Dynamic self-assembly of mannosylated-calix[4]arene into micelles for the delivery of hydrophobic drugs.

Carbohydrate-lectin interactions and glycol-molecule-driven self-assembly are powerful yet challenging strategies to create supramolecular nanostructures for biomedical applications. Herein, we develop a modular approach of micellization with a small molecular mannosylated-calix[4]arene synthetic core, CA4-Man3, to generate nano-micelles, CA4-Man3-NPs, which can target cancer cell surface receptors and facilitate the delivery of hydrophobic cargo. The oligomeric nature of the calix[4]arene enables the dynamic self-assembly of calix[4]arene (CA4), where an amphiphile, functionalized with mannose units (CA-glycoconjugates) in the upper rim and alkylated lower rim, afforded the CA4-Man3-NPs in a controllable manner. The presence of thiourea units between calixarene and tri-mannose moiety facilitated the formation of a stable core with bidentate hydrogen bonds, which in turn promoted mannose receptor targeted uptake and helped in the intracellular pH-responsive release of antineoplastic doxorubicin (Dox). Physiochemical features including the stability of the nanomicelle could circumvent the undesirable leakage of the cargoes, ensuring maximum therapeutic output with minimum off-targeted toxicity. Most importantly, surface-enhanced Raman scattering (SERS) was utilized for the first time to evaluate the critical micelle concentration during the formation, cellular uptake and intracellular drug release. The present study not only provides an architectural design of a new class of organic small molecular nanomicelles but also unveils a robust self-assembly approach that paves the way for the delivery of a wide range of hydrophobic chemotherapeutic drugs.

Pd-Catalyzed oxidative annulation of enamides with diazabicyclic olefins: rapid access to cyclopentene fused 2-pyrrolines.

An efficient stereoselective route for the synthesis of cyclopentene fused 2-pyrrolines has been established via a Pd-catalyzed C-H activation/oxidative coupling of aryl enamides with diazabicyclic olefins. The proposed two-stage mechanism was successfully proven by isolating the intermediate trans-disubstituted cyclopentene.

Interaction between Octenidine-based Solution and Sodium Hypochlorite: A Mass Spectroscopy, Proton Nuclear Magnetic Resonance, and Scanning Electron Microscopy-based Observational Study.

INTRODUCTION: Octenisept (OCT; Schülke & Mayr, Nordersdedt, Germany), an antimicrobial, antibiofilm agent and a promising root canal irrigant, can be potentially combined with sodium hypochlorite (NaOCl) during endodontic treatment. The aim of this study was first to identify the precipitate formed on the interaction between OCT and NaOCl and secondly to compare its effect on dentinal tubules with that of precipitate formed on combining chlorhexidine (CHX) and NaOCl. METHODS: This observational study was conducted in 3 stages. Initially, the color changes and precipitate formation were assessed when the test solution 0.1% OCT and 5.2% NaOCl were mixed. Color changes were compared with those observed when 2% CHX was mixed with 5.2% NaOCl. The residue obtained on combining OCT and NaOCl was subjected to proton nuclear magnetic resonance (1H NMR) and mass spectrometric (MS) analysis. In the final stage, dentinal surfaces irrigated alternatively with OCT and NaOCl were compared using scanning electron microscopy (SEM) with the dentinal surface irrigated with CHX and NaOCl. RESULTS: The OCT-NaOCl mixture changed in color from initial milky white to transparent over time, whereas the CHX-NaOCl mixture showed an immediate peach-brown discoloration. 1H NMR and MS analysis established that the whitish precipitate obtained on combining OCT and NaOCl solutions correlated with the structure of phenoxyethanol (PE). SEM revealed dense precipitate occluding the dentinal tubules with the CHX and NaOCl group, whereas the precipitate was sparse and partially occluded in the OCT and NaOCl group. CONCLUSIONS: The whitish precipitate formed with the OCT-NaOCl mixture was identified as PE, a compound already present in OCT, and it partly occluded the dentinal tubules.

A bentonite-gold nanohybrid as a heterogeneous green catalyst for selective oxidation of silanes.

A highly efficient, environmentally benign and reusable heterogeneous bentonite-gold nanohybrid catalyst was designed and synthesized. This heterogeneous catalyst could efficaciously catalyse the oxidation of organosilanes to silanols. The reaction is 98.7% atom economical and the products were obtained in excellent yield without the formation of disiloxanes as byproducts. The catalyst was also well applicable for the gram scale preparation of silanols.

Ethyl p-methoxycinnamate isolated from a traditional anti-tuberculosis medicinal herb inhibits drug resistant strains of Mycobacterium tuberculosis in vitro.

Many plants are used in Ayurveda for the treatment of tuberculosis. Our aim was to examine if these plants possess any specific molecule that inhibits Mycobacterium tuberculosis. One of them, Kaempferia galanga, yielded an anti-TB molecule, ethyl p-methoxycinnamate (EPMC). By resazurin microtitre assay (REMA), EPMC was shown to inhibit M. tuberculosis H37Ra, H37Rv, drug susceptible and multidrug resistant (MDR) clinical isolates (MIC 0.242-0.485mM). No cross resistance was observed to any standard anti-TB drugs in the MDR strains. The compound did not inhibit any prototype bacteria tested. EPMC seems to be a potential anti-TB lead molecule.

A new Hg(2+) -selective fluorescent sensor based on a 1,3-alternate thiacalix[4]arene anchored with four 8-quinolinoloxy groups.

A new thiacalix [4]arene derivative in a 1,3-alternate conformation bearing four quinolinoloxy groups through propyl chains has been synthesized, and its metal ion-binding and fluorescence-sensing properties were investigated in both THF and 10% H2O-THF systems. The designed ligand exhibited pronounced Hg2+ -selective on-off type fluoroionophoric properties among the representative transition and heavy metal ions including Cu2+. The detection limit for Hg2+ was found to be 2.0 x 10(-6) M in the mixed H2O-THF system. Detailed spectral studies including 1H NMR and MALDI-TOF mass spectroscopy reveal the unusual formation of a tetramercury complex with the ligand, in which the four propyl arms containing the quinolinoloxy groups adopt a "tetrapodand" conformation enclosing one Hg2+ ion each in the four cavities thus formed.

The three-component reaction of dicarbomethoxycarbene, aldehydes, and beta-nitrostyrenes: a stereoselective synthesis of substituted tetrahydrofurans.

The Rh(II)-catalyzed reaction of dimethyl diazomalonate with aryl aldehydes and beta-nitrostyrenes results in the formation of highly substituted tetrahydrofurans. The reaction may be considered to involve the Huisgen dipolar cycloaddition of the carbonyl ylide, generated from the dicarbomethoxycarbene and the aldehyde, to the beta-nitrostyrene. The diastereoselectivity of the reaction may be attributed to the concerted nature of the carbonyl ylide cycloaddition.