive Organosilica Composite Nanocarriers
for Biomedical Applications

Abstract: Organosilica composite nanocarriers obtained from organoalkoxysilanes have attracted much interest in the material science community for their potential in biomedical applications. The key interest of such nanomaterials is to benefit from the processability and stability of silica matrices via sol-gel processes, while incorporating additional organic functions in high content. Here we present three kinds of light-responsive organosilica nanocomposites, namely periodic mesoporous organosilica (PMO),1 bridged silsesquioxane (BSQ),2 and organically-modified silica (ORMOSIL)3 nanomaterials for various applications such as cargo release, drug delivery, and biomedical imaging. PMO nanoparticles were applied as two-photon drug-delivery and photodynamic therapy platform, while BSQ nanocapsules and ORMOSIL colloidosome nanosystems were designed as proof of principle for light-triggered release.

Research paper thumbnail of 1st Young Researcher's Mediterranean Workshop of the Société Chimique de France (Montpellier, FRANCE)

Two-photon-triggered camptothecin delivery with nanoimpellers was studied in MCF-7 breast cancer ... more Two-photon-triggered camptothecin delivery with nanoimpellers was studied in MCF-7 breast cancer cells. A fluorophore with a high two-photon absorption cross-section was first incorporated in the nanoimpellers. FRET transfer from the fluorophore to the azobenzene moiety was demonstrated. Two-photon imaging and therapy of cancer cells were then performed. The nanoimpellers were shown to be efficient in cancer cell killing induced by two-photon excitation.

Research paper thumbnail of Nano-Hybrid 9 Conference

An important problem in nanomedicine is to achieve a space, time, and amount controlled delivery ... more An important problem in nanomedicine is to achieve a space, time, and amount controlled delivery of cargo molecules through nanoparticles. Recently, the plasmonic properties of metal nanoparticles, such as gold nanoparticles, appeared as good candidate for a remote triggered-release of payload through the photo-thermal conversion of laser energy. Although the photothermal and plasmonic heating properties of gold nanoparticles were used in this context, none of them fully resolved the former problem of a strict controlled release in a robust matrix which avoids various side effects. Herein, we describe a unique one-pot synthesis of core-shell gold@mesoporous silica nanoparticles (Au@MSN) via the cetyltrimethylammonium bromide (CTAB) mediated autoreduction of gold precursor. Furthermore, a thermosensitive molecular mechanization of the silica pores was used to tailor smart multifunctional nanocarriers, which released on demand loaded dyes under the internal heat produced by the laser irradiation of the gold cores. Such systems displayed sufficient local heat to induce local plasmonic heating on the silica surface.

Research paper thumbnail of BACK COVER Angewandte Chemie International Edition

Electrostatic Assembly/Disassembly of Nanoscaled Colloidosomes for Light‐Triggered Cargo Release

The designed Back Cover was selected for the renown international Chemistry journal Angewandte.