Face-Directed Assembly of Molecular Cubes: In Situ Substitution of a Predetermined Concave Cluster

Systematic design and self-assembly of metal–organic polyhedra with predictable configurations has been a long-standing challenge in crystal engineering. Herein a concave polyoxovanadate cluster, [V₆O₆(OCH₃)₉(SO₄)₄]⁵⁻, which can be generated in situ under specific reaction conditions, is reported. Based on this cluster, a potential trivalent molecular building block, [V₆O₆(OCH₃)₉(SO₄)(CO₂)₃]²⁻, can be obtained by the bridging-ligand-substitution strategy and it possesses appropriate angle information for the design of molecular cubes. Utilizing the face-directed assembly of the trivalent molecular building block and a diverse set of tetratopic carboxylate linkers, a series of metal–organic cubes ( VMOC-1 – VMOC-5 ) with the same topology but different functionalities and dimensions were designed and constructed. An inclusion study using VMOC-3 shows that they are potential molecular receptors for selective capture of size-matching polycyclic aromatic hydrocarbon guest molecules.     

The recent progress of functionally graded CNT reinforced composites and structures

In the last decade,the functionally graded carbon nanotube reinforced composites(FG-CNTRCs)have attracted considerable interest due to their excellent mechanical properties,and the structures made of FG-CNTRCs have found broad potential applications in aerospace,civil and ocean engineering,automotive industry,and smart structures.Here we review the literature regarding the mechanical analysis of bulk CNTR nanocomposites and FG-CNTRC structures,aiming to provide a clear picture of the mechanical modeling and properties of FG-CNTRCs as well as their composite structures.The review is organized as follows:(1)a brief introduction to the functionally graded materials(FGM),CNTRCs and FG-CNTRCs;(2)a literature review of the mechanical modeling methodologies and properties of bulk CNTRCs;(3)a detailed discussion on the mechanical behaviors of FG-CNTRCs;and(4)conclusions together with a suggestion of future research trends.     

An improved LC–MS/MS method for determination of docetaxel and its application to population pharmacokinetic study in Chinese cancer patients

Because of its unpredictable side effects and efficacy, the anticancer drug docetaxel (DTX) requires improved characterisation of its pharmacokinetic profiles through population pharmacokinetic studies. A sensitive and rugged LC–MS/MS method for the detection of DTX in human plasma was developed and optimised using paclitaxel as an internal standard (IS). The plasma samples underwent rapid extraction using hybrid solid-phase extraction-protein precipitation. The analyte and IS were separated with an isocratic system on a Zorbax Eclipse Plus C₁₈ column using water containing 0.05% acetic acid along with 20 μM of sodium acetate and methanol (30/70, v/v) as the mobile phase. Quantification was performed using a triple quadrupole mass spectrometer through multiple reaction monitoring in positive mode, using the m/z 830.3 → 548.8 and m/z 876.3 → 307.7 transitions for DTX and paclitaxel, respectively. The range of the calibration curve was 1–500 ng/mL for DTX, and the linear correlation coefficient was >0.99. The accuracies ranged from −4.6 to 4.2%, and the precision was no higher than 7.0% for the analytes. No significant matrix effect was observed. Both DTX and the IS showed considerable recovery. This method was finally applied to the establishment of a population pharmacokinetic model to optimise the clinical use of DTX.     

Fast Liquid Phase Epitaxial Growth for Perovskite Single Crystals

Semiconductors grown by the solution-processed method have shown low-cost,facile fabrication process and comparable performance.However,there are many reasons why it is difficult to achieve high quality films.For example,lattice constant mismatch is one of the problems when photovoltaic devices made of organ metallic perovskites.In this work,MAPbBr^{MA=CH3NH3^+}perovskites single crystals grown on the surface of MAPbBr2.5 CI0.5 perovskites single crystals via liquid epitaxial growth method is demonstrated.It is found that when the lattice constants of the two perovskite single crystals are matched,another crystal can be grown on the surface of one crystal by epitaxial growth.The whole epitaxy growth process does not require high heating temperature and long heating time.X-ray diffraction method is used to prove the lattice plane of the substrate and the epitaxial grown layer.A scanning electron microscope is used to measure the thickness of the epitaxial layer.Compared with perovskite-based photodetectors without epitaxial growth layer,perovskite-based photodetectors with epitaxial growth layer have lower dark current density and higher optical responsibility.     

Multi-reference lens-less Fourier-transform holography with a Greek-ladder sieve array

Lens-less Fourier-transform holography has been actively studied because of its simple optical structure and its single-shot recording.However,a low-contrast interferogram between the reference and object waves limits its signal to noise ratio.Here,multi-reference lens-less Fourier-transform holography with a Greek-ladder sieve array is proposed in the experiment and demonstrated effectively to improve the signal to noise ratio.The key technique in our proposed method is a Greek-ladder sieve array,which acts as not only a wave-front modulator but also a beam splitter.With advantages of the common path,single shot,and no need for a lens,this system has enormous potential in imaging and especially in extreme ultraviolet and soft X-ray holography.     

Investigation of Suzuki–Miyaura catalyst‐transfer polycondensation of AB‐type fluorene monomer using coordination‐saturated aryl Pd(II) halide complexes as initiators

Novel triarylamine‐based coordination‐saturated aryl Pd(II) halide complexes ligated by PEt₃, PCy₃, and P(o‐tol)₃ were successfully synthesized by direct oxidative addition of aryl halide to the corresponding Pd(0) precursors. Suzuki–Miyaura coupling polymerization of 2‐(7‐halide‐9,9‐dioctylfluoren‐2‐yl)?1,3,2‐dioxaborinane with these Pd(II) complexes as initiators was investigated for the synthesis of poly(fluorene)s with triarylamine end group. Pd(II) complexes with PCy₃ or P(o‐tol)₃ exhibited catalytic activity and realized the catalyst‐transfer polycondensation at 75 °C and room temperature, respectively, while the polymerization using Pd(II) catalyst ligated by PEt₃ did not proceed, which indicated that the bulky phosphine ligands could facilitate the reductive elimination and further promote the polymerization. In addition, the dimeric Pd(II) complex with P(o‐tol)₃ can convert into monomeric Pd(II) intermediate with an open coordination site, which had a higher activity. The end groups of the afforded polyfluorene were analyzed by matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry, in which the Ar/H end groups are indicative of the catalyst‐transfer polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1457–1463     

Synthesis of tertiary amine‐based pH‐responsive polymers by RAFT Polymerization

Well‐defined tertiary amine‐based pH‐responsive homopolymers and block copolymers were synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization using 4‐cyanopentanoic acid dithiobenzoate (CPAD) as the RAFT agent for homopolymers and a poly(ethylene glycol) (PEG) macro‐RAFT agent for the block copolymers. ¹H NMR and gel permeation chromatography results confirmed the successful synthesis of these homopolymers and block copolymers. Kinetics studies indicated that the formation of both the homopolymers and the block copolymers were well defined. The pKa titration experiments suggested that the homopolymers and the related block copolymers have a similar pKa. The dynamic light scattering investigation showed that all of the block copolymers underwent a sharp transition from unimers to micelles around their pKa and the hydrodynamic diameter (D_h) was not only dependent on the molecular weight but also on the composition of the block copolymers. The polymer solution of PEG‐b‐PPPDEMA formed the largest micelle compare to the PEG‐b‐PDPAEMA and PEG‐b‐PDBAEMA with a similar molecular weight. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1010–1022