Redox-Responsive Gold Nanoparticles Coated with Hyaluronic Acid and Folic Acid for Application in Targeting Anticancer Therapy.

Methotrexate (MTX) has poor water solubility and low bioavailability, and cancer cells can become resistant to it, which limits its safe delivery to tumor sites and reduces its clinical efficacy. Herein, we developed novel redox-responsive hybrid nanoparticles (NPs) from hyaluronic acid (HA) and 3-mercaptopropionic acid (MPA)-coated gold NPs (gold@MPA NPs), which were further conjugated with folic acid (FA). The design of FA-HA-ss-gold NPs aimed at enhancing cellular uptake specifically in cancer cells using an active FA/HA dual targeting strategy for enhanced tumor eradication. MTX was successfully encapsulated into FA-HA-ss-gold NPs, with drug encapsulation efficiency (EE) as high as >98.7%. The physicochemical properties of the NPs were investigated in terms of size, surface charges, wavelength reflectance, and chemical bonds. MTX was released in a sustained manner in glutathione (GSH). The cellular uptake experiments showed effective uptake of FA-HA-ss-gold over HA-ss-gold NPs in the deep tumor. Moreover, the release studies provided strong evidence that FA-HA-ss-gold NPs serve as GSH-responsive carriers. In vitro, anti-tumor activity tests showed that FA-HA-ss-gold/MTX NPs exhibited significantly higher cytotoxic activity against both human cervical cancer (HeLa) cells and breast cancer (BT-20) cells compared to gold only and HA-ss-gold/MTX NPs while being safe for human embryonic kidney (HEK-293) cells. Therefore, this present study suggests that FA-HA-ss-gold NPs are promising active targeting hybrid nanocarriers that are stable, controllable, biocompatible, biodegradable, and with enhanced cancer cell targetability for the safe delivery of hydrophobic anticancer drugs.

Biological Stimuli-Induced Phase Transition of a Synthesized Block Copolymer: Preferential Interactions between PNIPAM-b-PNVCL and Heme Proteins.

The beguiling world of functional polymers is dominated by thermoresponsive polymers with unique structural and molecular attributes. Limited work has been reported on the protein-induced conformational transition of block copolymers; furthermore, the literature lacks a clear understanding of the influence of proteins on the phase behavior of thermoresponsive copolymers. Herein, we have synthesized poly(N-isopropylacrylamide)-b-poly(N-vinylcaprolactam) (PNIPAM-b-PNVCL) by RAFT polymerization using N-isopropylacrylamide and N-vinylcaprolactam. Furthermore, using various biophysical techniques, we have explored the effect of cytochrome c (Cyt c), myoglobin (Mb), and hemoglobin (Hb) with varying concentrations on the aggregation behavior of PNIPAM-b-PNVCL. Absorption and steady-state fluorescence spectroscopy measurements were performed at room temperature to examine the copolymerization effect on fluorescent probe binding and biomolecular interactions between PNIPAM-b-PNVCL and proteins. Furthermore, temperature-dependent fluorescence spectroscopy and dynamic light scattering studies were performed to get deeper insights into the lower critical solution temperature (LCST) of PNIPAM-b-PNVCL. Small-angle neutron scattering (SANS) was also employed to understand the copolymer behavior in the presence of heme proteins. With the incorporation of proteins to PNIPAM-b-PNVCL aqueous solution, LCST has been varied to different extents owing to the preferential, molecular, and noncovalent interactions between PNIPAM-b-PNVCL and proteins. The present study can pave new insights between heme proteins and block copolymer interactions, which will help design biomimetic surfaces and aid in the strategic fabrication of copolymer-protein bioconjugates.

Potential Anti-Aging Substances Derived from Seaweeds.

Aging is a major risk factor for many chronic diseases, such as cancer, cardiovascular disease, and diabetes. The exact mechanisms underlying the aging process are not fully elucidated. However, a growing body of evidence suggests that several pathways, such as sirtuin, AMP-activated protein kinase, insulin-like growth factor, autophagy, and nuclear factor erythroid 2-related factor 2 play critical roles in regulating aging. Furthermore, genetic or dietary interventions of these pathways can extend lifespan by delaying the aging process. Seaweeds are a food source rich in many nutrients, including fibers, polyunsaturated fatty acids, vitamins, minerals, and other bioactive compounds. The health benefits of seaweeds include, but are not limited to, antioxidant, anti-inflammatory, and anti-obese activities. Interestingly, a body of studies shows that some seaweed-derived extracts or isolated compounds, can modulate these aging-regulating pathways or even extend lifespans of various animal models. However, few such studies have been conducted on higher animals or even humans. In this review, we focused on potential anti-aging bioactive substances in seaweeds that have been studied in cells and animals mainly based on their anti-aging cellular and molecular mechanisms.

Grafting of Poly(poly(ethylene glycol) methacrylate) onto Halloysite Nanotubes via Surface-Initiated Atom Transfer Radical Polymerization.

A synthetic strategy for the functionalization of halloysite nanotubes (HNTs) with poly(poly(ethylene glycol) methacrylate) (PPEGMA) via surface-initiated atom transfer radical polymerization (SIATRP). The covalent immobilization of PPEGMA was confirmed by FT-IR analysis. The preparation of the nanohybrids was further evidenced by the XPS and EDX studies. The morphologies of functionalized HNTs were investigated by FE-SEM analysis. TGA results suggested that the nanohybrids can be used in high temperature applications. Thus, this newly developed surface functionalization protocol offers the tailoring of the HNTs surface with wide functionalities and is potentially useful to the biomedical applications.

Glutathione Capped CdSe Quantum Dots: Synthesis, Characterization, Morphology, and Application as a Sensor for Toxic Metal Ions.

Glutathione (GSH) functionalized CdSe quantum dots (QDs) (GSH-f-CdSe QDs) were prepared via a simple one-pot strategy at low temperature. The as-synthesized CdSe QDs were characterized by FT-IR and XPS analyses. The morphology, physical structure and size distribution of GSH-f-CdSe QDs were investigated by TEM, XRD and DLS analyses, respectively. The GSH-f-CdSe QDs exhibited excellent stability of optical properties as investigated by UV-Vis absorption and photoluminescence (PL) spectroscopy. The high affinity of GSH towards heavy metal ions made the GSH-f-CdSe QDs quite susceptible to Pb2+ ion which poses serious threat to the health and environment. The PL intensity of GSH-f-CdSe QDs was observed to be apparently quenched in the presence of Pb2+ ions in aqueous solution rendering their potentialities as a sensor for detection of toxic heavy metal ions.

Combined Minimum-Run Resolution IV and Central Composite Design for Optimized Removal of the Tetracycline Drug Over Metal⁻Organic Framework-Templated Porous Carbon.

In this study, a minimum-run resolution IV and central composite design have been developed to optimize tetracycline removal efficiency over mesoporous carbon derived from the metal-organic framework MIL-53 (Fe) as a self-sacrificial template. Firstly, minimum-run resolution IV, powered by the Design-Expert program, was used as an efficient and reliable screening study for investigating a set of seven factors, these were: tetracycline concentration (A: 5-15 mg/g), dose of mesoporous carbons (MPC) (B: 0.05-0.15 g/L), initial pH level (C: 2-10), contact time (D: 1-3 h), temperature (E: 20-40 °C), shaking speed (F: 150-250 rpm), and Na+ ionic strength (G: 10-90 mM) at both low (-1) and high (+1) levels, for investigation of the data ranges. The 20-trial model was analyzed and assessed by Analysis of Variance (ANOVA) data, and diagnostic plots (e.g., the Pareto chart, and half-normal and normal probability plots). Based on minimum-run resolution IV, three factors, including tetracycline concentration (A), dose of MPC (B), and initial pH (C), were selected to carry out the optimization study using a central composite design. The proposed quadratic model was found to be statistically significant at the 95% confidence level due to a low P-value (<0.05), high R2 (0.9078), and the AP ratio (11.4), along with an abundance of diagnostic plots (3D response surfaces, Cook's distance, Box-Cox, DFFITS, Leverage versus run, residuals versus runs, and actual versus predicted). Under response surface methodology-optimized conditions (e.g., tetracycline concentration of 1.9 mg/g, MPC dose of 0.15 g/L, and pH level of 3.9), the highest tetracycline removal efficiency via confirmation tests reached up to 98.0%-99.7%. Also, kinetic intraparticle diffusion and isotherm models were systematically studied to interpret how tetracycline molecules were absorbed on an MPC structure. In particular, the adsorption mechanisms including "electrostatic attraction" and "π-π interaction" were proposed.

Development of a Spoke Type Torque Sensor Using Painting Carbon Nanotube Strain Sensors.

This study reports a hub-spoke type joint torque sensor involving strain gauges made of multiwalled carbon nanotubes (MWCNT). We developed the novel joint torque sensor for robots by means of MWCNT/epoxy strain sensors (0.8 wt%, gauge factor 2) to overcome the limits of conventional foil strain gauges. Solution mixing process was hired to fabricate a liquid strain sensor that can easily be installed on any complicated surfaces. We painted the MWCNT/epoxy mixing liquid on the hub-spoke type joint torque sensor to form the piezoresistive strain gauges. The painted sensor converted its strain into torque by mean of the installed hub-spoke structure after signal processing. We acquired sufficient torque voltage responses from the painted MWCNT/epoxy strain sensor.

Synthesis of PbMoO4 Nanoparticles Using a Facile Surfactant-Assisted Microwave Process and Their Photocatalytic Activity.

Lead molybdate (PbMoO4) materials were successfully synthesized using a facile surfactant-assisted microwave process and characterized by XRD, Raman, PL, BET and DRS. We also investigated the photocatalytic activity of these materials for the decomposition of Rhodamine B under UV-light irradiation. The XRD and Raman results revealed the successful synthesis of 42­69 nm, well-crystallized PbMoO4 crystals with a facile surfactant-assisted microwave process. The PbMoO4 catalysts prepared using microwave process enhanced the photocatalytic activity compared to PbMoO4 catalyst prepared by hydrothermal method. The PbMoO4 catalyst prepared at 100 °C showed the highest photocatalytic activity. The PL peak was appeared at about 540 nm for all catalysts and the excitonic PL signal was proportional to the photocatalytic activity for the decomposition of Rhodamine B.

Synthesis and Characterization of Multiwalled Carbon Nanotubes/Poly(HEMA-co-MMA) by Utilizing Click Chemistry.

The hybrid material consisting of multi walled carbon nanotubes (MWNTs) and poly(2-hydroxyethylmethacrylate-co-methylmethacrylate) [poly(HEMA-co-MMA)] was synthesized by a combination of RAFT and Click chemistry. In the primary stage, the copolymer poly(HEMA-co-MMA) was prepared by applying RAFT technique. Alkynyl side groups were incorporated onto the poly(HEMA-co-MMA) backbone by esterification reaction. Then, MWNTs-N3 was prepared by treating MWNTs with 4-azidobutylamine. The click coupling reaction between azide-functionalized MWNTs (MWNTs-N3) and the alkyne-functionalized random copolymer ((HEMA-co-MMA)-Alkyne) with the Cu(I)-catalyzed [3+2] Huisgen cycloaddition afforded the hybrid compound. The structure and properties of poly(MMA-co-HEMA)-g-MWNTs were investigated by FT-IR, EDX and TGA measurements. The copolymer brushes were observed to be immobilized onto the functionalized MWNTs by SEM and TEM analysis.

Surface Enrichment of Fluorocarbon End-Capped Polymers with Different Fluorocarbon Lengths.

This study investigated the surface structure of fluorocarbon end-capped l-poly(lactide)s (F-PLLA) with different fluorocarbon lengths by electron spectroscopy for chemical analysis (ESCA). Fluorocarbon chains of three lengths (F(CF2)n(CH2)2, where n = 6, 8, and 10) have been synthesized as the terminal group to PLLA. Angular dependent ESCA revealed that the fluorocarbon groups are segregated at the surface. Further, the results show the surface coverage of fluorocarbon groups rapidly increases with increasing the length of fluorocarbon end groups (synergy effect). The surface composition of F-PLLAs can be controlled by changing the length of fluorocarbon.

Covalent Immobilization of Biotin on Magnetic Nanoparticles: Synthesis, Characterization, and Cytotoxicity Studies.

A simple protocol for covalent immobilization of biotin onto the surface of Fe3O4 magnetic nanoparticles (MNPs) for improving the biocompatibility of original MNPs has been realized. MNPs were first prepared by co-precipitation method which was subsequently anchored with functionalized biotin. The as-synthesized MNPs were observed to be monocrystalline as evidenced from XRD and TEM images. The covalent grafting of biotin to MNPs was confirmed by FT-IR. The XPS analysis suggested the successful preparation of Biotin-f-MNPs. The as-synthesized Biotin-f-MNPs were found to be superparamagnetic character as recorded by SQUID. Cell viability studies revealed that the biocompatibility of MNPs was improved upon Biotin immobilization.

Fabrication of Phenanthroline Modified Graphene Nanosheets Decorated with Palladium Nanoparticles.

Palladium nanoparticles decorated modified reduced graphene oxide (RGO) composite was synthesized by a two-step process using 1,10-Phenanthroline (PHEN) as bridging agent. Firstly, the graphene oxide (GO) was non-covalently modified with the PHEN molecules through π-π interaction between two components. Then, the modified GO was complexed with Pd precursor and subsequently reduced from Pd2+ to Pd0 using NaBH4 to yield Pd dispersed modified RGO sheets. The structure and morphology of the resulting composites were characterized by FTIR, TGA, EDX, FESEM, HRTEM and XRD measurements. XPS results revealed that the reduction of Pd2+ to metal-lic Pd was successfully achieved, while the HRTEM and FESEM micrographs suggested that the Pd nanoparticles were well-dispersed on the functionalized graphene sheets.

Preparation of ß-Cyclodextrin Multi-Decorated Halloysite Nanotubes as a Catalyst and Nanoadsorbent for Dye Removal.

Hybrid materials of ß-cyclodextrin multi-decorated halloysite nanotubes (HNTs-g-ßCD) were prepared by a facile route, which showed high efficiency for catalysis and dye adsorption. Initially, the surface of halloysite nanotubes (HNTs) was modified with poly(glycidyl methacrylate) by the reversible addition fragmentation chain transfer (RAFT) polymerization of glycidyl methacrylate having epoxy groups as a monomer. Subsequently, ß-cyclodextrin was conjugated with the modified HNTs to produce HNTs-g-ßCD by the epoxide ring-opening reaction of mono-6-deoxy-6-hexanediamine-ß-cyclodextrin. The nanocomposites were characterized by FT-IR, TGA, SEM, and TEM. The HNTs-g-ßCD composites could be used as a nano adsorbent for methylene blue and a catalyst in the oxidation reaction of benzyl alcohol owing to the unique structure of ß-cyclodextrin. The HNTs-g-ßCD shows promiseas potential multi-functional materials by a combination of ß-cyclodextrin and HNTs properties.

Hydrogenolysis of Glycerol to Propylene Glycol on Nanosized Cu-Zn-Al Catalysts Prepared Using Microwave Process.

Cu-Zn-Al catalysts were prepared using microwave-assisted process and co-precipitation methods. The prepared catalysts were characterized by XRD, BET, XPS and TPD of ammonia and their catalytic activity for the hydrogenolysis of glycerol to propylene glycol was also examined. The XRD patterns of Cu/Zn/Al mixed catalysts show CuO and ZnO crystalline phase regardless of preparation method. The highest glycerol hydrogenolysis conversion is obtained with the catalyst having a Cu/Zn/Al ratio of 2:2:1. Hydrogen pre-reduction of catalysts significantly enhanced both glycerol conversions and selectivity to propylene glycol. The glycerol conversion increased with an increase of reaction temperature. However, the selectivity to propylene glycol increased with an increase of temperature, and then declined to 30.5% at 523 K.

Catalytic combustion of benzene over CuO-CeO2 mixed oxides.

Catalytic combustion of benzene over CuO-CeO2 mixed oxides has been investigated. The CuO-CeO2 mixed oxides were prepared by the combustion method using malic acid as an organic fuel and characterized by XRD, XPS and TPR. For the CuO-CeO2 catalyst with a Cu/(Cu + Ce) molar ratio of more than 0.4, highly dispersed copper oxide species were shown at 2θ = 35.5 degrees and 38.8 degrees. The CuO-CeO2 catalyst prepared using 2.0 M malic acid showed the highest activity, with conversion reaching nearly 100% at 350 degrees C. In addition, the highest activity is shown on Cu0.40 (the index denotes the molar ratio Cu/(Cu + Ce)) sample and then it decreases on Cu0.5 and Cu0.7 samples.

One-pot synthesis of conducting poly(3-methylthiophene)-grafted-graphene nanosheets.

We report a simple one-pot synthesis of graphene nanosheets wrapped poly(3-methylthiophene) (GNs-f-P3MT) composites. At first, natural graphite was oxidized using the Hummer's method followed by chemical reduction with hydrazine monohydrate to yield GNs. Subsequently, in-situ chemical oxidative polymerization of 3-methylthiophene was carried out to obtain noncovalently bonded GNs-f-P3MT composites. The morphology and microstructure of the composites together with pure graphene oxide and GNs were characterized using XPS, XRD, FT-IR, FESEM, HRTEM and TGA. The microscopic results indicated the homogeneous dispersion of GNs throughout the polymer matrix. Furthermore, thermogravimetric results illustrated that the addition of GNs into the P3MT matrix led to improvement in the thermal stability of the composites.

Water soluble graphene oxide/poly(1-vinylimidazole) composites: synthesis and characterization.

Modified graphene oxide/poly(1-vinylimidazole) (mGO/PVIm) composites were prepared via surface-initiated free radical graft polymerization. First, the hydroxyl-enriched GO sheets were functionalized with 3-methacryloxypropyltrimethoxysilane to introduce active-vinyl groups on the GO surfaces. Subsequently, 1-vinylimidazole was chemically grafted and polymerized in the presence of mGO. The chemical structures and morphology of the covalently bonded composites were characterized using FTIR, XPS, TGA, HRTEM, FESEM and XRD measurements. The mGO/PVIm composites exhibit a stable dispersion in water and show high storage stability (>10 days). Furthermore, the morphological analysis showed that mGO was homogeneously dispersed in the polymer matrix.

Synthesis of PbMoO4 nanoparticles by microwave-assisted hydrothermal process and their photocatalytic activity.

Lead molybdate (PbMoO4) was successfully synthesized using a microwave-assisted method and characterized by XRD, Raman spectroscopy, SEM, PL and DRS. We also investigated the photocatalytic activity of these materials for the decomposition of Rhodamin B under UV-light irradiation. The XRD and Raman results revealed the successful synthesis of 42-52 nm, well-crystallized PbMoO4 crystals with the microwave-assisted hydrothermal method. The PbMoO4 catalysts prepared using the microwave-assisted process enhanced the photocatalytic activity compared to that prepared by hydrothermal method and the catalysts prepared at a solution pH = 11 and temperature of 105 degrees C showed the highest photocatalytic activity. The PL peaks appeared at about 540 nm for all catalysts and the excitonic PL signal was proportional to the photocatalytic activity for the decomposition of Rhodamin B.

Controlled synthesis, optical properties and cytotoxicity studies of CdSe-poly(lactic acid) multifunctional nanocomposites by ring-opening polymerization.

A facile synthetic route has been developed for the covalent grafting of biocompatible poly(lactic acid) (PLA) onto CdSe Quantum Dots (QDs) using surface initiated ring opening polymerization (ROP) to afford CdSe-g-PLA nanocomposites. At first, 2-mercaptoethanol (ME) capped CdSe QDs were synthesized through a wet chemical process. The surface initiated ROP of lactide was accomplished with Sn(Oct)2 to give CdSe-g-PLA nanocomposites having surface hydroxyl functionality. FT-IR data suggested that a robust covalent bond was formed between ME capped CdSe QDs and polymer moieties. The grafting density of PLA on CdSe QDs was found to be moderate as measured by TGA analysis. The CdSe QDs were well dispersed in CdSe-g-PLA nanocomposites matrices as captured by TEM. The cubic phase crystal structure of CdSe QDs in the nanocomposites was determined by XRD. The optical properties of the CdSe-g-PLA nanocomposites were investigated by UV-vis and photoluminescence spectroscopy which suggested their potentialities as optical materials in biomedical application. Cell viability studies revealed that the biocompatibility of CdSe QDs was improved upon PLA immobilization.

Uncatalyzed synthesis and characterization of a water-soluble polyacetylene: poly[2-ethynyl-N-(propylsulfonate)pyridinium betaine].

A new ionic conjugated polymer was prepared by the activated polymerization of 2-ethynylpyridine with the ring-opening of 1,3-propanesultone without any additional initiator or catalyst. This polymer was characterized by various instrumental methods to have conjugated polymer backbone system with pendant N-propylsulfonate functional groups. The photoluminescence spectrum of polymer showed that the PL peak is located at 552 nm corresponding to the photon energy of 2.25 eV. The cyclovoltammograms of polymer exhibited the irreversible electrochemical behaviors between the oxidation and reduction peaks. The oxidation current density of polymer versus the scan rates is approximately linear relationship in the range of 30-120 mV/sec. It was found that the kinetics of the redox process is almost controlled by the reactant diffusion process from the oxidation current density of polymer versus the scan rates.