Visible light promoted photoredox C(sp3)-H bond functionalization of tetrahydroisoquinolines in flow.

A merger of organocatalysis and visible light photoredox catalysis performed in flow allowed access to a wide range of functionalized N-aryl-substituted tetrahydroisoquinolines (THIQs) in a formal C-H oxidation/Mannich reaction. Strecker type functionalization and copper-catalyzed alkynylation of several N-aryl-substituted THIQs were also successfully performed in flow, giving valuable products with high efficiencies. The use of custom-made porous polymeric type microreactors proved to be crucial regarding the C-H oxidation step and overall reaction performance.

Ultrafast humidity sensor based on liquid phase exfoliated graphene.

Humidity sensing is important to a variety of technologies and industries, ranging from environmental and industrial monitoring to medical applications. Although humidity sensors abound, few available solutions are thin, transparent, compatible with large-area sensor production and flexible, and almost none are fast enough to perform human respiration monitoring through breath detection or real-time finger proximity monitoring via skin humidity sensing. This work describes chemiresistive graphene-based humidity sensors produced in few steps with facile liquid phase exfoliation followed by Langmuir-Blodgett assembly that enables active areas of practically any size. The graphene sensors provide a unique mix of performance parameters, exhibiting resistance changes up to 10% with varying humidity, linear performance over relative humidity (RH) levels between 8% and 95%, weak response to other constituents of air, flexibility, transparency of nearly 80%, and response times of 30 ms. The fast response to humidity is shown to be useful for respiration monitoring and real-time finger proximity detection, with potential applications in flexible touchless interactive panels.

Full-Self-Powered Humidity Sensor Based on Electrochemical Aluminum-Water Reaction.

A detailed examination of the principle of operation behind the functioning of the full-self-powered humidity sensor is presented. The sensor has been realized as a structure consisting of an interdigitated capacitor with aluminum thin-film digits. In this work, the details of its fabrication and activation are described in detail. The performed XRD, FTIR, SEM, AFM, and EIS analyses, as well as noise measurements, revealed that the dominant process of electricity generation is the electrochemical reaction between the sensor's aluminum electrodes and the water from humid air in the presence of oxygen, which was the main goal of this work. The response of the sensor to human breath is also presented as a demonstration of its possible practical application.

Influence of the electron donor properties of hypericin on its sensitizing ability in DSSCs.

Rising demands for renewable energy sources have led to the development of dye sensitized solar cells. It is a challenge to find a good and low cost sensitizer, which has a low environmental impact. In this work, we conducted spectroscopic and electrochemical experiments, as well as quantum-chemical calculations of the natural pigment hypericin, in order to provide insight into its sensitizing efficiency. To this end, three identical cells were made and characterized. Although this pigment exhibited good adsorption onto a semiconductor surface, a high molar absorption coefficient (43 700 L mol-1 cm-1) and favorable alignment of energy levels and provided a long lifetime of electrons (17.8 ms) in the TiO2 photoanode, it was found that the efficiency of hypericin-sensitized solar cells was very low, only 0.0245%. We suggest that this inefficiency originated from a low injection of electrons into the conduction band of TiO2. This conclusion is supported by the density functional theory calculations which revealed a low electron density in the anchoring groups of electronically excited hypericin. The results of this work could be valuable not only in the photovoltaic aspect, but also for application of hypericin in medicine in photodynamic therapy.

Removal of Nickel Ions from Aqueous Solutions by 2-Hydroxyethyl Acrylate/Itaconic Acid Hydrogels Optimized with Response Surface Methodology.

The adsorption of Ni2+ ions from water solutions by using hydrogels based on 2-hydroxyethyl acrylate (HEA) and itaconic acid (IA) was studied. Hydrogel synthesis was optimized with response surface methodology (RSM). The hydrogel with the best adsorption capacity towards Ni2+ ions was chosen for further experiments. The hydrogel was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis before and after the adsorption of Ni2+ ions. Batch equilibrium experiments were conducted to investigate the influence of solution pH, hydrogel weight, ionic strength, adsorption time, temperature and initial concentration of nickel ions on the adsorption. Time-dependent adsorption fitted the best to the pseudo-second-order kinetic model. A thermodynamic study revealed that the adsorption was an exothermic and non-spontaneous process. Five isotherm models were studied, and the best fit was obtained with the Redlich-Peterson model. Consecutive adsorption/desorption studies indicated that the HEA/IA hydrogel can be efficiently used as a sorbent for the removal of Ni2+ ions from the water solution. This study develops a potential adsorbent for the effective removal of trace nickel ions.

Monolithically Integrated Diffused Silicon Two-Zone Heaters for Silicon-Pyrex Glass Microreactors for Production of Nanoparticles: Heat Exchange Aspects.

We present the design, simulation, fabrication and characterization of monolithically integrated high resistivity p-type boron-diffused silicon two-zone heaters in a model high temperature microreactor intended for nanoparticle fabrication. We used a finite element method for simulations of the heaters' operation and performance. Our experimental model reactor structure consisted of a silicon wafer anodically bonded to a Pyrex glass wafer with an isotropically etched serpentine microchannels network. We fabricated two separate spiral heaters with different temperatures, mutually thermally isolated by barrier apertures etched throughout the silicon wafer. The heaters were characterized by electric measurements and by infrared thermal vision. The obtained results show that our proposed procedure for the heater fabrication is robust, stable and controllable, with a decreased sensitivity to random variations of fabrication process parameters. Compared to metallic or polysilicon heaters typically integrated into microreactors, our approach offers improved control over heater characteristics through adjustment of the Boron doping level and profile. Our microreactor is intended to produce titanium dioxide nanoparticles, but it could be also used to fabricate nanoparticles in different materials as well, with various parameters and geometries. Our method can be generally applied to other high-temperature microsystems.

Chitosan Oligosaccharide Lactate Coated Hydroxyapatite Nanoparticles as a Vehicle for the Delivery of Steroid Drugs and the Targeting of Breast Cancer Cells.

Low targeting efficiency and fast metabolism of antineoplastic drugs are hindrances to effective chemotherapies and there is an ongoing search for better drugs, but also better carriers. Steroid derivatives, 3ß-hydroxy-16-hydroxymino-androst-5-en-17-one (A) and 3ß,17ß-dihydroxy-16-hydroxymino-androst-5-ene (B) as cancer growth inhibitors were chemically synthesized and captured in a carrier composed of hydroxyapatite (HAp) nanoparticles coated with chitosan oligosaccharide lactate (ChOLS). The only difference between the two derivatives is that A has a carbonyl group at the C17 position of the five-membered ring and B has a hydroxyl. This small difference in the structure resulted not only in different physicochemical properties of the A- and B-loaded HAp/ChOSL, but also in different biological activities. The morphology of drug-loaded HAp/ChOSL particles was spherical, but the size depended on the drug identity: d50=138 nm for A-loaded HAp/ChOSL and d50=223 nm for B-loaded HAp/ChOSL. Cell-selective toxicity was tested against human breast carcinoma (MCF7 and MDA-MB-231), human lung carcinoma (A549) and human lung fibroblasts (MRC-5). The small selectivity of pure derivatives A and B toward breast cancer cells became drastically increased when they were delivered using HAp/ChOSL particles. Whereas the ratio of the cytotoxicity imposed onto breast cancer cells and the cytotoxicity imposed onto healthy MRC-5 fibroblasts ranged from 1.5 to 1.7 for pure A and from 1.5 to 2.3 for pure derivative B depending on the concentration, it increased to 5.4 for A-loaded HAp/ChOSL and 5.1 for B-loaded HAp/ChOSL. FACS analysis demonstrated poor uptake of HAp/ChOSL particles by MCF7 cells, suggesting that the drug release occurs extracellularly. The augmented activity of the drugs was most likely due to sustained release, although the favorable positive charge of the carrier, allowing it to adhere to the negatively charged plasma membrane and release the drugs steadily and directly to the hydrophobic cell membrane milieu, was delineated as a possible complementary mechanism.

Inactivation of nanocrystalline C60 cytotoxicity by gamma-irradiation.

We investigated the effect of gamma-irradiation on the cytotoxicity of pure C60 solubilized in water by using tetrahydrofuran (THF/n-C60 or THF/n-C60). In contrast to THF/n-C60, its gamma-irradiated counterpart failed to generate oxygen radicals and cause extracellular signal-regulated kinase (ERK)-dependent necrotic cell death in various types of mammalian cells. Moreover, gamma-irradiated THF/n-C60 protected cells from the oxidative stress induced by native THF/n-C60 or hydrogen peroxide. The observed biological effects were associated with gamma-irradiation-mediated decomposition of THF and subsequent derivatization of the n-C60 surface. These results for the first time demonstrate gamma-irradiation-mediated changes in the physico-chemical properties of THF-prepared nanocrystalline C60, resulting in a complete loss of its cytotoxic effect and its conversion to a cytoprotective agent.

Selective anticancer activity of hydroxyapatite/chitosan-poly(d,l)-lactide-co-glycolide particles loaded with an androstane-based cancer inhibitor.

In an earlier study we demonstrated that hydroxyapatite nanoparticles coated with chitosan-poly(d,l)-lactide-co-glycolide (HAp/Ch-PLGA) target lungs following their intravenous injection into mice. In this study we utilize an emulsification process and freeze drying to load the composite HAp/Ch-PLGA particles with 17ß-hydroxy-17α-picolyl-androst-5-en-3ß-yl-acetate (A), a chemotherapeutic derivative of androstane and a novel compound with a selective anticancer activity against lung cancer cells. 1H NMR and 13C NMR techniques confirmed the intact structure of the derivative A following its entrapment within HAp/Ch-PLGA particles. The thermogravimetric and differential thermal analyses coupled with mass spectrometry were used to assess the thermal degradation products and properties of A-loaded HAp/Ch-PLGA. The loading efficiency, as indicated by the comparison of enthalpies of phase transitions in pure A and A-loaded HAp/Ch-PLGA, equaled 7.47wt.%. The release of A from HAp/Ch-PLGA was sustained, neither exhibiting a burst release nor plateauing after three weeks. Atomic force microscopy and particle size distribution analyses were used to confirm that the particles were spherical with a uniform size distribution of d50=168nm. In vitro cytotoxicity testing of A-loaded HAp/Ch-PLGA using MTT and trypan blue dye exclusion assays demonstrated that the particles were cytotoxic to the A549 human lung carcinoma cell line (46±2%), while simultaneously preserving high viability (83±3%) of regular MRC5 human lung fibroblasts and causing no harm to primary mouse lung fibroblasts. In conclusion, composite A-loaded HAp/Ch-PLGA particles could be seen as promising drug delivery platforms for selective cancer therapies, targeting malignant cells for destruction, while having a significantly lesser cytotoxic effect on the healthy cells.

Structure and properties of thermoplastic polyurethanes based on poly(dimethylsiloxane): assessment of biocompatibility.

Properties and biocompatibility of a series of thermoplastic poly(urethane-siloxane)s (TPUSs) based on α,ω-dihydroxy ethoxy propyl poly(dimethylsiloxane) (PDMS) for potential biomedical application were studied. Thin films of TPUSs with a different PDMS soft segment content were characterized by (1) H NMR, quantitative (13) C NMR, Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), contact angle, and water absorption measurements. Different techniques (FTIR, AFM, and DMA) showed that decrease of PDMS content promotes microphase separation in TPUSs. Samples with a higher PDMS content have more hydrophobic surface and better waterproof performances, but lower degree of crystallinity. Biocompatibility of TPUSs was examined after attachment of endothelial cells to the untreated copolymer surface or surface pretreated with multicomponent protein mixture, and by using competitive protein adsorption assay. TPUSs did not exhibit any cytotoxicity toward endothelial cells, as measured by lactate dehydrogenase and 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl-tetrazolium bromide assays. The untreated and proteins preadsorbed TPUS samples favored endothelial cells adhesion and growth, indicating good biocompatibility. All TPUSs adsorbed more albumin than fibrinogen in competitive protein adsorption experiment, which is feature regarded as beneficial for biocompatibility. The results indicate that TPUSs have good surface, thermo-mechanical, and biocompatible properties, which can be tailored for biomedical application requirements by adequate selection of the soft/hard segments ratio of the copolymers.

In vitro biocompatibility evaluation of novel urethane-siloxane co-polymers based on poly(ϵ-caprolactone)-block-poly(dimethylsiloxane)-block-poly(ϵ-caprolactone).

Novel polyurethane co-polymers (TPUs), based on poly(ϵ-caprolactone)-block-poly(dimethylsiloxane)-block-poly(ϵ-caprolactone) (PCL-PDMS-PCL) as soft segment and 4,4'-methylenediphenyl diisocyanate (MDI) and 1,4-butanediol (BD) as hard segment, were synthesized and evaluated for biomedical applications. The content of hard segments (HS) in the polymer chains was varied from 9 to 63 wt%. The influence of the content and length of the HS on the thermal, surface, mechanical properties and biocompatibility was investigated. The structure, composition and HS length were examined using (1)H- and quantitative (13)C-NMR spectroscopy. DSC results implied that the synthesized TPUs were semicrystalline polymers in which both the hard MDI/BD and soft PCL-PDMS-PCL segments participated. It was found that an increase in the average HS length (from 1.2 to 14.4 MDI/BD units) was accompanied by an increase in the crystallinity of the hard segments, storage moduli, hydrophilicity and degree of microphase separation of the co-polymers. Depending on the HS content, a gradual variation in surface properties of co-polymers was revealed by FT-IR, AFM and static water contact angle measurements. The in vitro biocompatibility of co-polymers was evaluated using the endothelial EA.hy926 cell line and protein adsorption on the polyurethane films. All synthesized TPUs adsorbed more albumin than fibrinogen from multicomponent protein mixture, which may indicate biocompatibility. The polyurethane films with high HS content and/or high roughness coefficient exhibit good surface properties and biocompatible behavior, which was confirmed by non-toxic effects to cells and good cell adhesion. Therefore, the non-cytotoxic chemistry of the co-polymers makes them good candidates for further development as biomedical implants.