Light-Induced Self-Escape of Spherical Nucleic Acid from Endo/Lysosome for Efficient Non-Cationic Gene Delivery
(WILEY-V C H VERLAG GMBH, 2020) Shi, Leilei; Wu, Wenbo; Duan, Yukun; Xu, Li; Xu, Yingying; Hou, Lidan; Meng, Xiangjun; Zhu, Xinyuan; Liu, Bin; Prof Bin Liu; MATERIALS SCIENCE AND ENGINEERING; CHEMICAL & BIOMOLECULAR ENGINEERING
Developing non-cationic gene carriers and achieving efficient endo/lysosome escape of functional nucleic acids in cytosol are two major challenges faced by the field of gene delivery. Herein, we demonstrate the concept of self-escape spherical nucleic acid (SNA) to achieve light controlled non-cationic gene delivery with sufficient endo/lysosome escape capacity. In this system, Bcl-2 antisense oligonucleotides (OSAs) were conjugated onto the surface of aggregation-induced emission (AIE) photosensitizer (PS) nanoparticles to form core–shell SNA. Once the SNAs were taken up by tumor cells, and upon light irradiation, the accumulative O produced by the AIE PSs ruptured the lysosome structure to promote OSA escape. Prominent in vitro and in vivo results revealed that the AIE-based core–shell SNA could downregulate the anti-apoptosis protein (Bcl-2) and induce tumor cell apoptosis without any transfection reagent. 1 2
Synthesis and characterization of a water-soluble carboxylated polyfluorene and its fluorescence quenching by cationic quenchers and proteins
(2008-04-07) Zhang, Y.; Liu, B.; Cao, Y.; CHEMICAL & BIOMOLECULAR ENGINEERING
We have developed a new intermediate monomer, 2,7-[bis(4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl)-9,9-bis(3-(tert-butyl propanoate))]fluorene, that allows the easy synthesis of water-soluble carboxylated polyfluorenes. As an example, poly[9,9′-bis(3″-propanoate)fluoren-2,7-yl] sodium salt was synthesized by the Suzuki coupling reaction, and the properties of the polymer were studied in aqueous solutions of different pH. Fluorescence quenching of the polymer by different cationic quenchers (MV2+, MV4+, and NO2MV2+; MV=methyl viologen) was studied, and the quenching constants were found to be dependent on the charge and electron affinity of the quencher molecule and the pH of the medium. The largest quenching constant was observed to be 1.39×108M-1 for NO2MV2+ at pH 7. The change in polymer fluorescence upon interaction with different proteins was also studied. Strong fluorescence quenching of the polymer was observed in the presence of cytochrome c, whereas weak quenching was observed in the presence of myoglobin and bovine serum albumin. Lysozyme quenched the polymer emission at low protein concentrations, and the quenching became saturated at high protein concentrations. Under similar experimental conditions, the polymer showed improved quenching efficiencies toward cationic quenchers and a more selective response to proteins relative to other carboxylated conjugated polymers. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.
Chemiluminescence-Guided Cancer Therapy Using a Chemiexcited Photosensitizer
(Elsevier Inc., 2017-12-14) MAO DUO; WU WENBO; Ji, Shenglu; Chen, Chao; Hu, Fang; Kong, Deling; Ding, Dan; LIU BIN; Dr Mao Duo; MATERIALS SCIENCE AND ENGINEERING; CHEMICAL & BIOMOLECULAR ENGINEERING
Image-guided therapy is one of the most promising strategies for efficiently curing a tumor. Here, a novel nanomaterial with chemiexcited far-red/near-infrared (FR/NIR) emission and singlet oxygen (1O2) generation is reported for precise diagnosis and treatment of tumors. Bis[2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl] oxalate (CPPO) and a specially designed photosensitizer TBD with aggregation-induced FR/NIR emission were co-encapsulated by pluronic F-127 and soybean oil to form C-TBD nanoparticles (C-TBD NPs). These NPs serve as a specific H2O2 probe to precisely track tumors in vivo through chemiluminescence imaging. In addition, effective 1O2 generation by C-TBD NPs in response to tumor H2O2 was observed, which could efficiently induce tumor cell apoptosis and inhibit tumor growth. Both the chemiluminescence response and the therapeutic function were further enhanced when β-phenylethyl isothiocyanate was used to enhance the H2O2 production at the tumor site. Our results prove that C-TBD NPs provide a new strategy for intelligent, accurate, and non-invasive tumor therapy. Precise image-guided therapy is key to eradicating tumors in clinical practice. Here, we report a new nanomaterial based on a chemiexcited photosensitizer, which can be specifically activated by H2O2 within the tumor environment to produce far-red/near-infrared luminescence and singlet oxygen. Using such a nanoparticle, primary and metastatic breast tumors can be clearly identified through chemiluminescence imaging with a very high signal-to-noise ratio. Accompanied by the use of an anti-tumor drug, FEITC, the signal of the tumor could be further enhanced as a result of elevated H2O2 production at the tumor site. More importantly, specific tumor killing can be achieved through chemiexcited singlet oxygen production, and the effect of therapy is also increased in the presence of FEITC. Considering the multiple advantages of simultaneous tumor theranostics, our nanoparticle design represents a promising strategy for future clinical tumor therapy. Organic nanoparticles exhibiting intense FR/NIR chemiluminescence and strong chemiexcited singlet oxygen generation in the presence of H2O2 have been successfully used for selective tumor imaging and therapy. Both tumor chemiluminescent signals and singlet oxygen production can be further enhanced in the presence of an anti-tumor drug, FEITC, which could increase the amount of H2O2 at the tumor site for effective tumor treatment. Our design represents a new strategy for light-source-free image-guided tumor therapy.
Significance of decoy receptor 3 (Dcr3) and external-signal regulated kinase 1/2 (Erk1/2) in gastric cancer
(BioMed Central Ltd., 2012) Yang D.; Fan X.; Yin P.; Wen Q.; Yan F.; Yuan S.; Liu B.; Zhuang G.; Liu Z.; CHEMICAL & BIOMOLECULAR ENGINEERING
Near-infrared fluorescence amplified organic nanoparticles with aggregation-induced emission characteristics for in vivo imaging
(2014-01-21) Geng, J.; Zhu, Z.; Qin, W.; Ma, L.; Hu, Y.; Gurzadyan, G.G.; Tang, B.Z.; Liu, B.; CHEMICAL & BIOMOLECULAR ENGINEERING
Near-infrared (NIR) fluorescence signals are highly desirable to achieve high resolution in biological imaging. To obtain NIR emission with high brightness, fluorescent nanoparticles (NPs) are synthesized by co-encapsulation of 2,3-bis(4-(phenyl(4-(1,2,2-triphenylvinyl)phenylamino)phenyl)fumaronitrile (TPETPAFN), a luminogen with aggregation-induced emission (AIE) characteristics, and a NIR fluorogen of silicon 2,3-naphthalocyanine bis(trihexylsilyloxide) (NIR775) using 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N- [methoxy(polyethylene glycol)-2000] as the encapsulation matrix. The good spectral overlap between the emission of TPETPAFN and the absorption of NIR775 leads to efficient energy transfer, resulting in a 47-fold enhancement of the NIR775 emission intensity upon excitation of TPETPAFN at 510 nm as compared to that upon direct excitation of NIR775 at 760 nm. The obtained fluorescent NPs show sharp NIR emission with a band width of 20 nm, a large Stokes shift of 275 nm, good photostability and low cytotoxicity. In vivo imaging study reveals that the synthesized NPs are able to provide high fluorescence contrast in live animals. The Förster resonance energy transfer strategy overcomes the intrinsic limitation of broad emission spectra for AIE NPs, which opens new opportunities to synthesize organic NPs with high brightness and narrow emission for potential applications in multiplex sensing and imaging. © 2013 The Royal Society of Chemistry.
Cationic polyelectrolyte amplified bead array for DNA detection with zeptomole sensitivity and single nucleotide polymorphism selectivity
(2010-08-23) Wang, C.; Zhan, R.; Pu, K.-Y.; Liu, B.; CHEMICAL & BIOMOLECULAR ENGINEERING
A highly sensitive strand specific DNA assay, which consists of a peptide nucleic acid (PNA) probe, a cationic conjugated polymer (PFVP), and selfassembled polystyrene beads in microwell arrays on silicon chip, is reported. PFVP, as an efficient signal amplifier and signal reporter, has been specially designed and synthesized to be compatible with commercial confocal microscopes for sensing on solid substrates. The assay operates on the net increase in negative charge at the PNA surface that occurs upon singlestranded DNA hybridization, which subsequently allows complex formation with the positively charged PFVP to favor energy transfer between the polymer and Cy5-labeled target. With maximized surface contact provided by bead arrays and signal amplification provided by PFVP, this assay allows detection of -300 copies of Cy5-labeled DNA using a commercial confocal microscope. In addition, the same strategy is also extended for label-free DNA detection with a detection sensitivity of 150 attomole. Excellent discrimination against single nucleotide polymorphism (SNP) is also demonstrated for both Cy5-labeled and label-free target detection. This study indicates that cationic conjugated polymers have great potential to be incorporated into the widely used microarray technology for simplified process with improved detection sensitivity. © 2010 WlLEY-VCH VerlagCmbH & Co. KCaA, Weinheirn.
A tetraphenylethene-based red luminophor for an efficient non-doped electroluminescence device and cellular imaging
(2012-06-14) Zhao, Z.; Geng, J.; Chang, Z.; Chen, S.; Deng, C.; Jiang, T.; Qin, W.; Lam, J.W.Y.; Kwok, H.S.; Qiu, H.; Liu, B.; Tang, B.Z.; CHEMICAL & BIOMOLECULAR ENGINEERING
An efficient red luminophor (TTPEBTTD) consisting of a 4,7-di(thiophen-2- yl)benzo-2,1,3-thiadiazole core and tetraphenylethene peripheries is developed. The non-doped electroluminescence device based on TTPEBTTD radiates red light with high efficiency up to 3.7%. The nanoparticles of TTPEBTTD are promising fluorescent visualizers for cellular imaging with low cytotoxicity. © 2012 The Royal Society of Chemistry.
Water-soluble conjugated polymers as the platform for protein sensors
(2010-05) Li, K.; Liu, B.; CHEMICAL & BIOMOLECULAR ENGINEERING
The booming development of protein detection requires simple, sensitive, and reliable biosensor systems. Water-soluble conjugated polymers have been widely used for protein sensing due to their distinct optical response in the presence of different analytes. This review summarizes the recent developments in water-soluble conjugated polymer-based protein sensors. Based on the different optical responses of conjugated polymers to proteins, these assays are categorized into three groups. The conformational change of cationic poly(thiophene)s is used to generate unique colorimetric or fluorescent transduction upon interaction with target proteins. Super-quenching of water-soluble poly(phenylene vinylene)s and poly(phenylene ethynylene)s has been developed into fluorescence turn-on and turn-off protein assays. Energy transfer between poly(fluorene-co-phenylene) derivatives and acceptor dyes is also utilized to develop fluorescence turn-on protein assays with amplified signal output. The fine-tuning of conjugated polymer structures will benefit the design of versatile optical probes to satisfy the sophisticated requirements for protein sensors. © 2010 The Royal Society of Chemistry.
Facile synthesis of stable and water-dispersible multihydroxy conjugated polymer nanoparticles with tunable size by dendritic cross-linking
(2012) Zhou, L.; Geng, J.; Wang, G.; Liu, J.; Liu, B.; CHEMICAL & BIOMOLECULAR ENGINEERING
A new strategy has been developed to synthesize conjugated polymer (CP) nanoparticles (CPNs) with numerous surface hydroxyl groups via click chemistry between a CP and hyperbranched polyglycerol (HPG) in miniemulsion. Laser light scattering and TEM characterizations indicate that the synthesized CPNs have spherical shapes with uniform sizes tunable in the range of 40-210 nm simply by adjusting the feed amount of the oil phase or surfactant in the miniemulsion. The obtained CPNs have good water dispersibility and orange emission with high fluorescence quantum yields of 23 ± 2%. Detailed spectroscopy studies reveal that the CPNs have shown stable fluorescence against pH change, ionic strength variation, or protein disturbance. In addition, they have good photostability and low cytotoxicity, which make them an ideal fluorescent moiety for cellular imaging. This study provides important fundamental understanding of cross-linking modification on CP to form CPNs, which will stimulate further research on synthesis and application of advanced CPNs. © 2012 American Chemical Society.
Metal-Organic Framework as a Simple and General Inert Nanocarrier for Photosensitizers to Implement Activatable Photodynamic Therapy
(Wiley-VCH Verlag, 2018-05-09) Hu, Fang; MAO DUO; KENRY; WANG YUXIANG; Wu, Wenbo; Zhao Dan; Kong, Deling; LIU BIN; Dr Mao Duo; CHEMICAL & BIOMOLECULAR ENGINEERING
There has been a surging interest in the synthesis of activatable photosensitizers (PSs) as they can be selectively activated with minimum nonspecific phototoxic damages for photodynamic therapy (PDT). Conventional strategies to realize activatable PSs are only applicable to a limited number of molecules. Herein, a simple and general strategy to yield activatable PSs by coupling MIL-100 (Fe) (MIL: Materials Institute Lavoisier) with different kinds of PSs is presented. Specifically, when PSs are encapsulated into MIL-100 (Fe), the photosensitization capability is suppressed due to their isolation from O2. After the reaction between iron(III) in MIL-100 (Fe) and H2O2 occurs, the framework of MIL-100 (Fe) collapses and the encapsulated PSs regain contact with O2, leading to activation of photosensitization. In addition, the decomposition of H2O2 can generate O2 to relieve tumor hypoxia and enhance PDT effect. As O2 is an indispensable factor for PDT, the activation strategy should be generally applicable to different PSs for activatable PDT.

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