Dendritic polyurethane-based prodrug as unimolecular micelles for precise ultrasound-activated localized drug delivery

Ultrasound has been recognized as an exciting tool to enhance the therapeutic efficacy in tumor chemotherapy owing to the triggered drug release, facilitated intracellular drug delivery, and improved spatial precision. Aiming for a precise localized drug delivery, novel dendritic polyurethane-based prodrug (DOX-DPU-PEG) was fabricated with a drug content of 18.9% here by conjugating DOX onto the end groups of the functionalized dendritic polyurethane via acid-labile imine bonds. It could easily form unimolecular micelles around 38 nm. Compared with the non-covalently drug-loaded unimolecular micelles (DOX@Ph-DPU-PEG), they showed excellent pH/ultrasound dual-triggered drug release performance, with drug leakage of only 4% at pH 7.4, but cumulative release of 14% and 88% at pH 5.0 without and with ultrasound, respectively. The ultrasound responsiveness was attributed to the unique strawberry-shaped topological structure of the DOX-DPU-PEG, in which DOX was embedded in the skin layer of the hydrophobic DPU cores. With ultrasound, the DOX-DPU-PEG unimolecular micelles possessed enhanced tumor growth inhibition than free DOX but showed no obvious cytotoxicity on the tumor cells without ultrasound. Such feature makes them promising potential for precise localized drug delivery.     

石墨基液流电池复合双极板

液流电池是一种安全性高、使用寿命长、可扩展的大规模储能系统,可以协助电网调峰储能,提高能源利用率,发展前景广阔。双极板是液流电池的重要组成部分。功能上起到了分隔、串联电池、传导电流、为电堆提供结构支撑等作用。从成本构成角度看,双极板的价格占电堆成本的比重也较大。开发高性能、低成本的双极板对加快液流电池的商业化应用具有重要意义,也是目前业界的迫切需求。虽然文献上报道了许多针对液流电池双极板开发的工作,但是目前高性能、低成本的液流电池双极板产品仍无法充分满足市场需求。本文着重介绍了石墨基复合双极板的研究现状,介绍了材料选择、工艺流程对关键性能的影响,对相关工作进行了评述,并为液流电池双极板的开发提出了建议。     

Characterization and gas adsorption of a novel three‐dimensional metal–organic framework (MOF) generated from a new polydentate fluorene‐bridged ligand

A polydentate ligand bridged by a fluorene group, namely 9,9‐bis(2‐hydroxyethyl)‐2,7‐bis(pyridin‐4‐yl)fluorene (L), has been prepared under solvothermal conditions in acetonitrile. Crystals of the three‐dimensional metal–organic framework (MOF) poly[[[μ₃‐9,9‐bis(2‐hydroxyethyl)‐2,7‐bis(pyridin‐4‐yl)fluorene‐κ³N:N′:O]bis(methanol‐κO)(μ‐sulfato‐κ²O:O′)nickel(II)] methanol disolvate], {[Ni(SO₄)(C₂₇H₂₄N₂O₂)(CH₃OH)]·2CH₃OH}_n, (I), were obtained by the solvothermal reaction of L and NiSO₄ in methanol. The ligand L forms a two‐dimensional network in the crystallographic bc plane via two groups of O—H…N hydrogen bonds and neighbouring two‐dimensional planes are completely parallel and stack to form a three‐dimensional structure. In (I), the Ni^II ions are linked by sulfate ions through Ni—O bonds to form inorganic chains and these Ni‐containing chains are linked into a three‐dimensional framework via Ni—O and Ni—N bonds involving the polydentate ligand L. With one of the hydroxy groups of L coordinating to the Ni^II atom, the torsion angle of the hydroxyethyl group changes from that of the uncoordinated molecule. In addition, the adsorption properties of (I) with carbon dioxide were investigated.     

Fabrication of an ionic‐liquid‐based polymer monolithic column and its application in the fractionation of proteins from complex biosamples

An ionic‐liquid‐based polymer monolithic column was synthesized by free radical polymerization within the confines of a stainless‐steel column (50 mm × 4.6 mm id). In the processes, ionic liquid and stearyl methacrylate were used as dual monomers, ethylene glycol dimethacrylate as the cross‐linking agent, and polyethylene glycol 200 and isopropanol as co‐porogens. Effects of the prepolymerization solution components on the properties of the resulting monoliths were studied in detail. Scanning electron microscopy, nitrogen adsorption–desorption measurements, and mercury intrusion porosimetry were used to investigate the morphology and pore size distribution of the prepared monoliths, which showed that the homemade ionic‐liquid‐based monolith column possessed a relatively uniform macropore structure with a total macropore specific surface area of 44.72 m²/g. Compared to a non‐ionic‐liquid‐based monolith prepared under the same conditions, the ionic‐liquid‐based monolith exhibited excellent selectivity and high performance for separating proteins from complex biosamples, such as egg white, snailase, bovine serum albumin digest solution, human plasma, etc., indicating promising applications in the fractionation and analysis of proteins from the complex biosamples in proteomics research.     

An organoantimony nitrate complex with azastibocine framework as water tolerant Lewis acid catalyst for the synthesis of 1,2-disubstitued benzimidazoles

A novel organoantimony complex of 6-cyclohexyl-6,7-dihydrodibenzo[c,f] [1,5]azastibocin-12(5H)-yl nitrate ( 2 ) was synthesized and systematically characterized by techniques such as NMR spectra, TG-DSC, and X-ray diffraction. It was found that the complex 2 exhibits relatively strong Lewis acidity (3.3 < Ho ≤ 4.8) and could be employed as a water tolerant Lewis acid catalyst for the synthesis of synthetically valuable benzimidazole derivatives starting from aldehydes and arylenediamines. This catalytic system shows excellent tolerance toward a wide variety of functional groups, such as methyl, methoxyl, fluoro, chloro, bromo, nitro, cyan, trifluoromethyl, 1-naphthaldehyde, furfural and n-butyl, together with facile reusability in 5 times scale enlarged synthesis.     

Interaction between the end groups and the main chain of conjugated polymers by time-resolved EPR and fluorescence spectroscopy

ABSTRACT

Interaction between a zinc porphyrin (ZnPor) as the end-group and poly(9,9-di-n-octylfluorene-2,7-vinylene) (PFV) as the main chain in a porphyrin end-modified fluorescent conjugated polymer, ZnPFV, was studied by time-resolved electron paramagnetic resonance (EPR) and fluorescence spectroscopy. While fluorescence from the PFV part of ZnPFV showed a spectral profile almost identical to that of a PFV oligomer without end-modification, the emission spectrum of the ZnPor part exhibited a much broader profile compared to that of the reference zinc porphyrin monomer. Based on the analysis of lifetimes and quantum yields, it was found that radiative rate constant of the ZnPor part was enhanced by nearly three times. The observed unusual enhancement in the radiative rate constant was rationalised in terms of a partial π-conjugation between the end group and the main chain, as a result of co-planarisation in fluid solution. On the other hand, the time-resolved EPR spectrum of ZnPFV at 100?K basically showed a similar spectral pattern to that of the reference zinc porphyrin, but with significant differences in zero-field spitting parameters and initial population ratios. The π-system of the excited triplet state is deduced to deviate from D_4h symmetry in the end zinc porphyrin groups. The obtained results show that interaction of the porphyrin end group with the main chain of the polymer significantly influences the excited singlet state properties of the porphyrin, while its triplet state properties were affected to a lesser extent.     

Covalent Attachment of Fibronectin onto Emulsion‐Templated Porous Polymer Scaffolds Enhances Human Endometrial Stromal Cell Adhesion,Infiltration, and Function

A novel strategy for the surface functionalization of emulsion‐templated highly porous (polyHIPE) materials as well as its application to in vitro 3D cell culture is presented. A heterobifunctional linker that consists of an amine‐reactive N‐hydroxysuccinimide ester and a photoactivatable nitrophenyl azide, N‐sulfosuccinimidyl‐6‐(4′‐azido‐2′‐nitrophenylamino)hexanoate (sulfo‐SANPAH), is utilized to functionalize polyHIPE surfaces. The ability to conjugate a range of compounds (6‐aminofluorescein, heptafluorobutylamine, poly(ethylene glycol) bis‐amine, and fibronectin) to the polyHIPE surface is demonstrated using fluorescence imaging, FTIR spectroscopy, and X‐ray photoelectron spectroscopy. Compared to other existing surface functionalization methods for polyHIPE materials, this approach is facile, efficient, versatile, and benign. It can also be used to attach biomolecules to polyHIPE surfaces including cell adhesion‐promoting extracellular matrix proteins. Cell culture experiments demonstrated that the fibronectin‐conjugated polyHIPE scaffolds improve the adhesion and function of primary human endometrial stromal cells. It is believed that this approach can be employed to produce the next generation of polyHIPE scaffolds with tailored surface functionality, enhancing their application in 3D cell culture and tissue engineering whilst broadening the scope of applications to a wider range of cell types.     

Polymer complexes. LXXVI. Synthesis,characterization, CT‐DNA binding,molecular docking and thermal studies of sulfoxine polymer complexes

Novel polymer complexes of 8‐hydroxyquinoline‐5‐sulfonic acid hydrate ( H ₂ L ) with Cu²⁺, Co²⁺ and Ni²⁺ chloride were prepared and characterized. Microanalysis, magnetic susceptibility, IR spectra, electron spin resonance, mass spectra, X‐ray, molar conductance, thermal, and UV–Vis spectra studies have been used to confirm the structure of the prepared polymer complexes. The molecular and electronic structures of the hydrogen bond conformers for ligand ( H ₂ L ) were optimized theoretically and the quantum chemical parameters were calculated. On the basis of elemental and IR data, the chemical structure of metal chelates commensurate that the tri‐dentate (H₂L) coordinate to metal chlorides through oxygen atom of phenolic OH and oxygen atom of SO₃‐H group by replacing H atoms and nitrogen of the quinoline ring. The magnetic studies suggested the octahedral geometrical structure for all produced polymer complexes with general formula {[ML (OH₂)₃] .xH₂O}_n (M = Cu²⁺, x = 1.; Co²⁺, x = 2 and Ni²⁺, x = 2) in molar ratio (1:1). Coats–Redfern and Horowitz–Metzger methods have been used for calculating the activation thermodynamic parameters of the thermal decomposition for H ₂ L and its polymer complexes. The interaction between H ₂ L and its transition metal complexes with the calf thymus DNA (CT‐DNA) was determined by UV–Vis spectra. Binding efficiency between H ₂ L with the receptors of the prostate cancer (PDB code 2Q7L Hormone) and the breast cancer (PDB code 1JNX Gene regulation) was studied by molecular docking. The inhibition behaviour of H ₂ L against the corrosion of carbon steel / HCl (2 M) solution was studied by weight loss, Tafel polarisation, electrochemical impedance spectroscopy (EIS) and electrochemical frequency modulation (EFM) techniques. The adsorption isotherm was found to be Friendlish isotherm. The morphology of inhibited carbon steel? s surface was studied using scanning electron microscope (SEM) and energy dispersive X‐ray spectroscopy (EDS).     

Melting thermodynamics of oligonucleic acids conjugated with relatively solvophobic linear polymers: A coarse‐grained molecular simulation study

Oligonucleic acids (ONAs), such as DNA and RNA, are used in various biotechnology and nanotechnology applications due to their ability to form a double helix that is stable at low temperature and melts at high temperatures. The melting temperature (T_m) of ONA duplexes can be tuned by the ONA composition, sequence, length and concentration, solvent quality, and salt concentration and by conjugation to other macromolecules. In this article, we use coarse‐grained (CG) molecular simulations to study ONAs conjugated with linear homopolymers that are relatively more solvophobic than the ONA. We study charged and stiff 8‐mer ONAs (e.g., DNA) and neutral and flexible 8‐mer ONAs (e.g., peptide nucleic acids or PNA), and vary the composition (or G‐C content) and sequence of ONA, conjugated homopolymer lengths and solvent quality for the polymer. For neutral and flexible ONAs, as the solvent quality worsens for the polymer, the ONA melting temperature increases from that of unconjugated ONA. The melting curves broaden with polymer length and worsening solvent quality, especially for ONAs with higher G‐C content. For charged and stiff ONAs, as the solvent quality worsens, the ONA melting temperature decreases compared to unconjugated ONA while the width of the melting curve remains the same. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1196–1208     

A chlorinated non-fullerene acceptor for efficient polymer solar cells

Improving the performance and reducing the manufacturing costs are the main directions for the development of organic solar cells in the future. Here, the strategy that uses chemical structure modification to optimize the photoelectric properties is reported. A new narrow bandgap (1.30 eV) chlorinated non-fullerene electron acceptor (Y15), based on benzo[d][1,2,3] triazole with two 3-undecyl-thieno[2′,3′:4,5] thieno[3,2-b] pyrrole fused -7-heterocyclic ring, with absorption edge extending to the near-infrared (NIR) region, namely A-DA'D-A type structure, is designed and synthesized. Its electrochemical and optoelectronic properties are systematically investigated. Benefitting from its NIR light harvesting, the fabricated photovoltaic devices based on Y15 deliver a high power conversion efficiency (PCE) of 14.13%, when blending with a wide bandgap polymer donor PM6. Our results show that the A-DA'D-A type molecular design and application of near-infrared electron acceptors have the potential to further improve the PCE of polymer solar cells (PSCs).