Silver–titanium dioxide nanocomposites as effective antimicrobial and antibiofilm agents

Recent studies have revealed the existence of liver cancer stem cells (CSCs). Therefore, there is an urgent need for new and effective treatment strategies specific to liver CSCs. In this work, the poly(d,l-lactide-coglycolide) nanoparticles containing paclitaxel were prepared by emulsification-solvent evaporation method. The nanoparticles decorated with anti-CD133 antibody, termed targeted nanoparticles, were prepared by carbodiimide chemistry for liver CSCs. The physicochemical characteristics of the nanoparticles (i.e., encapsulation efficiency, particle size distribution, morphology, and in vitro release) were investigated. Cellular uptake and accumulation in tumor tissue of nanoparticles were observed. To assess anti-tumor activity of nanoparticles in vitro and in vivo, cell survival assay and tumor regression study were carried out using liver cancer cell lines (Huh7 and HepG2) and their xenografts. Particle size of targeted nanoparticles was 429.26 ± 41.53 nm with zeta potential of ?11.2 mV. Targeted nanoparticles possessed spherical morphology and high encapsulation efficiency (87.53 ± 5.9 %). The accumulation of targeted nanoparticles depends on dual effects of passive and active targeting. Drug-loaded nanoparticles showed cytotoxicity on the tumor cells in vitro and in vivo. Targeted nanoparticles resulted in significant improvement in therapeutic response through selectively eliminating CD133 positive subpopulation. These results suggested that the novel nanoparticles could be a promising candidate with excellent therapeutic efficacy for targeting liver CSCs.     

Evaluation of Activation Energies for Pairwise and Non-Pairwise Hydrogen Addition to Propyne Over Pd/Aluminosilicate Fiberglass Catalyst by Parahydrogen-Induced Polarization (PHIP)

Hydrogenation of propyne to propene over Pd/aluminosilicate fiberglass catalyst in the temperature range 175–350 °C was investigated with the use of parahydrogen-induced polarization (PHIP) technique. Activation energies for both pairwise and non-pairwise H₂ addition routes were estimated. It was found that at 175–275 °C the activation energies for hydrogen addition to the triple bond of propyne have similar values (about 60–70 kJ/mol) for both routes of hydrogen addition. At higher temperatures (275–350 °C), the rate constant for pairwise hydrogen addition reaches a maximum value while the rate constant for non-pairwise hydrogen addition continues to increase with increasing temperature.     

A new ONO3- trianionic pincer-type ligand for generating highly nucleophilic metal-carbon multiple bonds

Appending an amine to a C═C double bond drastically increases the nucleophilicity of the β-carbon atom of the alkene to form an enamine. In this report, we present the synthesis and characterization of a novel CF(3)-ONO(3-) trianionic pincer-type ligand, rationally designed to mimic enamines within a metal coordination sphere. Presented is a synthetic strategy to create enhanced nucleophilic tungsten-alkylidene and -alkylidyne complexes. Specifically, we present the synthesis and characterization of the new CF(3)-ONO(3-) trianionic pincer tungsten-alkylidene [CF(3)-ONO]W═CH(Et)(O(t)Bu) (2) and -alkylidyne {MePPh(3)}{[CF(3)-ONO]W≡C(Et)(O(t)Bu)} (3) complexes. Characterization involves a combination of multinuclear NMR spectroscopy, combustion analysis, DFT computations, and single crystal X-ray analysis for complexes 2 and 3. Exhibiting unique nucleophilic reactivity, 3 reacts with MeOTf to yield [CF(3)-ONO]W═C(Me)(Et)(O(t)Bu) (4), but the bulkier Me(3)SiOTf silylates the tert-butoxide, which subsequently undergoes isobutylene expulsion to form [CF(3)-ONO]W═CH(Et)(OSiMe(3)) (5). A DFT calculation performed on a model complex of 3, namely, [CF(3)-ONO]W≡C(Et)(O(t)Bu) (3'), reveals the amide participates in an enamine-type bonding combination. For complex 2, the Lewis acids MeOTf, Me(3)SiOTf, and B(C(6)F(5))(3) catalyze isobutylene expulsion to yield the tungsten-oxo complex [CF(3)-ONO]W(O)((n)Pr) (6).     

Palladium(II)-catalyzed enyne cyclization strategies toward the podophyllotoxin ring system

A functionally enriched ABCD ring system of podophyllotoxin was generated through Pd(II)-templated cyclization of an alkynoic alkene, prepared in five steps from commercially available 6-bromopiperonal. This research expands upon the recent carboesterification methodology of Dong et al. (Angew. Chem., Int. Ed. 2009, 48, 9690–9692) by the application of PdCl₂(MeCN)₂, LiCl, and CuCl₂ conditions, which yielded the desired podophyllotoxin scaffold with an embedded vinyl chloride moiety. Likewise, these conditions were successfully applied to a propargylic alkene prepared in three steps from 6-bromopiperonal. The resulting product contains the ABCD ring system of podophyllotoxin, but substitutes a D-ring furan for the D-ring lactone. Application of the recent methodology of Lu et al. (J. Org. Chem. 1995, 60, 1160–1169) on a related 1,6-enyne substrate led to functionalized α-methylene γ-butyrolactones instead (Pd₂(dba)₃·CHCl₃, LiBr, and CuBr₂). The latter conditions applied to an alkynoic alkene afforded the ABCD ring system of podophyllotoxin with a vinyl bromide group. These vinyl halides allow for derivatization at a critical juncture in order to access novel podophyllotoxin analogs.     

Synthesis of dipeptide isosteres by cross-metathesis

This work describes the attachment of two amino acid derivatives by olefin cross-metathesis using Grubbs' second generation catalyst. They were connected at the carboxyl termini. In addition, a cyclic dilactam scaffold was used, which reacted with only a fraction of the amino acid derivatives. The remaining fraction coupled directly coupled with no scaffold. This highly trans-selective double attachment resulted in the cross-metathesis of a variety of amino acids in a single reaction.     

Synthesis and Stereochemistry of Novel Dibrominated 1,5-Dioxaspiro[5.5]undecane Derivatives

Summary.  The synthesis and stereochemistry of new dibrominated spiro-1,3-dioxane derivatives are reported. Investigations by means of NMR methods and single crystal X-ray diffraction for two compounds revealed the high regio- and diastereoselectivity of the bromination reaction of some new spiro-1,3-dioxanes and the asymmetric induction of the chiral carbon atom located in the spiro skeleton. Received July 13, 1999. Accepted October 21, 1999     

Detecting Mechanochemical Degradation of Nitrocellulose by Combining Dynamic Mechanical Analysis with Mass Spectrometry

Summary: Dynamic mechanical analysis is combined with mass spectrometry to study nitrocellulose under oscillating strain. At a constant temperature (150–160 °C) and frequency (400–600 Hz) nitrocellulose fractures demonstrating a modulus drop and release of products with m/z: 30 and 44. At linear heating (2 °C · min⁻¹) and a frequency of 10–50 Hz similar products are released in two steps, the second of which demonstrates a modulus drop and a temperature increase indicating ignition.

Data for an isothermal dynamic mechanical analysis–mass spectrometry experiment performed at 160 °C.     

The synthesis of free-standing films of polymer/nanocarbon composites using the carbon nanopowder's buoyancy

In this work we report the synthesis of free-standing films of polymer/nanocarbon composites. The method consists in forming a thin film of carbon nanoparticles onto the water's surface. Through the free infiltration of the polymer between the nanoparticles which form the film, after the polymer is cured, we obtain free-standing films of polymer/nanocarbon composites. The composite films are homogeneous; they have 5 wt.% carbon nanoparticles within the polymer matrix and are a few micrometers in thickness.     

Random repeated quantum interactions and random invariant states

We consider a generalized model of repeated quantum interactions, where a system ${\mathcal{H}}$ is interacting in a random way with a sequence of independent quantum systems ${\mathcal{K}_n, n \geq 1}$ . Two types of randomness are studied in detail. One is provided by considering Haar-distributed unitaries to describe each interaction between ${\mathcal{H}}$ and ${\mathcal{K}_n}$ . The other involves random quantum states describing each copy ${\mathcal{K}_n}$ . In the limit of a large number of interactions, we present convergence results for the asymptotic state of ${\mathcal{H}}$ . This is achieved by studying spectral properties of (random) quantum channels which guarantee the existence of unique invariant states. Finally this allows to introduce a new physically motivated ensemble of random density matrices called the asymptotic induced ensemble.     

Cation transport by a redox-active synthetic ion channel

The synthesis, cation binding and transmembrane conductive properties of a novel group of synthetic ion channels containing a redox-active centre are described. Experiments using a black lipid membrane preparation revealed that these compounds function effectively as ion channels. Subsequent 23Na NMR spectroscopy studies focused on a synthesized ion channel with a ferrocene centre. When incorporated in vesicular bilayers, this channel was demonstrated to support a Na+ flux that was at least six times faster than ion transport by monensin. Since oxidation of the ferrocene moiety completely inhibited the Na+ transport, the redox-active centre provides a potential mechanism for controlling ion flux.