Luminescent amphiphilic nanogels by terpyridine-Zn(II) complexation of polymeric micelles

In this work, we investigated terpyridine (tpy)/Zn(II) complexation for the crosslinking of polymeric micelles of the branched poly(ethylene oxide)–poly(propylene oxide) block copolymer Tetronic® 1107 (T1107) in water and produce physically stable amphiphilic luminescent nanogels. Nanoparticles displayed a size of 235 ± 25 and 318 ± 57 nm before and after Zn(II) crosslinking, respectively, as measured by dynamic light scattering. High-resolution scanning electron microscopy analysis revealed the multimicellar nature of the crosslinked nanoparticles. In addition, Zn(II) complexation prevented nanoparticle disassembly after extreme dilution below the critical micellar concentration and reduced the minimum concentration required for the reverse thermal gelation of concentrated aqueous T1107 systems. The cell compatibility and uptake were initially assessed in the murine macrophage cell line RAW 264.7. Results showed that complexation increases the cell compatibility of the nanoparticles with respect to the non-complexed counterparts. In addition, non-crosslinked nanoparticles accumulated in the cell membrane, while the complexed ones were internalized, as observed by confocal laser scanning fluorescence microscopy. Then, the antiproliferative activity of the crosslinked nanoparticles was confirmed in the rhabdomyosarcoma cell line Rh30; their inhibitory concentration 50 (IC₅₀) being 101 μg/mL (6.7 μM). Finally, the encapsulation and release of the hydrophobic antiretroviral efavirenz was characterized in vitro. Complexation slightly reduced the release kinetics with respect to the pristine nanoparticles. Overall results demonstrate the promise of this simple modification strategy to produce amphiphilic nanogels with a set of advantageous physicochemical, optical, and biological properties.     

浅谈P4的生长

P_4(白磷的分子式)及其衍生物的结构是化学竞赛的热点之一。本文简介了P_4的生长,对近年与本知识相关的几道竞赛题进行了解析,并提出了几点教学建议。     

Variations in T(2)* and fat content of murine brown and white adipose tissues by chemical-shift MRI

Purpose

The purpose was to compare T₂* relaxation times and proton density fat-fraction (PDFF) values between brown (BAT) and white (WAT) adipose tissue in lean and ob/ob mice.

Materials and Methods

A group of lean male mice (n=6) and two groups of ob/ob male mice placed on similar 4-week (n=6) and 8-week (n=8) ad libitum diets were utilized. The animals were imaged at 3 T using a T₂*-corrected chemical-shift-based water–fat magnetic resonance imaging (MRI) method that provides simultaneous estimation of T₂* and PDFF on a voxel-wise basis. Regions of interest were drawn within the interscapular BAT and gonadal WAT depots on co-registered T₂* and PDFF maps. Measurements were assessed using analysis of variance, Bonferroni-adjusted t test for multigroup comparisons and the Tukey post hoc test.

Results

Significant differences (P<.01) in BAT T₂* and PDFF were observed between the lean and ob/ob groups. The ob/ob animals exhibited longer BAT T₂* and greater PDFF than lean animals. However, only BAT PDFF was significantly different (P<.01) between the two ob/ob groups. When comparing BAT to WAT within each group, T₂* and PDFF values were consistently lower in BAT than WAT (P<.01). The difference was most prominent in the lean animals. In both ob/ob groups, BAT exhibited very WAT-like appearances and properties on the MRI images.

Conclusion

T₂* and PDFF are lower in BAT than WAT. This is likely due to variations in tissue composition. The values were consistently lower in lean mice than in ob/ob mice, suggestive of the former's greater demand for BAT thermogenesis and reflective of leptin hormone deficiencies and diminished BAT metabolic activity in the latter.     

Effect of particulate filler on cell size in membranes formed via liquid–liquid thermally induced phase separation

This paper discusses the effects of adding particulate filler to a system undergoing liquid–liquid thermally induced phase separation (L–L TIPS). While much is known about the growth of droplets in L–L TIPS, little is known about the effect particular fillers have on droplet growth and the final cell size in the resulting microporous membranes. In this work, zeolite particles are shown to have a significant effect on the final cell size of these microporous membranes, the extent of which depends on the particle loading and processing conditions used to form the membrane. Two polymer–diluent–zeolite systems are reported: isotactic polypropylene–diphenyl ether and poly(methyl methacrylate)–cyclohexanol, both with zeolite 4A particles.     

Aggregation-Induced Emission by Molecular Design: A Route to High-Performance Light-Emitting Electrochemical Cells

The emission efficiency of organic semiconductors (OSCs) often suffers from aggregation caused quenching (ACQ). An elegant solution is aggregation-induced emission (AIE), which constitutes the design of the OSC so that its morphology inhibits quenching π–π interactions and non-radiative motional deactivation. The light-emitting electrochemical cell (LEC) can be sustainably fabricated, but its function depends on motion of bulky ions in proximity of the OSC. It is therefore questionable whether the AIE morphology can be retained during LEC operation. Here, we synthesize two structurally similar OSCs, which are distinguished by that 1 features ACQ while 2 delivers AIE. Interestingly, we find that the AIE-LEC significantly outperforms the ACQ-LEC. We rationalize our finding by showing that the AIE morphology remains intact during LEC operation, and that it can feature appropriately sized free-volume voids for facile ion transport and suppressed non-radiative excitonic deactivation.     

Influence of the size and the morphology of ZnO nanoparticles on cell viability

Zinc oxide has attracted wide research interest due to its unique properties. Its band gap width, high refractive index, high electrical conductivity, and high optical transmission in the visible, etc., have made it suitable for a variety of applications, such as gas sensors, varistors, optoelectronic devices, etc. The first part of the paper presents three methods for the synthesis of zinc oxide nanoparticles: sol–gel, polyol, and hydrothermal methods. Then, we report on the characteristics of the powders in terms of structure, composition and morphology as well as of in-vitro testing on cell cultures. The influence of the nanoparticles on cell viability was evaluated by the lactate dehydrogenase method. It turns out that all ZnO powders tested present high cytotoxicity. Also, it is found that the synthesis method significantly influences cell viability, the lowest one being obtained for nanopowders synthesized by the sol–gel method.     

Biodegradation-induced surface change of polymer microspheres and its influence on cell growth

Biodegradable microspheres were fabricated by poly(?-caprolactone) (PCL) homopolymer and poly(?-caprolactone-b-ethylene oxide) (PCL-b-PEO) amphiphilic block copolymer. The regulation of microsphere surface morphology was successfully achieved by controlled enzymatic degradation. The morphological changes induced by biodegradation and their influences on the growth of MG-63 human osteosarcoma cells were studied. Results based on the evaluation of cytotoxicity and the morphological observation of MG-63 cells cultivated on microspheres showed better growth of cells on the surface of degraded microspheres than on the surface of those undegraded microspheres no matter they were fabricated by homopolymers or copolymers. The influences of morphological changes of microsphere surface before and after biodegradation on MG-63 cell growth were discussed. The results of this work indicated that the biodegradation-induced morphological changes of microspheres could be well controlled and were favorable for MG-63 cell attachment and proliferation.     

Ratiometric fluorescent Zn chemosensor constructed by appending a pair of carboxamidoquinoline on 1,2-diaminocyclohexane scaffold

By appending a pair of carboxamidoquinoline pendants onto 1,2-diaminocyclohexane scaffold via N-alkylation, multifunctionalized ACAQ was designed and synthesized as a water soluble fluorescent ratiometric chemosensor for Zn²⁺. In 50% aqueous methanol buffer pH 7.4 solution, upon excitation at 316 nm, ACAQ (5 μM) displayed a selective ratiometric fluorescence changes with a shift from 410 to 490 nm in response to the interaction with Zn²⁺. After binding with 1 equiv of Zn²⁺, ACAQ exhibited a 12-fold enhancement in I₄₉₀/I₄₁₀ characterized by a clear isoemissive point at 440 nm. The metal sensor binding mode was established by Job’s plot and the combined fluorescence and ¹H NMR spectroscopic method. The selectivity of the probe toward biological relevant cations and transition metal ions was proven to be good. In addition, the interference caused by Cu²⁺ and Cd²⁺ in the quantitation of Zn²⁺ can be completely eliminated by the use of diethyldithiocarbamate as the screening agent. Exploitation of ACAQ as the sensing probe, ratiometric determination of Zn²⁺ with the limit of detection (LOD) at 28.3 nm can be realized. In addition, the unique responsive properties of the probe toward Fe³⁺ and Zn²⁺ were used to construct a fluorescent switch. The membrane permeability of ACAQ to living cells and bio-imaging of Zn²⁺ were demonstrated.