Pd‐Catalyzed Cycloisomerization of 4‐Aza‐1,6‐enynes to 3‐Aza‐bicyclo[4.1.0]hept‐2‐enes

A method for the synthesis of bicyclo[4.1.0]heptenes from 1,6‐enynes through Pd‐catalyzed cycloisomerization has been developed. N‐ and O‐tethered 1,6‐enynes were successfully transformed to their corresponding 3‐aza‐ and 3‐oxabicyclo[4.1.0]heptenes in reasonable‐to‐high yields using the catalysts [PdCl₂(CH₃CN)₂]/P(OPh)₃ or [Pd(maleimidate)₂(PPh₃)₂] in toluene. The computational calculations using density functional theory indicate that [PdCl₂{P(OPh)₃}] in the oxidation state Pd^II acts as the active catalyst species for the formation of 3‐azabicyclo[4.1.0]heptenes through 6‐endo‐dig cyclization.     

Synergism of cellulosic nanowhiskers and graft structure in stereocomplex-based materials: formation in solution and a stereocomplex memory study

Stereocomplexation is one of the approaches to improve polylactide's properties. Along with improving its properties, it also limits stereocomplex formation through solution and stereocomplex memory. The graft structure and presence of nanoparticles have a synergetic effect, improving the stereocomplex formation and its memory. The bio-stereocomplex-nanocomposite materials are generated by stereocomplexation of polylactide-graft-acetylated cellulosic nanowhiskers in the solution. The graft structure containing well-distributed acetylated cellulose nanowhiskers results in unusual stereocomplexation in the solution and influences the stereocomplex memory of the bio-stereocomplex-nanocomposite materials. Perfect stereocomplexes are easily obtained in a relatively short mixing time (5 min) from various solution concentrations up to 20 % (w/v). The bio-stereocomplex-nanocomposites have excellent stereocomplex memory to re-form the stereocomplex after melting, which is the main limitation of stereocomplex materials in industrial processes. This fully bio-based material is a potential ecofriendly candidate for the future.     

Thermoresponsive hybrid hydrogel of oxidized nanocellulose using a polypeptide crosslinker

Thermoresponsive hybrid nanocellulose hydrogels were prepared from a mixture of oxidized nanocellulose and elastin-like polypeptide (ELP). Positively charged ELP was used as a polymeric crosslinker for conjugation with negatively charged nanocellulose. Hydrogel formation was triggered by a simple increase in temperature, and the hydrogel was reversibly returned to the liquid phase by decreasing temperature. Surface potential measurement confirmed the electrostatic properties of oxidized nanocellulose and ELP molecules. The surface morphology of hydrogels was observed by atomic force microscopy and field emission-scanning electron microscopy. Conformational changes in the ELP/nanocellulose hybrid were characterized by circular dichroism. The ELP/nanocellulose hybrid hydrogel was noncytotoxic and suitable for encapsulating cells, indicating its potential for biomedical applications.     

Stabilization of Catalytically Active Cu+ Surface Sites on Titanium–Copper Mixed‐Oxide Films

The oxidation of CO is the archetypal heterogeneous catalytic reaction and plays a central role in the advancement of fundamental studies, the control of automobile emissions, and industrial oxidation reactions. Copper‐based catalysts were the first catalysts that were reported to enable the oxidation of CO at room temperature, but a lack of stability at the elevated reaction temperatures that are used in automobile catalytic converters, in particular the loss of the most reactive Cu⁺ cations, leads to their deactivation. Using a combined experimental and theoretical approach, it is shown how the incorporation of titanium cations in a Cu₂O film leads to the formation of a stable mixed‐metal oxide with a Cu⁺ terminated surface that is highly active for CO oxidation.     

Phosphonated Near‐Infrared Fluorophores for Biomedical Imaging of Bone

The conventional method for creating targeted contrast agents is to conjugate separate targeting and fluorophore domains. A new strategy is based on the incorporation of targeting moieties into the non‐delocalized structure of pentamethine and heptamethine indocyanines. Using the known affinity of phosphonates for bone minerals in a model system, two families of bifunctional molecules that target bone without requiring a traditional bisphosphonate are synthesized. With peak fluorescence emissions at approximately 700 or 800 nm, these molecules can be used for fluorescence‐assisted resection and exploration (FLARE) dual‐channel imaging. Longitudinal FLARE studies in mice demonstrate that phosphonated near‐infrared fluorophores remain stable in bone for over five weeks, and histological analysis confirms their incorporation into the bone matrix. Taken together, a new strategy for creating ultra‐compact, targeted near‐infrared fluorophores for various bioimaging applications is described.     

Hierarchical Self‐Assembly of Poly‐Pseudorotaxanes into Artificial Microtubules

Hierarchical self‐assembly of building blocks over multiple length scales is ubiquitous in living organisms. Microtubules are one of the principal cellular components formed by hierarchical self‐assembly of nanometer‐sized tubulin heterodimers into protofilaments, which then associate to form micron‐length‐scale, multi‐stranded tubes. This peculiar biological process is now mimicked with a fully synthetic molecule, which forms a 1:1 host‐guest complex with cucurbit[7]uril as a globular building block, and then polymerizes into linear poly‐pseudorotaxanes that associate laterally with each other in a self‐shape‐complementary manner to form a tubular structure with a length over tens of micrometers. Molecular dynamic simulations suggest that the tubular assembly consists of eight poly‐pseudorotaxanes that wind together to form a 4.5 nm wide multi‐stranded tubule.     

Simultaneous separation and determination of 20 potential adulterant antigout and antiosteoporosis pharmaceutical compounds in herbal food products using LC with electrospray ionization MS/MS and LC with quadrupole‐time‐of‐flight MS

An analytical method for the simultaneous and reliable determination of 20 antigout and antiosteoporosis pharmaceutical compounds in adulterated health food products was developed using liquid chromatography with electrospray ionization tandem mass spectrometry and liquid chromatography with quadrupole‐time‐of‐flight mass spectrometry. The method was validated through the determination of specificity, linearity, limit of detection, and limit of quantification, method detection limit, method quantitation limit, precision, accuracy, recovery, and stability. The matrix effect was also determined. The validation results of the developed method are as follows: for solid and liquid blank samples, limits of detection ranged from 0.05 to 5.00 ng/mL and limits of quantification ranged from 0.15 to 15.00 ng/mL. Linearity was acceptable, and the correlation coefficients (R²) were ≥0.99 for all target compounds. Both intra and interday precision were less than 9.16% RSD, and accuracies ranged from 95.31 to 116.68%. Mean recoveries for different types of dietary supplements classified as powders, liquids, tablets, and capsules were found to be 80.81 to 117.62% with less than 15.00% relative standard deviation. The stability of the standard mixture solution was less than 11.72% relative standard deviation after 48 h. By the proposed method, the presence of dexamethasone was determined in seized herbal food products at concentrations that ranged from 126 to 215 µg/g.     

Micellar core-shell-type acrylic-polyurethane hybrid materials with self-polishing property

Abstract

Marine fouling can be a serious problem in the shipping industry, since it increases the surface roughness of the hull and hence its frictional resistance to its movement through water. Antifouling paint can be defined as preventing the attachment of marine organisms onto surfaces. However, the most commonly used antifouling coating which is the tributyltin-based self-polishing copolymer causes the severe pollution of marine environment. Ammonium salt-based paints include tertiary amines as biocides which have effective biocidal and biodegradable properties without accumulation in the sea environment. However, ammonium salt-based coatings were too sensitive to seawater and became swollen. In this study, polyurethane-acrylic copolymers were synthesized by radical polymerization. These hybrid materials were found to form core–shell structures in aqueous media. Synthesis and properties of copolymers were investigated by Fourier transform-infrared spectrometer, proton-nuclear magnetic resonance, transmission electron microscopy, and dynamic light scattering. The polishing rate of self-polishing copolymer was determined from the reduction in dry film thickness after artificial seawater immersion under a dynamic condition.