A Study of Hydrophobically Modified Pullulan Nanoparticles with Different Hydrophobic Densities on the Effect of Anti-Colon Cancer Cell Efficiency.

To discuss the effect of hydrophobic groups of a polymer on the structural properties and function of polymer nanoparticles (NPs), we grafted chenodeoxycholic acid (CDCA) with pullulan (PU) to form hydrophobically modified PU (PUC). Three PUC polymers, namely, PUC-1, PUC-2, and PUC-3, with different degrees of substitution were designed by changing the feed ratio of CDCA and PU. 1H-NMR spectra showed that the PUC polymer was successfully synthesized, and the degrees of hydrophobic substitution for PUC-1, PUC-2, and PUC-3 were calculated to be 10.66%, 13.92%, and 16.94%, respectively. The PUC NPs were prepared by the dialysis method and were shown to be uniformly spherical by transmission electron microscopy (TEM). The average sizes were about (220±10) nm, (203±7) nm, and (163±6) nm under dynamic light scattering (DLS) for PUC-1 NPs, PUC-2 NPs, and PUC-3 NPs, respectively. Drug release experiments showed that the three PUC/DOX NPs exhibited good sustained release. At 48 h, the IC50 of doxorubicin in inhibiting colon cancer HCT116 cells was 0.0904 µg/mL. A cell study showed that PUC-3/DOX NPs had the highest uptake efficiency by HCT116 cells with the most cytotoxicity and inhibited the migration of HCT116 cells with the highest efficiency. The structural properties and function of polymer NPs were closely related to the hydrophobic groups in the polymer, and NPs with higher hydrophobicity showed a smaller size, higher drug capacity, and greater cell efficiency.

Simple and rapid nicotine analysis using a disposable silica nanochannel-assisted electrochemiluminescence sensor.

Nicotine analysis is essential to medicine, toxicology and the tobacco industry. However, no simple, portable and disposable method was developed to meet their demands. Here, we report a simple, rapid and disposable silica nanochannel (SAN)-based electrochemiluminescence (ECL) sensor for nicotine analysis by simply assembling a SAN electrode with a paper cover. The sensing principle of the disposable sensor is based on the size exclusion effect and charge selectivity, which obviously prolong the sensor service time. We find that the sensor exhibits good specificity to nicotine, and most of the complex matrices are unlikely to impact the detection. The performance of the disposable sensor in cigarettes, e-cigarettes, nicotine gums, and lozenges is fully validated, showing satisfactory linearity, sensitivity (a limit of detection of 27.82 nM), and accuracy (a recovery between 96.00% and 106.51%). The disposable sensor can be potentially applied for on-site nicotine analysis.

mPEG-icariin nanoparticles for treating myocardial ischaemia.

Icariin (ICA), a major active ingredient from Chinese medicine, has unique pharmacological effects on ischaemic heart disease. However, its hydrophobic property limits its administration and leads to poor efficacy. This work aimed to change its hydrophobic property and improve the treatment efficacy. We designed a new nano-drug to increase the ICA delivery. ICA was modified with hydrophilic polyethylene glycol monomethyl ether (mPEG) by a succinic anhydride linker to form a polyethylene glycol-icariin (mPEG-ICA) polymer. The structure of this polymer was identified by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. The content of ICA in the polymer was 32% as detected by ultraviolet spectrophotometry. mPEG-ICA nanoparticles, of 143.3 nm, were prepared by the dialysis method, and zeta potential was 0.439 mV by dynamic light scattering. The nanoparticles had a spherical shape on transmission electron microscopy. In media with pH 7.4 and 6.8, ICA release from mPEG-ICA nanoparticles after 72 h was about 0.78% and 64.05%, respectively, so the ICA release depended on the release media pH. On MTT and lactate dehydrogenase activity assay, mPEG-ICA nanoparticles could reduce cell damage induced by oxgen-glucose deprivation. Hoechst 33258 staining and TUNEL and AnnexinV-FITC/PI double staining showed that ICA nanoparticles could increase the activity of H9c2 cardiomyocytes under oxgen-glucose deprivation conditions by decreasing apoptosis. ICA modified by hydrophilic mPEG could improve its efficacy.

Novel Delivery of Mitoxantrone with Hydrophobically Modified Pullulan Nanoparticles to Inhibit Bladder Cancer Cell and the Effect of Nano-drug Size on Inhibition Efficiency.

Reducing the dosage of chemotherapeutic drugs via enhancing the delivery efficiency using novel nanoparticles has great potential for cancer treatment. Here, we focused on improving mitoxantrone delivery by using cholesterol-substituted pullulan polymers (CHPs) and selected a suitable nano-drug size to inhibit the growth of bladder cancer cells. We synthesized three kinds of CHPs, named CHP-1, CHP-2, CHP-3. Their chemical structures were identified by NMR, and the degree of cholesterol substitution was 6.82%, 5.78%, and 2.74%, respectively. Their diameters were 86.4, 162.30, and 222.28 nm. We tested the release rate of mitoxantrone in phosphate-buffered saline for 48 h: the release rate was 38.73%, 42.35%, and 58.89% for the three CHPs. The hydrophobic substitution degree in the polymer was associated with the self-assembly process of the nanoparticles, which affected their size and therefore drug release rate. The release of the three drug-loaded nanoparticles was significantly accelerated in acid release media. The larger the nanoparticle, the greater the drug release velocity. At 24 h, the IC50 value was 0.25 M, for the best inhibition of mitoxantrone on bladder cancer cells.3-(4,5-Dimethyl-2-thiazolyl)-2,5-diphenyl-2-H-tetrazolium bromide (MTT) experiments demonstrated that drug-loaded CHP-3 nanoparticles with the largest size were the most toxic to bladder cancer cells. Immunofluorescence and flow cytometry revealed that drug-loaded CHP-3 nanoparticles with the largest size had the strongest effect on promoting apoptosis of bladder cancer cells. Also, the three drug-loaded nanoparticles could all inhibit the migration of MB49 cells, with large-size CHP-3 nanoparticles having the most powerful inhibition.

TsOH·H2O-mediated N-amidation of quinoline N-oxides: facile and regioselective synthesis of N-(quinolin-2-yl)amides.

An operationally simple method with 100% atom economy has been developed for the synthesis of various N-(quinolin-2-yl)amides via the TsOH·H2O-mediated N-amidation of quinoline N-oxides using inexpensive and commercially available nitriles as the amidation reagents. Mechanistic exploration suggested that the reaction probably proceeds through an acid-assisted 1,3-dipolar cycloaddition and an N-O bond cleavage followed by a dehydro-aromatization process.

In Situ Generated HypoIodite Activator for the C2 Sulfonylation of Heteroaromatic N-oxides.

A mild approach for direct C2 sulfonylation of heteroaromatic N-oxides with sulfonyl hydrazides affording 2-sulfonyl quinolines/pyridines has been developed. A variety of heteroaromatic N-oxides and sulfonyl hydrazides participate effectively in this transformation which uses hypoiodites (generated in situ from NaI and TBHP) as a means of substrate activators. In this reaction, the N-oxide plays a dual role, acting as a traceless directing group as well as a source of oxygen atom.

Polar modified post-cross-linked resin and its adsorption toward salicylic acid from aqueous solution: Equilibrium, kinetics and breakthrough studies.

A novel polar modified post-cross-linked resin PDMPA was synthesized, characterized and evaluated for adsorption of salicylic acid from aqueous solution. PDMPA was prepared by a suspension polymerization of methyl acrylate (MA) and divinylbenzene (DVB), a Friedel-Crafts reaction and an amination reaction. After characterization of the chemical and pore structure of PDMPA, the adsorption behaviors of salicylic acid on PDMPA were determined in comparison with the precursor resins. The equilibrium adsorption capacity of salicylic acid on PDMPA was much larger than the precursor resins and the equilibrium data were correlated by both of the Langmuir and Freundlich models. The pseudo-second-order rate equation fitted the kinetic data better than the pseudo-first-order rate equation, and the micropore diffusion model could characterize the kinetic data very well. The dynamic experimental results showed that the breakthrough point and saturated point of salicylic acid on PDMPA were 40.3 and 92.4BV (1BV=10mL) at a feed concentration of 995.8mg/L and a flow rate of 1.4mL/min, and the resin column could be regenerated by 16.0BV of a mixture desorption solvent containing 0.01mol/L of NaOH (w/v) and 50% of ethanol (v/v).

Adsorption behaviors of a novel carbonyl and hydroxyl groups modified hyper-cross-linked poly(styrene-co-divinylbenzene) resin for beta-naphthol from aqueous solution.

A series of novel hyper-cross-linked resins were synthesized from macroporous cross-linked chloromethylated poly(styrene-co-divinylbenzene) by adding different dosage of hydroquinone in Friedel-Crafts reaction. The results of the pore structures revealed that the prepared resins possessed micropores, mesopores and macropores, and the chloromethyl groups and the uploaded hydroquinone were partly oxidized according to the results of Fourier-transformed infrared ray spectra. Among these hydroquinone modified resins, HJ-Y06 resin held the largest adsorption capacity for beta-naphthol, and its adsorption capacity was comparable with XAD-4 while much larger than X-5. The adsorption kinetics could be characterized by pseudo-second-order rate equation and intra-particle diffusion model was the rate-limiting step at the initial process. The adsorption was favorable at solution pH lower than 6.5. The adsorption isotherms could be fitted by Langmuir model and the adsorption was an endothermic process. Hydrogen bonding between formaldehyde carbonyl and quinone carbonyl groups on HJ-Y06 and phenolic hydroxyl groups of beta-naphthol was the main driving force for the adsorption.

Synthesis, characterization and antibacterial activities of some new ferrocene-containing penems.

The synthesis and structure-activity relationships of a series of new penems bearing ferrocenyl group attached to the C-2 position of the penem nucleus were described. The beta-lactanic derivatives obtained had been characterized as sodium salts, through (1)H NMR and IR, as well as through element analysis. Their in vitro antibacterial activities against both Gram-positive including meticillin-resistant Staphylococcus aureus (MRSA) and Gram-negative bacteria were tested. Most of the penems exhibited superior or equivalent efficacy of antibacterial activity as well as high stability to renal dehydropeptidase-I (DHP-I) compared with faropenem. In particular, the compound 14h having a heterocyclic group showed the most potent antibacterial activity.

Surface modification on a hyper-cross-linked polymeric adsorbent by multiple phenolic hydroxyl groups to be used as a specific adsorbent for adsorptive removal of p-nitroaniline from aqueous solution.

A hyper-cross-linked polymeric adsorbent functionalized with multiple phenolic hydroxyl groups HJ-03 was prepared in this study and its adsorptive characteristics for p-nitroaniline from aqueous solution were studied as compared with Amberlite XAD-4. The adsorption of p-nitroaniline was sensitive to the solution pH and the maximum adsorption capacity was observed at pH of 3.5. The adsorption kinetics obeyed the pseudo-second-order rate equation and the adsorption isotherms could be correlated to Langmuir isotherm model. The adsorption enthalpy, adsorption free energy, and adsorption entropy were calculated to be negative and the adsorption was mainly driven by enthalpy change. The polarity matching between HJ-03 resin and p-nitroaniline, the pore structure of HJ-03, and the size matching between the pore diameter of HJ-03 and the molecular size of p-nitroaniline brought the larger adsorption capacity and higher adsorption affinity.

Synthesis of dipicolylamino substituted quinazoline as chemosensor for cobalt(II) recognition based on excited-state intramolecular proton transfer.

A new fluorescent chemosensor for sensing Co(II) using di(2-picolyl)amino (DPA) as a recognition group and quinazoline as a reporting group has been synthesized and characterized. The quinazoline derivative contains an intramolecular hydrogen bond, which would undergo excited-state intramolecular proton transfer (ESIPT) at illumination. The fluorescence quenching is attributed to cation-induced inhibition of ESIPT, which constitutes the basis for the determination of Co(II) with the prepared chemosensor. The fluorophore forms 1:1 cobalt(II) complex with the logarithm of apparent dissociation constant log K(a)=6.8. The analytical performance characteristics of the proposed Co(II)-sensitive sensor were investigated. The chemosensor exhibits a linear response toward Co(II) in the concentration range 3.2 x 10(-8) to 1.4 x 10(-6) M, with a working pH range from 7.0 to 9.5 and high selectivity.

A fluorescent chemosensor for copper(II) based on a carboxylic acid-functionalized tris(2,2'-bipyridine)-ruthenium(II) complex.

In this research, bis(2,2'-bipyridine)(4-methyl-2,2'-bipyridine-4'-carboxylic acid)ruthenium(II).2PF(6)- complex (1), was first used as a fluorescent chemosensor to recognize Cu(II) in EtOH/H(2)O (1:1, v/v) solution. The response of the sensor is based on the fluorescence quenching of complex 1 by binding with Cu(II). The analytical performance characteristics of the proposed Cu(II)-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Cu(II) with a linear range covering from 5.0 x 10(-8) to 1.0 x 10(-4) M and a detection limit of 4.2 x 10(-8) M. The experiment results show that the response behavior of 1 to Cu(II) is pH independent in medium condition (pH 4.0 - 8.0), and show excellent selectivity for Cu(II) over other transition metal cations.

A fluorescent chemical sensor for Hg(II) based on a corrole derivative in a PVC matrix.

A fluorescent chemical sensor for Hg(II) using 5,10,15-tris(pentafluorophenyl)corrole (H(3)(tpfc)) as fluorophore is described in this paper. The response of the sensor is based on the fluorescence quenching of H(3)(tpfc) by coordination with Hg(II). H(3)(tpfc) based sensor shows a linear response towards Hg(II) in the concentration range from 1.2x10(-7) to 1.0x10(-4)M, with a working pH range from 5.0 to 8.0. The response time for Hg(II) concentration