Total Synthesis of (+)‐β‐Himachalene

An enantioselective synthesis of (+)‐β‐himachalene ( 2 ) was accomplished starting from (1S,2R)‐1,2‐epoxy‐p‐menth‐8‐ene ( 3 ) in 15 or 16 steps with an overall yield of ca. 6% (Schemes 3, 5, and 6). Key transformations include an Ireland–Claisen rearrangement, a Corey oxidative cyclization, and a ring expansion.     

CIDEP studies of the photolysis of the lignin model compound α-guaiacoxylacetoveratrone: the role of triplet reactions in aqueous and hydroxylic solvents

Free radical reactions induced by the photolysis of the lignin model compound α-guaiacoxylacetoveratrone have been studied by conventional and time-resolved ESR spectroscopy. In the presence of efficient hydrogen donors such as aqueous and hydroxylic solvents the primary reaction involves photoreduction of the triplet phenacyl ether to form the ketyl radical followed by rapid cleavage to the phenacyl radical and guaiacol. Subsequent formation of polarized guaiacoxyl radicals is due to secondary photo-oxidation. The cleavage of the ketyl radical is retarded in basic media and accelerated in acetic acid. Minor reaction pathways involving excited singlets cannot be ruled out by the current CIDEP observations.     

Non-covalent reconfigurable microgel colloidosomes with a well-defined bilayer shell

Microgels are extremely interfacially active and are widely used to stabilize emulsions. However, they are commonly used to stabilize oil-in-water emulsions due to their intrinsic hydrophilicity and initially dispersed in water. In addition, there have been no attempts to control microgel structural layers that are formed at the interface and as a result it limits applications of microgel in advanced materials. Here, we show that by introducing octanol into poly(N-isopropylacrylamide-co-methacrylic acid) (PNIPAM-co-MAA) microgels, octanol-swollen microgels can rapidly diffuse from the initially dispersed oil phase onto the water droplet surface. This facilitates the formation of microgel-laden interfacial layers with strong elastic responses and also generates stable inverse water-in-oil Pickering emulsions. These emulsions can be used as templates to produce microgel colloidosomes, herein termed ‘microgelsomes’, with shells that can be fine-tuned from a particle monolayer to a well-defined bilayer. The microgelsomes can then be used to encapsulate and/or anchor nanoparticles, proteins, vitamin C, bio-based nanocrystals or enzymes. Moreover, the programmed release of these substances can be achieved by using ethanol as a trigger to mediate shell permeability. Thus, these reconfigurable microgelsomes with a microgel-bilayer shell can respond to external stimuli and demonstrate tailored properties, which offers novel insights into microgels and promise wider application of Pickering emulsions stabilized by soft colloids.

Inverse W/O Pickering emulsions and reconfigurable microgelsomes with a well-defined bilayer structure are prepared from octanol-swollen PNIPAM-co-MAA microgels and the combination of binary microgels, which promise wider application of soft colloids.     

Determination of Diuretics in Urine Using Immobilized Multi‐Walled Carbon Nanotubes in Hollow Fiber Liquid‐Phase Microextraction Combined with Liquid Chromatography‐Tandem Mass Spectrometry

A novel technique utilizing the adsorptive potential of immobilized multi‐walled carbon nanotubes (I‐MWCNT) in hollow fiber liquid‐phase microextraction (HF‐LPME) was developed for the determination of diuretics in urine. In this study, the potential of carbon nanotubes as a sorbent for three‐phase liquid‐phase microextraction of diuretics from urine samples was evaluated. Analysis was performed using liquid chromatography‐tandem mass spectrometry (LC‐MS/MS). A novel method was applied to detect acetazolamide (AAA), chlorothiazide (CTA), hydrochlorothiazide (HCT), hydroflumethiazide (HFT), clopamide (CA), trichlormethiazide (TCM), althiazide (AT) and bendroflumethiazide (BFT) in urine. Two‐step extractions using different times and temperatures for each step were adopted. Parameters influencing the extraction efficiency, including the extraction solvent, sample pH, salt concentration, extraction time and extraction temperature were systematically optimized. Under the resulting optimal extraction conditions, this method showed good linearity over an analytes concentration range of 1 to 1000 ng/mL, high extraction repeatability with relative standard deviations of less than 6%, and low detection limits (0.09 to 0.51 ng/mL). The application of the methods to the determination of diuretics in real samples was tested by analyzing urine samples of patient.     

Halogen-Bonding Strapped Porphyrin BODIPY Rotaxanes for Dual Optical and Electrochemical Anion Sensing

Anion receptors employing two distinct sensory mechanisms are rare. Herein, we report the first examples of halogen-bonding porphyrin BODIPY [2]rotaxanes capable of both fluorescent and redox electrochemical sensing of anions. ¹H NMR, UV/visible and electrochemical studies revealed rotaxane axle triazole group coordination to the zinc(II) metalloporphyrin-containing macrocycle component, serves to preorganise the rotaxane binding cavity and dramatically enhances anion binding affinities. Mechanically bonded, integrated-axle BODIPY and macrocycle strapped metalloporphyrin motifs enable the anion recognition event to be sensed by the significant quenching of the BODIPY fluorophore and cathodic perturbations of the metalloporphyrin P/P^+. redox couple.     

Theoretical investigation of the molecular structure,vibrational spectra,and molecular docking of tramadol using density functional theory

The optimized molecular structures, harmonic vibrational wavenumbers, and the corresponding vibrational assignments of (1S,2S)-tramadol and (1R,2R)-tramadol are computationally examined using the B3LYP density functional theory method together with the standard 6–311++G(d,p) and def2-TVZP basis sets. The optimized structures show that phenolic rings of both 1R,2R and 1S,2S tramadol adopt planar geometry, which are slightly distorted due to the substitution at the meta-position; and the six-membered cyclohexane adopts a slightly distorted chair conformation. The 1S,2S enantiomer is energetically more favorable than 1R,2R with the energy differences of 1.32 and 1.03 kcal/mol obtained at B3LYP/6–311++G(d,p) and B3LYP/Def2-TVZP levels, respectively. The analysis of the binding pocket in the silico molecular docking with the m-opioid receptor shows that it originated two clusters with the 1S,2S enantiomer and one cluster with the 1R,2R enantiomer of tramadol. The results point to a more stable complex of the m-opioid receptor with the 1R,2R enantiomer of tramadol.     

Chemical Antibody Mimics Inhibit Cadherin-Mediated Cell–Cell Adhesion: A Promising Strategy for Cancer Therapy

One of the most promising strategies to treat cancer is the use of therapeutic antibodies that disrupt cell–cell adhesion mediated by dysregulated cadherins. The principal site where cell–cell adhesion occurs encompasses Trp2 found at the N-terminal region of the protein. Herein, we employed the naturally exposed highly conserved peptide Asp1-Trp2-Val3-Ile4-Pro5-Pro6-Ile7, as epitope to prepare molecularly imprinted polymer nanoparticles (MIP-NPs) to recognize cadherins. Since MIP-NPs target the site responsible for adhesion, they were more potent than commercially available therapeutic antibodies for inhibiting cell–cell adhesion in cell aggregation assays, and for completely disrupting three-dimensional tumor spheroids as well as inhibiting invasion of HeLa cells. These biocompatible supramolecular anti-adhesives may potentially be used as immunotherapeutic or sensitizing agents to enhance antitumor effects of chemotherapy.     

Iron‐Catalyzed Highly Enantioselective cis‐Dihydroxylation of Trisubstituted Alkenes with Aqueous H2O2

Reliable methods for enantioselective cis‐dihydroxylation of trisubstituted alkenes are scarce. The iron(II) complex cis‐α‐[Fe^II(2‐Me₂‐BQPN)(OTf)₂], which bears a tetradentate N₄ ligand (Me₂‐BQPN=(R,R)‐N,N′‐dimethyl‐N,N′‐bis(2‐methylquinolin‐8‐yl)‐1,2‐diphenylethane‐1,2‐diamine), was prepared and characterized. With this complex as the catalyst, a broad range of trisubstituted electron‐deficient alkenes were efficiently oxidized to chiral cis‐diols in yields of up to 98 % and up to 99.9 % ee when using hydrogen peroxide (H₂O₂) as oxidant under mild conditions. Experimental studies (including ¹⁸O‐labeling, ESI‐MS, NMR, EPR, and UV/Vis analyses) and DFT calculations were performed to gain mechanistic insight, which suggested possible involvement of a chiral cis‐Fe^V(O)₂ reaction intermediate as an active oxidant. This cis‐[Fe^II(chiral N₄ ligand)]²⁺/H₂O₂ method could be a viable green alternative/complement to the existing OsO₄‐based methods for asymmetric alkene dihydroxylation reactions.     

Measurement of στ product of solid state laser materials by an alternative method: Application to Nd3+ doped YVO4 crystal for 4 F 3/2→4 I 11/2 transition

In this paper an alternative approach for measurement of στ product for ⁴ F _3/2→⁴ I _11/2 transition of Nd³⁺ doped YVO₄ crystal is reported. In this method a microchip laser is formed by keeping a small piece of the sample in plane-plane resonator and a diode laser (808 nm) is used for pumping. The pump power induced thermal lensing effect is used to make the cavity stable. The cavity mode area is estimated by measuring the thermal lens focal length at the threshold and the average pump area is measured by Gaussian fit to the intensity profiles of the pump beam. The value of στ product of Nd:YVO₄ crystal obtained by this method is within 10% of the reported values. The advantage of this method is that it is a simple method for direct measurement of στ product of laser crystals.     

Raman spectra of crystalline iron perchlorate hexahydrate

Raman studies of crystalline iron perchlorate hexahydrate (Fe(ClO₄)₂·6H₂O) in the region of lattice and anion internal modes were carried out in the temperature range 80–385 K. The temperature‐dependent Raman results are consistent with those from previous works, showing that two phase transitions occur around 336 and 245 K. The transition at 336 K may be considered as an order–disorder transformation, while the one at 245 K is associated with the configurational disorder of the tetrahedron of the perchlorate ions. Copyright © 2008 John Wiley & Sons, Ltd.