Ratiometric Detection of microRNA Using Hybridization Chain Reaction and Fluorogenic Silver Nanoclusters

miRNA (miR)-155 is a potential biomarker for breast cancers. We aimed at developing a nanosensor for miR-155 detection by integrating hybridization chain reaction (HCR) and silver nanoclusters (AgNCs). HCR serves as an enzyme-free and isothermal amplification method, whereas AgNCs provide a built-in fluorogenic detection probe that could simplify the downstream analysis. The two components were integrated by adding a nucleation sequence of AgNCs to the hairpin of HCR. The working principle was based on the influence of microenvironment towards the hosted AgNCs, whereby unfolding of hairpin upon HCR has manipulated the distance between the hosted AgNCs and cytosine-rich toehold region of hairpin. As such, the dominant emission of AgNCs changed from red to yellow in the absence and presence of miR-155, enabling a ratiometric measurement of miR with high sensitivity. The limit of detection (LOD) of our HCR-AgNCs nanosensor is 1.13 fM in buffered solution. We have also tested the assay in diluted serum samples, with comparable LOD of 1.58 fM obtained. This shows the great promise of our HCR-AgNCs nanosensor for clinical application.     

煤直接液化油中混合酚的分离研究

利用分子筛择形特点，对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物，采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变，分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响，以获得高性能固相吸附剂，并将其应用于180-190℃馏分段混合酚分离。结果表明，当分子筛硅铝比为25、粒径为3-5 μm时，分子筛的孔口结构调节效果最优；当正硅酸乙酯的最小用量为0.2 mL/g时，固相吸附剂的吸附量为0.03 g/g，对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化，导致对甲酚选择性的提高。进一步采用HZSM-5（1）吸附剂对真实煤直接液化油混合酚的分离中发现，苯酚和对甲酚的选择性均达到100%。     

Polypyrrole Shell@3D‐Ni Metal Core Structured Electrodes for High‐Performance Supercapacitors

Three‐dimensional (3D) nanometal films serving as current collectors have attracted much interest recently owing to their promising application in high‐performance supercapacitors. In the process of the electrochemical reaction, the 3D structure can provide a short diffusion path for fast ion transport, and the highly conductive nanometal may serve as a backbone for facile electron transfer. In this work, a novel polypyrrole (PPy) shell@3D‐Ni‐core composite is developed to enhance the electrochemical performance of conventional PPy. With the introduction of a Ni metal core, the as‐prepared material exhibits a high specific capacitance (726 F g^?1 at a charge/discharge rate of 1 A g^?1), good rate capability (a decay of 33 % in C_sp with charge/discharge rates increasing from 1 to 20 A g^?1), and high cycle stability (only a small decrease of 4.2 % in C_sp after 1000 cycles at a scan rate of 100 mV s^?1). Furthermore, an aqueous symmetric supercapacitor device is fabricated by using the as‐prepared composite as electrodes; the device demonstrates a high energy density (≈21.2 Wh kg^?1) and superior long‐term cycle ability (only 4.4 % and 18.6 % loss in C_sp after 2000 and 5000 cycles, respectively).     

Enantiomeric Cyclic Peptides with Different Caco‐2 Permeability Suggest Carrier‐Mediated Transport

Recently, oral absorption of cyclic hexapeptides was improved by N‐methylation of their backbone amides. However, the number and position of N‐methylations or of solvent exposed NHs did not correlate to intestinal permeability, measured in a Caco‐2 model. In this study, we investigate enantiomeric pairs of three polar and two lipophilic peptides to demonstrate the participation of carrier‐mediated transporters. As expected, all the enantiomeric peptides exhibited identical lipophilicity (logD_7.4) and passive transcellular permeability determined by the parallel artificial membrane permeability assay (PAMPA). However, the enantiomeric polar peptides exhibited different Caco‐2 permeability (P_app) in both directions a–b and b–a. The same trend was observed for one of the lipophilic peptide, whereas the second lipophilic enantiomer pair showed identical Caco‐2 permeability (within the errors). These findings provide the first evidence for the involvement of carrier‐mediated transport for peptides, especially for those of polar nature.     

Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Can a Procedure for the Growth of Single-layer Graphene on Copper be used in Different Chemical Vapor Deposition Reactors?

In the last decade, catalytic chemical vapor deposition (CVD) has been intensively explored for the growth of single-layer graphene (SLG). Despite the scattering of guidelines and procedures, variables such as the surface texture/chemistry of catalyst metal foils, carbon feedstock, and growth process parameters have been well-scrutinized. Still, questions remain on how best to standardize the growth procedure. The possible correlation of procedures between different CVD setups is an example. Here, two thermal CVD reactors were explored to grow graphene on Cu foil. The design of these setups was entirely distinct, one being a “showerhead” cold-wall type, whereas the other represented the popular “tubular” hot-wall type. Upon standardizing the Cu foil surface, it was possible to develop a procedure for cm²-scale SLG growth that differed only by the carrier gas flow rate used in the two reactors.     

Tuning the Basicity of Cyano‐Containing Ionic Liquids to Improve SO2 Capture through Cyano–Sulfur Interactions

A new approach has been developed to improve SO₂ sorption by cyano‐containing ionic liquids (ILs) through tuning the basicity of ILs and cyano–sulfur interaction. Several kinds of cyano‐containing ILs with different basicity were designed, prepared, and used for SO₂ capture. The interaction between these cyano‐containing ILs and SO₂ was investigated by FTIR and NMR methods. Spectroscopic investigations and quantum chemical calculations showed that dramatic effects on SO₂ capacity originate from the basicity of the ILs and enhanced cyano–sulfur interaction. Furthermore, the captured SO₂ was easy to release by heating or bubbling N₂ through the ILs. This efficient and reversible process, achieved by tuning the basicity of ILs, is an excellent alternative to current technologies for SO₂ capture.     

Negatively Charged Metallacarborane Redox Couples with Both Members Stable to Air

The metallacarborane [3,3′‐Co(1,2‐closo‐C₂B₉H₁₁)₂]^? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E_1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C₂B₉H₇I₄)₂]^? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed.     

Selective Catalytic Isomerization of β-Pinene Oxide to Perillyl Alcohol Enhanced by Protic Tetraimidazolium Nitrate

A series of tetraimidazolium salts with different anions was prepared and applied in the isomerization of β-pinene oxide. After examining the activity of different catalysts, a remarkable enhancement of the selectivity of perillyl alcohol (47 %) was obtained over [PEimi][HNO₃]₄ under mild reaction conditions and using DMSO as the solvent. Furthermore, noncovalent interactions between solvent molecules and the catalyst were found by FT-IR spectroscopy and confirmed by computational chemistry. The homogeneous catalyst showed excellent stability and was reused up to six times without significant loss.