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Hyperbilirubinemia caused severe hepatobiliary diseases with various causes, especially hepatic fibrosis and cirrhosis caused by end-stage hepatitis B and C. Plasma adsorption perfusion (PP) has a tremendous advantage in treating patients with hyperbilirubinemia and liver failure, wherein, a safe and effective adsorbent is the key to filter out bilirubin successfully in PP. In this work, a simple engineering strategy, a new porous polymer adsorption resin ERM-0100 based on the homopolymer predispersion system, is proposed to produce high-performance bilirubin adsorbents. Preliminary experimental results show that ERM-0100 exhibits a large surface area and uniformly porous structure. Experimental results verify that ERM-0100 has high biocompatibility and bilirubin adsorption efficiency (TBIL:35%, direct bilirubin [DBIL]:30%, IBIL:87%) that is significantly higher than most of the reported adsorbents. Animal experiments prove that ERM-0100 has high bilirubin adsorption efficiency and can improve the liver function of animals. The combination of high biocompatibility and high adsorption capacity positions the ERM-0100 as a promising candidate for bilirubin removal.

3-Trifluoromethylpyrazole and its derivatives are of major interest to both the agrochemical and pharmaceutical industry for their diverse biological activities. Reported routes for the synthesis of 3-trifluoromethylpyrazoles are hindered by poor regioselectivity and limited scope of application. Here we report a directed Lewis base catalyzed intermolecular triazene-alkyne cycloaddition. It is featured that the combination of 1,8-diazabicyclo[5.4.0]undec-7-ene and 2,2,2-trifluorodiazoethane produces reactive triazene intermediates, which readily participate in cycloaddition reactions with terminal/internal alkynes, thus assembling densely substituted 3-trifluoromethylpyrazole scaffolds with environmental friendliness and operational simplicity. Synthetic utility of the protocol is highlighted by late-stage functionalization and scaffolds diversification. The practical value is also emphasized in potential platelet aggregation inhibitor synthesis. Trifluoromethyl diazomethane is a versatile reagent with a variety of applications. Here its 1,3-dipolar cycloaddition across internal and terminal alkynes is shown to provide an efficient route to trifluoromethyl-substituted pyrazoles, including derivatives of marketed drugs, natural products, and bioactive heterocycles.

Mono‐ and 1,6‐disubstituted pyrene derivatives bearing perfluorotoluene or perfluorobenzonitrile moieties were synthesized by nucleophilic substitution processes. The compounds were characterized by NMR, UV‐vis, photoluminescence (PL), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), cyclic voltametry (CV) and density functional theory (DFT) calculations. We found that derivatives substituted with perfluorobenzonitrile showed better thermal stability, stronger electron with‐drawing ability and better fluorescence properties than the corresponding perfluorotoluyl‐pyrene systems

Palladium-catalyzed dearomative [2+2+1] annulations of aryl ethers with alkynes are reported via para-selective C–H functionalization, providing highly functionalized spirocyclohexadienones in mode...

Two pyrene derivatives, substituted with 2-methylnaphthalene units on 1,3-position and 1,6-position of pyrene backbones, were designed and synthesized. DFT calculation confirmed that the two molecules were highly twisted and the dihedral angles between pyrene backbone and naphthalene unit were over 80°, being attributed to the steric hindrance of ortho-methyl group and the substitution position of pyrene itself. As a result, the intermolecular aggregation was greatly inhibited in the solid state, being beneficial for suppressing the fluorescence quenching. By analyzing the optical and thermal properties, it was found that the π-π conjugation extension could be adjusted and a balance for high fluorescent efficiency and avoiding quenching at the same time could be reached, which may guide the molecular design in the future. The electroluminescence properties of the non-doped devices were enhanced with the double hole-transporting layers by optimizing the energy level matching. The stable blue EL emission, with the Commission Internationaled’Eclairage (CIEx,y) color coordinates of (0.15, 0.13) and (0.15, 0.11) at 7, 8, 9 and 10 V respectively, was obtained.

A series of promising candidates for n-type semiconductors, which were based on pyrene-thiophene backbone 1,6-, 1,8- and mono-substituted with cyano group and dicyanovinylene moieties, were synthesized. The compounds were characterized with nuclear magnetic resonance (NMR), elemental analysis, UV-vis, photoluminescence (PL), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), cyclic voltametry (CV) and Density functional theory (DFT) calculations. The effects of substitution position and substituent type on molecular properties were studied in detail. We found that the dicyanovinylene substitution enhanced the coplanarity of the π-conjugated systems compared with cyano substitution. The lowest unoccupied molecular orbital (LUMO) energy level was located deeply, and one of them had LUMO of below -4.00 eV, indicating that they may be promising candidates of n-type semiconductors.

Two bipolar blue-emitting materials, composed of the electron-withdrawing triphenyl-triazine core and the peripheral electron-donating 1-position substituted and 2-positon substituted pyrene moieties respectively, were designed, synthesized, and fully characterized by spectroscopies, cyclic voltammetry (CV) and Gaussian 03 molecular orbital calculations. The relationship between the structure and property was clearly demonstrated from the observed spectroscopic features (UV/Vis, photoluminescence and the solvatochromism) and molecular configuration. 1-Position substituted analogue exhibited a large twist angle of 52.0° and a strong electronic coupling between the core and the peripheral moieties, resulting in the strong dipolar property and the high fluorescent quantum efficiency of over 80% in the solution and the solid state. With the 1-position substituted analogue as the guest, the doped electroluminescence device showed a stable and efficient blue emission with the maximum luminance of 4306 cd/m 2 , the current efficiency of 1.15 cd/A, the external quantum efficiency of 0.97% and the CIE coordinate of (0.13, 0.06).

Three non-covalent metallotetraphenylporphyrin/fullerene (MTPPS4 (M=Zn2+, Fe2+, Co2+)/C60) nanocomposites were prepared by π-π molecular interaction and characterized by scanning electron microscopy and UV-Vis absorption spectroscopy. Electrocatalytic studies indicated that the MTPPS4/C60 nanocomposites which were embedded in TOAB film on the glassy carbon electrode (GCE) (TOAB/MTPPS4/C60/GCE) exhibited a high electrocatalytic activity for H2O2. MTPPS4 enhanced the electrocatalytic ability of C60 in the increasing order of TOAB/ZnTPPS4/C60/GCE, TOAB/FeTPPS4/C60/GCE and TOAB/CoTPPS4/C60/GCE. The measurement with the differential pulse voltammetry (DPV) exhibited that there is a well-defined linear relationship between the reduction currents and H2O2 concentrations in the range from 0.3 to 1.0 mM, with the detection limit of 0.07 mM at the TOAB/ZnTPPS4/C60/GCE electrode, of 0.08 mM at the TOAB/FeTPPS4/C60/GCE electrode, of 0.04 mM at the TOAB/CoTPPS4/C60/GCE electrode, respectively. The biosensors showed a good anti-interfering ability towards glucose, ascorbic acid and L-cysteine and a high potential practicality.

An expedient and efficient method for selective methylation of catechol coumarins by working with different alkalis under appropriate reaction conditions is reported. Esculetins were selectively methylated at position 6 and position 7 in good yield using CH3I in the presence of NaH and Na2CO3, respectively. However, daphnetins showed less regioselectivity under the same reaction conditions. Furthermore, the site preference for the methylation reaction was interpreted by the density functional theory at B3LYP/6-31+G(d) level.

There have been many reports on the application of pyrene derivatives as organic semiconductors, but 1,8-subsituted pyrene semiconductors are less well-developed. Two p-type 1,8-substituted pyrene derivatives were synthesized that were composed of a pyrene core, thiophene or bithiophene arms, and end-capped octyl chains. These structures were not completely symmetrical and the dihedral angles between the pyrene core and the adjacent thiophene units had a difference of approximately two degrees. The field-effect performance of these materials was tested on a variety of dielectric surfaces. The performance of both materials with a spin-coated polystyrene layer on SiO2 (PS-treated SiO2 ) was better than that with an octadecyltrichlorosilane self-assembled monolayer on SiO2 (OTS-treated SiO2 ), which was mainly attributed to the presence of large grains on the low-leakage and high-capacitance PS films. The thiophene-contained compound presented a hole mobility of up to 0.18 cm2 V-1 s-1 on PS-treated SiO2 , which was 45 times that of the bithiophene-contained compound, owing to less steric hindrance, high crystallinity, and large grain size.

Two kinds of cyanophenyl terminated pyrene derivatives for organic light-emitting diodes were synthesized and characterized by UV/Vis, fluorescence (FL), 1H NMR, MALDI-TOF, CV and TGA. Both compounds exhibited blue photoluminescence and high fluorescent quantum yield of 85% and 75% in solutions. Due to the presence of acetylene spacer, the compound distinguishes itself by high coplanarity, high thermal stability, little Stokes' shift and clear excimer formation in the solid state from the acetylene-free compound. In order to suppress the molecular aggregation, the electroluminescent properties were studied by doing the materials in PVK. The result proved that energy transfer happened from the host PVK to the materials.

A general, organocatalytic inverse-electron-demand [3+2] cycloaddition reaction between a range of carbonyl compounds and diazoacetates has been developed. This reaction is catalyzed by secondary amines as a "green promoter" to generate substituted pyrazoles with high levels of regioselectivity. It is noteworthy that this [3+2] cycloaddition reaction proceeds efficiently at room temperature with a simple and inexpensive catalyst. Considering the large variety and ready availability of the starting materials (e.g. ketones, β-ketoesters, β-diketones, and aldehydes), as well as the operational simplicity of this process, a convenient, practical, and highly modular pyrazole synthesis has been developed. We believe that this work will arouse more research interest in the organocatalytic synthesis of other biologically active heterocycles. Such studies are currently underway in our laboratory.

A general, organocatalytic inverse-electron-demand [3+2] cycloaddition reaction between a range of carbonyl compounds and diazoacetates has been developed. This reaction is catalyzed by secondary amines as a "green promoter" to generate substituted pyrazoles with high levels of regioselectivity. It is noteworthy that this [3+2] cycloaddition reaction proceeds efficiently at room temperature with a simple and inexpensive catalyst. Considering the large variety and ready availability of the starting materials (e.g. ketones, β-ketoesters, β-diketones, and aldehydes), as well as the operational simplicity of this process, a convenient, practical, and highly modular pyrazole synthesis has been developed. We believe that this work will arouse more research interest in the organocatalytic synthesis of other biologically active heterocycles. Such studies are currently underway in our laboratory.