The syntheses of fluorescein-based conjugated microporous polymers by direct arylation polymerization and fluorescence sensing Fe3+ in aqueous solutions.

Determination of ferri ions in environment and human bodies is very important for environmental protection and disease diagnosis. Recently, conjugated microporous polymers (CMPs) used for fluorescence sensing metal ions have attracted much attention, but this technique is done in organic solvents. In this study, the two new fluorescein-based CMPs named FLEDOT and FLBTh were synthesized by "greener method", direct arylation polymerization, with tetraiodofluorescein sodium salt (TIFS) and 3,4-ethylenedioxy thiophene or 2,2'-bithiophene. Pleasely, the prepared fluorescein-based CMPs can fluorescently sense for Fe3+ in water with high sensitivity and selectivity. The quenching constants (KSV) of FLEDOT and FLBTh are 1.51 × 104 and 1.09 × 104 L mol-1, and the limits of detection (LODs) as low as 1.99 × 10-10 and 2.75 × 10-10 mol L-1, which are comparable to the sensitivity found in organic solvents' dispersions such as N,N-dimethylformamide (DMF)' dispersions. UV-Vis absorption spectra show that the fluorescence quenching mechanisms of Fe3+ are absorption competition quenching process and energy transfer process.

Fully Flexible Covalent Organic Frameworks for Fluorescence Sensing 2,4,6-Trinitrophenol and p-Nitrophenol.

Nitrophenols are important nitroaromatic compounds, both important environmental pollutants and dangerous explosives, posing a devastating danger and pollution threat to humans. It is vital to detect efficiently trace nitrophenols in the environment. In this contribution, a series of fully flexible cyclotriphosphazene-based COFs (FFCP COFs: HDADE, HBAPB, and HBPDA), prepared with both a flexible knot and flexible linkers of different lengths, were used for sensing 2,4,6-trinitrophenol (TNP) and p-nitrophenol (p-NP) in real time with excellent sensitivity and selectivity. The quenching constants of HDADE by TNP, HBAPB, and HBPDA by p-NP are 6.29 × 104, 2.17 × 105, and 2.48 × 105 L·mol-1, respectively. The LODs of TNP and p-NP are 1.19 × 10-11, 6.91 × 10-12, and 6.05 × 10-12 mol·L-1. Their sensitivities increase with the linker length, which is better than the corresponding COFs composed of rigid linkers. There is only a photoinduced electron transfer mechanism in the fluorescence quenching of HBPDA by p-NP. Meanwhile, the mechanisms of photoinduced charge transfer and resonance energy transfer exist in the fluorescence quenching of HDADE by TNP and the fluorescence quenching of HBAPB by p-NP.

Construction of dual-functional nitrogen-enriched fluorescent porous organic polymers for detecting m-dinitrobenzene, picric acid and capturing iodine.

Two novel nitrogen-enriched porous organic polymers (POPs), HBP and TBP, were constructed via nucleophilic substitution reactions with high nitrogen contents up to 24.91% and 32.92% for sensing to nitroaromatic compounds (NACs) and adsorbing iodine. They were all systematically characterized by solid-state 13C NMR, FT-IR, elemental analysis, solid-state UV-Vis, and other material analysis methods. The experimental data proved that both POPs possess high chemical and thermal stability, excellent fluorescence performance, and porous properties with Brunauer-Emmett-Teller (BET) specific surface areas of 32.88 and 68.00 m2 g-1. The two POPs have dual functions of fluorescence sensing and adsorption. On the one hand, due to their excellent conjugated properties and nitrogen-enriched structures, HBP and TBP exhibited incredibly high sensitivity to m-dinitrobenzene (m-DNB) and picric acid (PA) with KSV values of 2.57 × 105 and 4.93 × 104 L mol-1 and limits of detection of 1.17 × 10-11 and 6.08 × 10-11 mol L-1, respectively. On the other hand, owing to the plenty of nitrogen affinity sites, they exhibited excellent volatile iodine adsorption with 2.23 and 2.66 g g-1, respectively.

The effects of the crosslinking position and degree of conjugation in perylene tetraanhydride bisimide microporous polymers on fluorescence sensing performance.

In this study, two fluorescence conjugated microporous polymers based on perylene tetraanhydride bisimide (DP4A0 and DP4A2) were prepared via Sonogashira-Hagihara cross-coupling polymerization for the efficient detection of o-nitrophenol (o-NP). They were well characterized via FT-IR, solid state 13C NMR, elemental analysis, and other material characterization techniques. The experiments proved that both CMPs possess high thermal and chemical stability and a porous nature with Brunauer-Emmett-Teller (BET) specific surface areas of 41.3 and 402.1 m2 g-1. Importantly, owing to signal amplification by the conjugated skeleton, DP4A0 and DP4A2 exhibit extremely high sensitivity to o-NP with K sv values of 1.83 × 104 and 1.69 × 104 L mol-1 and limits of detection of 5.73 × 10-9 and 7.36 × 10-9 mol L-1, respectively. The sensing performance of DP4A0 and DP4A2 was dependent on the position of crosslinking points and crosslinking density. Finally, super amplified quenching was considered the electron transfer mechanism and hydrogen bond interactions were also present.

Fluorescent conjugated microporous polymer based on perylene tetraanhydride bisimide for sensing o-nitrophenol.

A novel conjugated microporous polymer based on perylene tetraanhydride bisimide (DP2A2) has been synthesized through Sonogashira-Hagihara cross-coupling polymerization of tetrabromo-substituted perylene tetraanhydride bisimide derivative (DPBr2ABr2) with 1,4-diethynylbenzene, whose Brunauer-Emmett-Teller (BET) specific surface area is about 378 m2 g-1. The fluorescence quenching behaviors of the DP2A2 were investigated. It is found that the DP2A2 shows high sensitivity and selectivity to tracing o-nitrophenol (o-NP) in THF with KsV constant of 2.00 × 104 L mol-1. The detection limit (LOD) is 1.50 × 10-9 mol L-1. The possible sensing mechanism for the luminescent quenching of DP2A2 towards o-NP exciting at 365 nm was considered the donor-acceptor electron transfer mechanism, which is a combined result from both dynamic (collisional) and static quenching. Moreover, the static quenching process is dominant for DP2A2.

Conjugated microporous polymers-based fluorescein for fluorescence detection of 2,4,6-trinitrophenol.

2,4,6-Trinitrophenol (TNP, also called picric acid, PA) pose a large threat to environmental health, public safety and military security. Conjugated microporous polymers are emerging new fluorescence sensing materials for TNP. In this paper, we report the synthesis of two fluorescein containing conjugated microporous polymers (DTF and TTF) through the palladium catalyzed Sonogashira-Hagihara polycondensation reactions of tetraiodofluorescein sodium salt (TIFA) with 1,4-diethynylbenzene (DEB) or 1,3,5-triethynylbenzene (TEB). DTF and TTF are porous with the BET surface areas of 705 and 712m2g-1 and exhibit high chemical and thermal stabilities. The formation of conjugated polymers with the incorporation of ethynyl groups leads to the fluorescent properties. The fluorescence quenching behaviors of DTF by nitroaromatic analytes in THF suspension are investigated. It is found that the fluorescence of DTF can be effectively quenched by 2,4,6-trinitrophenol over 2-nitrophenol (NP), 4-nitrotoluene (NT), nitrobenzene (NB), phenol (PhOH), p-dichlorobenzene (DClB) and 2,4-dinitrotoluene (DNT) with an SV constant of 2.08×103Lmol-1 and a detection limit of 7.22×10-7molL-1 (0.165mgL-1). In short, the DTF may be a new kind of fluorescence sensing material for detecting TNP.

IL-37 protects hepatocyte injury against hypoxia/reoxygenation by promoting polarization of M2-type macrophages / 复旦学报（医学版）

Objective To investigate the protective effect of IL-37 on hepatocyte injury against hypoxia/reoxygenation (H/R) by promoting polarization of M2-type macrophages and its molecular mechanisms.Methods Real-time fluorescent quantitative PCR (qRT-PCR) and Western blot were used to detect the levels of IL-37 mRNA and protein in human monocyte-macrophage THP-1 cells with different polarizations.The lentivirus with IL-37 gene was infected into THP-1 cells.The levels of CD206,CD86,ARG1 and iNOS mRNA was detected by qRT-PCR.The levels of CD163 and CD86 protein was detected by flow cytometric analysis.THP-1 cells and L02 cells were co-cultured by Transwell and treated with H/R.The survival rate and apoptotic rate of L02 cells were detected.The levels of alanine transaminase (ALT) and aspartate aminotransferase (AST) in culture medium were measured.The levels of STAT6 and its phosphorylation in THP-1 cells were detected by Western blot.Results The levels of IL-37 mRNA and protein were up-regulated in M2-type macrophages.IL-37 promoted the polarization of M2-type macropahges.M2-type macrophages induced by IL-37 were cocultured with L02 cells,the survival rate was significantly increased by H/R treatment (P =0.015),while the apoptotic rate,ALT level and AST level were significantly decreased (P＜0.001).The level of phosphorylated STAT6 in THP-1 cells overexpressing IL-37 was up-regulated (P ＜ 0.01).Conclusions IL-37 can induce polarization of M2-type macrophages and protect hepatocyte injury against H/R.Its mechanism may be related to STAT6 signal pathways.

Pinocembrin alleviates hypoxia reoxygenation injury in rat liver cell line BRL-3A / 基础医学与临床

Objcetive To investigate protective effect of pinocembrin ( PIN)on hepatocytes induced by hypoxia/reoxygenation ( H/R) as well as its relationship to the TLR 4/NF-κB signaling pathway .Methods The cells were randomly divided into 4 groups: control group, PIN group, hypoxia/reoxygenation injury group and PIN pretreatment group .The cell viability was measured with CCK-8.The apoptosis rate was determined by Annexin V-FITC/PI staining.The activity of ALT was detected .ELISA was used to evaluate the contents of TNF-αand IL-β.The mRNA and protein expression level of TLR 4, IκB-αand NF-κB P65 in cells was observed by quantita-tive real-time PCR or Western blot .Results The H/R stimulation decreased cell survival rate and enhanced the apoptosis .The activity of ALT was increased .The contents of TNF-αand IL-1βwere significantly enhanced , and the expression level of TLR4 and NF-κB P65 was markedly increased while IκB-αdecreased.After pretreatment with PIN, the cell survival rate increased while the apoptosis rate decreased .The activity of ALT was decreased. TNF-αand IL-1βwere reduced significantly and the expression level of TLR 4 and NF-κB P65 were decreased while IκB-αincreased.Conclusions PIN has protective effects on hypoxia/reoxygenation injury, which might be mediated in part by TLR4/NF-κB signaling pathway .

Fluorescent Polyamide-Based Rhodamine Hydrazide Moieties with Oxethyl as Spacer for Detection of Cr(3+), Fe(3+), and Hg(2+) Ions in Water.

An acrylic monomer bearing xanthene group, N-oxethyl acrylate-N'-rhodamine B hydrazide (ARBHE) was synthesized from N-hydroxyl ethyl-N'-rhodamine hydrazide (RBHE) and acryloyl chloride (Ac) in the presence of triethylamine in dry dichloromethane (CH2Cl2) at room temperature. The synthesized ARBHE was identified by FTIR, (1)H NMR spectra and elementary analysis. Copolymer poly(AM-ARBHE) of ARBHE and AM was synthesized with thermal initiator by free radical precipitation polymerization and it was characterized by the method of FTIR and (1)H NMR. Its molecular weights (Mη) was 7.03 × 10(3) g mol(-1) and the content of rhodamine units in the polymer chains was 1.44 % in mole fraction. The ability of the poly(AM-ARBHE) to detect different metal cations (Ag(+), Ba(2+), Cd(2+) Co(2+), Cr(3+), Cu(2+), Co(2+) K(+), La(3+), Mg(2+), Na(+), Ni(2+), Pb(2+), Fe(2+), Fe(3+), Hg(2+) and Zn(2+)) in water was investigated. Upon addition of Cr(3+), Fe(3+) or Hg(2+) ions to the aqueous solution, visual color change and fluorescence enhancement were observed. Moreover, other metal ions did not induce obvious changes to the fluorescence spectra except to Fe(2+). The detection limit of poly(AM-ARBHE) was less than 1 × 10(-11) M. The results suggest that this copolymer may offer potential as a polymeric sensor for Cr(3+), Fe(3+) and Hg(2+) ions in water.

Water-soluble polymeric chemosensor for selective detection of Hg(2+) in aqueous solution using rhodamine-based modified poly(acrylamide-acrylic acid).

We report the fabrication of a novel easily available turn-on fluorescent water-soluble polymeric chemosensor for Hg(2+) ions that was simply prepared by micellar free radical polymerization of a water-insoluble organic rhodamine-based Hg(2+)-recognizing monomer (GR6GH), with hydrophilic monomers acrylamide (AM) and acrylic acid (AA). The chemical structure of the polymeric sensor was characterized by FT-IR and (1)H NMR spectroscopy. The apparent viscosity average molecular weight Mη of poly(acrylamide-acrylic acid) [poly(AM-NaAA)] and the water-soluble polymeric chemosensor poly(AM-NaAA-GR6GH) were 1.76 × 10(6) and 6.84 × 10(4) g/mol, respectively. Because of its amphiphilic property, the water-soluble polymeric chemosensor can be used as a chemosensor in aqueous media. Upon addition of Hg(2+) ions to an aqueous solution of poly(AM-NaAA-GR6GH), fluorescence enhancements were observed instantly. Moreover, other metal ions did not induce obvious changes to the fluorescence spectra. This approach may provide an easily measurable and inherently sensitive method for Hg(2+) ion detection in environmental and biological applications.

Effects of single and double bonds in linkers on colorimetric and fluorescent sensing properties of polyving akohol grafting rhodamine hydrazides.

Two rhodamine derivatives, N-mono-maleic acid amide-N'-rhodamine B hydrazide (MRBH) and N-mono-succinic acid amide-N'-rhodamine 6G hydrazide (SR6GH), were synthesized by amidation with maleic anhydride (MAH), succinic anhydride (SAH) and rhodamine B hydrazide, rhodamine 6G hydrazide, which were identified by FTIR, (1)H NMR and elemental analysis. Two water-soluble fluorescent materials (PVA-MRBH and PVA-SR6GH) were prepared via esterification reaction with N-mono-maleic acyl chloride amide-N'-rhodamine B hydrazide (MRBHCl) or N-mono-maleic acyl chloride amide-N'-rhodamine 6G hydrazide (SR6GHCl) and poly(vinyl alcohol) (PVA) in DMSO solution. The sensing behaviors of PVA-MRBH and PVA-SR6GH were explored by recording the fluorescence spectra in completely aqueous solution. Upon the addition of Cu(2+) and Fe(3+) ions to the aqueous solution of PVA-MRBH, visual color change from rose pink to amaranth and orange for Cu(2+) and Fe(3+) ions, respectively, and fluorescence quenching were observed. Titration of Cu(2+), Fe(3+), Cr(3+) or Hg(2+) into the aqueous solution of PVA-SR6GH, although they induced fluorescence enhancement, only Fe(3+) made the color changing from colorless to yellow. Moreover, other metal ions did not induce obvious changes to color and the fluorescence spectra.

Fluorescence sensors for selective detection of Hg²âº ion using a water-soluble poly(vinyl alcohol) bearing rhodamine B moieties.

The novel water-soluble poly(vinyl alcohol) with pendant rhodamine B moiety as colorimetric and fluorescene chemosensor for Hg(2+) ions was prepared by grafting poly(vinyl alcohol) using rhodamine B hydrazide and hexamethylenediisocyanate as fluorescent dye and coupling agent, respectively. Because of their good water-solubility, the polymers binding rhodamine B can be used as chemosensors in aqueous media. With the addition of Hg(2+) ions into the aqueous solution, visual color changes and fluorescence enhancements were detected. In addition, we also noticed that other metal ions such as Ag(+), Cd(2+), Co(2+), Cu(2+), K(+), Mg(2+), Ba(2+), Fe(2+), Ni(2+), Pb(2+), Cr(3+), Fe(3+) and Zn(2+) cannot induce obvious changes to the fluorescence spectra of the polymer chemosensors. The combination of water solubility and positive fluorescence response as well as color change are hence particularly promising for the practical utility of the sensors.