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We report the hydrophobicity-enhanced reactivity of Cu2+ ions as an ester hydrolase.

A well-defined discoidal bicelle composed of three lipids, specifically zwitterionic long-chain 1,2‑dipalmitoyl phosphocholine (DPPC) and short-chain 1,2‑dihexanoyl phosphocholine (DHPC) doped with anionic 1,2‑dipalmitoyl phosphoglycerol (DPPG) provides a generalized template for the synthesis of hydrophobic polymer nano-rings. The lipid molar ratio of DPPC/DHPC/DPPG is 0.71/0.25/0.04. The detailed investigation and discussion were based on styrene but tested on three other vinyl monomers.The structure of nano-rings is identified through the detailed analysis of small angle X-ray/neutron scattering (SAXS and SANS) data and transmission electron micrographs (TEM), supported by the differential scanning calorimetric (DSC) data before and after polymerization. The investigation covers samples with a styrene-to-lipid ratio ranged varied from 1:50 to 1:10.The styrene monomers are initially located at both the discoidal planar (long-chain lipid rich) and rim (short-chain lipid rich) regions. During polymerization, they migrate to the more fluid rim regionsection. The formation mechanism involves the interplay of hydrophobic interaction, mismatched miscibility of polystyrene between the ordered and disordered phases, and crystallinity of the long lipid acyl chains. This facile synthesis is proven applicable for several hydrophobic monomers. The well-defined nano-rings greatly enhance the interfacial area and have the potential to be the building blocks for functional materials, if monomers are incorporated with desirable functions, for future applications.

Manipulating molecular and supramolecular interactions within cellulose nanocrystals (CNCs) to introduce different levels of assemblies combined with multiple functionalities is required for the development of degradable smart materials from renewable resources. To attain hierarchical structures and stimuli-responsive properties, a new class of liquid crystalline cellulosic hybrid materials is synthesized. Herein, main-chain rigid-rod-like oxidized cellulose (CNC-COOH) is prepared from a Cellulose Whatman filter paper (Cellulose W.P.) by acid hydrolysis and oxidized using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO). Thermotropic LC molecule, 4-cyano-4'-hydroxybiphenyl with a 12-methylene spacer (CB12-OH) is grafted onto the carboxylic acid group of CNC-COOH

Control of polymer assemblies in solution is of great importance to determine the properties and applications of these polymer nanostructures. We report a novel co-self-assembly strategy to control the self-assembly outcomes of a micelle-forming amphiphilic block copolymer (BCP) of poly(ethylene oxide) (PEO) and poly[3-(trimethoxysilyl)propyl methacrylate] (PTMSPMA), PEO114-b-PTMSPMA228. With a reactive and hydrophobic additive tetraethyl orthosilicate (TEOS), the assembly nanostructures of PEO114-b-PTMSPMA228 are tunable. The swelling of the PTMSPMA block by hydrophobic TEOS increases the hydrophobic-to-hydrophilic ratio that enables a continuous morphological evolution from spherical micelles to vesicles and eventually to large compound vesicles. TEOS that co-hydrolyzes with the PTMSPMA block can further stabilize and fix these hybrid nanostructures. With high TEOS concentrations, these polymer assemblies can be further converted through thermal annealing into unique silica nanomaterials, including nanospheres, hollow nanoparticles with dual shells, and mesoporous silica frameworks that cannot be synthesized through conventional syntheses otherwise.

The rupture of a pyogenic liver abscess (PLA) with peritonitis is a rare occurrence but a surgical emergency with a high mortality rate in the case of gas-forming PLA. Rare cases of ruptured PLA that recovered completely with only medical treatment have been reported. This paper reports a case of a large PLA rupture with peritonitis. In this case, surgical intervention was too risky because of the patient’s age and poor general condition. The patient recovered fully with appropriate antibiotic therapy and sufficient percutaneous drainage. Therefore, medical treatment may be considered an alternative option in cases of a ruptured large PLA with peritonitis if surgical intervention is too risky.

Antimicrobial pentatopic 2,2’:6’,2”-terpyridines that form 3-D supramolecular hexagonal prisms with Cd(2+) through coordination driven self-assembly, can be entrapped by lipid discoidal bicelles, composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, 1,2-dihexanoyl-sn-glycero-3-phosphocholine and 1,2-dipalmitoyl-sn-glycero-3-phospho-(1’-rac-glycerol) lipid, forming a well-defined nanocomplex. Structural characterization performed by very small angle neutron scattering, small angle X-ray scattering and transmission electron microscopy suggests that the hexagonal prisms preferably locate at the rim of bicellar discs with the hexagonal face in parallel with the bilayers, instead of face-to-face stacking. Such a configuration reduces the π–π interaction and consequently enhances the fluorescence emission. Since the novel supramolecule was reported to have antibiotic functions, this study provides the insight to the interactions of antimicrobial supermolecules with lipid membranes, leading to potential theranostic applications.

We report a new design of polymer-patched gold nanoparticles (AuNPs) with controllable interparticle interactions in terms of their direction and strength. Patchy AuNPs (pAuNPs) are prepared through hydrophobicity-driven surface dewetting under deficient ligand exchange conditions. Using the exposed surface on pAuNPs as seeds, a highly controllable growth of AuNPs is carried out

In this study, we established a feasible strategy to construct a new type of metallo-polymer with helicoidal structure through the combination of covalent polymerization and intramolecular coordination-driven self-assembly. In the design, a tetratopic monomer (M) was prepared with two terminal alkynes in the outer rim for polymerization, and two terpyridines (TPYs) in the inner rim for subsequent folding by selective intramolecular coordination. Then, the linear covalent polymer (P) was synthesized by polymerization of M via Glaser-Hay homocoupling reaction. Finally, intramolecular coordination interactions between TPYs and Zn(II) folded the backbone of P into a right- or left-handed metallo-helicoid (H) with double rims. Owing to multiple positive charges on the inner rim of helicoid, double-stranded DNA molecules (dsDNA) could interact with H through electrostatic interactions. Remarkably, dsDNA allowed exclusive formation of H with right handedness by means of chiral induction.

Peptide nucleic acids (PNAs) are nucleic acid analogs with superior hybridization properties and enzymatic stability than deoxyribonucleic acid (DNA). In addition to gene targeting applications, PNAs have garnered significant attention as bio-polymer due to the Watson-Crick -based molecular recognition and flexibility of synthesis. Here, we engineered PNA amphiphiles using chemically modified gamma PNA (8 mer in length) containing hydrophilic diethylene glycol units at the gamma position and covalently conjugated lauric acid (C12) as a hydrophobic moiety. Gamma PNA (γPNA) amphiphiles self-assemble into spherical vesicles. Further, we formulate nano-assemblies using the amphiphilic γPNA as a polymer via ethanol injection-based protocols. We perform comprehensive head-on comparison of the physicochemical and cellular uptake properties of PNA derived self- and nano-assemblies. Small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS) analysis reveal ellipsoidal morphology of γPNA nano-assemblies that results in superior cellular delivery compate to the spherical self-assembly. Next, we compare the functional activities of γPNA self-and nano-assemblies in lymphoma cells via multiple endpoints, including gene expression, cell viability, and apoptosis-based assays. Overall, we establish that γPNA amphiphile is a functionally active bio-polymer to formulate nano-assemblies for a wide range of biomedical applications.

Three dimensional (3D) supramolecules with giant cavities are attractive due to their wide range of applications. Herein, we used pentatopic terpyridine ligands with three types of coordination moieties to assemble two giant supramolecular hexagonal prisms with a molecular weight up to 42 608 and 43 569 Da, respectively. Within the prisms, two double-rimmed Kandinsky Circles serve as the base surfaces as well as the templates for assisting the self-sorting during the self-assembly. Additionally, hierarchical self-assembly of these supramolecular prisms into tubular-like nanostructures was fully studied by scanning tunneling microscopy (STM) and small-angle X-ray scattering (SAXS). Finally, these supramolecular prisms show good antimicrobial activities against Gram-positive pathogen methicillin-resistant Staphylococcus aureus (MRSA) and Bacillus subtilis (B. subtilis).

A key challenge to the development of polymer-based organic solar cells is the issue of long-term stability, which is mainly caused by the unstable time-dependent morphology of active layers. In this study, poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl C60-butyric acid methyl ester (PCBM) blend is used as a model system to demonstrate that the long-term stability of power conversion efficiency can be significantly improved by the addition of a small amount of amorphous regiorandom P3HT into semicrystalline regioregular one. The optical properties measured by UV–vis absorption and photoluminescence reveal that regiorandom P3HT can intimately mix with PCBM and prevent the segregation of PCBM. In addition, X-ray scattering techniques were adopted to evidence the retardation of phase separation between P3HT and PCBM when regiorandom P3HT is added, which is further confirmed by optical microscopy that shows a reduction of large PCBM crystals after annealing at high temperature in the presence of regiorandom P3HT. The improvement of the long-term stability is attributed to the capability of amorphous P3HT to be thermodynamically miscible with PCBM, which allows the active layer to form a more stable structure that evolves slower and hence decelerates the device decay. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016

A tailor-made donor–π–acceptor copolymer comprising of a medium electron-donating alkylthienyl-benzodithiophene (BDTT) moiety and a strong electron-accepting fluorinated thienyl-quinoxaline (TTFQ) segment with thiophene π-bridge units has been synthesized by Stille coupling polymerization and thoroughly characterized for use as a p-type semiconducting polymer. The semicrystalline copolymer PBDTT-TTFQ shows a broad visible-near-infrared absorption band with an optical bandgap of 1.67 eV and possesses a relatively low-lying HOMO level at −5.34 eV. In addition, the PBDTT-TTFQ neat film reveals a highly dense fibrillar nanostructure with a certain degree of long-range order, suggesting the nanoscale self-assembly of PBDTT and TTFQ segments. A bulk-heterojunction polymer solar cell based on the blend of 1 : 1 PBDTT-TTFQ:PC71BM shows an open circuit voltage of 0.75 V, a short circuit current density of 14.6 mA cm−2, and a fill factor of 56.1%, achieving a power conversion efficiency of 6.1% under the illumination of AM 1.5G, 100 mW cm−2. The results unambiguously indicate that the PBDTT-TTFQ is an auspicious candidate for next-generation solar cell materials.