Convenient Synthesis of Functionalized Bis‐ureidopyrimidinones Based on Thiol‐yne Reaction

Peng, Hui‐Qing; Sun, Cai‐Li; Xu, Jiang‐Fei; Niu, Li‐Ya; Chen, Yuzhe; Wu, Li‐Zhu; Tung, Chen‐Ho; Yang, Qing‐Zheng

doi:10.1002/chem.201402955

Cited by 18 publications

(18 citation statements)

References 41 publications

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“…Por(Pd)‐bisUPy was synthesized in ≈75% yield by thiol–yne reaction of the corresponding alkyne‐substituted porphyrin and UPy‐thiol . BF 2 ‐bisUPy was synthesized in ≈51% yield by thiol–ene reaction of the corresponding alkene‐substituted difluoroboron diketonate and UPy‐thiol; see the Experimental Section and Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

A Hydrogen‐Bonded‐Supramolecular‐Polymer‐Based Nanoprobe for Ratiometric Oxygen Sensing in Living Cells

Wang

Peng

Chen

et al. 2016

Adv Funct Materials

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5419wileyonlinelibrary.com signifi cant efforts have been devoted toward developing optical sensors for oxygen. [6][7][8][9][10][11] Quenching of phosphorescence is a powerful tool for oxygen sensing due to its invasiveness, selectivity, and (when applied in specifi c systems) sensitivity to oxygen. In addition, it can measure and map oxygen with high-resolution and in real-time in cells and tissues. Ratiometric oxygen sensing at two wavelengths allows for better calibration of oxygen levels and is more desirable in the chemical and medical fi elds than simple phosphorescence quenching. In a ratiometric sensor, oxygen concentration is calculated from the phosphorescence of an indicator dye and the fl uorescence of a reference dye. In the literature, such ratiometric oxygen sensors have been constructed by incorporation of phosphorescent dyes such as Pd(II)/Pt(II) porphyrin complexes inside conjugated polymer nanoparticles, [ 8 ] quantum dots, [ 9 ] silica gels, [ 10 ] and metal-organic frameworks. [ 11 ] Supramolecular polymers (SP), which are prepared from low-molecular-weight monomeric units that are associated through reversible noncovalent interactions (and thus different compositional constituents) can be effi ciently incorporated by copolymerization and provide a promising scaffold to fabricate phosphorescent functional nanomaterial for oxygen sensing. [ 12,13 ] In contrast to the rapid development of conjugated polymer nanoparticles for biosensing and bioimaging applications, [ 8 ] nanomaterials constructed from supramolecular polymers for sensing are still rare. [ 14 ] This can be attributed to the small number of examples of supramolecular polymers that have been found to form uniform nanostructures in water and are compatible with biological systems. Recently, we reported the construction of water-dispersible nanoparticles based on ureidopyrimidinone (UPy) quadruple hydrogen-bonded supramolecular polymers by a mini-emulsion method. [ 15 ] These nanoparticles exhibit several characteristics that make them ideal candidate for biological and biomedical applications. First, they have good structural and functional tunability because they are constructed from low-molecular-weight molecules, allowing synthetic elaborations for specifi c applications. Second, the nanoparticles are dispersed uniformly in aqueous solutions and stable for reasonably long periods. Third, the sizes of the nanoparticles are controllable by the concentration and type of the skeleton units. The small sizes of the nanoparticles should produce minimal cell damage and allow better cellular uptakeThe fi rst example of a ratiometric optical oxygen nanoprobe based on a hydrogen-bonded supramolecular polymer has been reported. The supramolecular polymer based nanoprobe (SPNP) is prepared from the co-assembly of a bis-ureidopyrimidinone (bis-UPy)-containing phosphorescent indicator (Por(Pd)-bisUPy), fl uorescent reference dye (BF 2 -bisUPy), and skeleton unit (DPA-bisUPy) through quadruple hydrogen bonds by a mini-emulsion method. The water-...

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Section: Resultsmentioning

confidence: 99%

A Hydrogen‐Bonded‐Supramolecular‐Polymer‐Based Nanoprobe for Ratiometric Oxygen Sensing in Living Cells

Wang

Peng

Chen

et al. 2016

Adv Funct Materials

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“…The detailed methods are as follows. Preparation of Pt-bisUPy: S3 (327.0 mg, 0.4532 mmol), UPy-SH [10] (353.0 mg, 1.13 mmol), and triethylamine (3 mL) were added to CH 2 Cl 2 (50 mL). After being stirred at room temperature for 12 h, ay ellow precipitate was collected, washed with diethyl ether and chloroform, and dried in vacuo.…”

Section: Synthesismentioning

confidence: 99%

“…Preparation of S2: S1 (78 mg, 0.24 mmol) was added to as olution of Pt(DMSO) 2 Cl 2 (101 mg, 0.24 mmol) in methanol (30 mL). The residue was purified by column chromatography by using CH 2 Cl 2 /CH 3 OH (100:1, v/v) as the eluent to afford the product (427 mg 41, 171.76, 157.50, 156.69, 156.32, 155.45, 150.95, 149.65, 132.39, 128.98, 126.26, 125.76, 122.47, 106.79, 102.08, 86.19, 64.87, 45.81, 40.53, 35.42, 33.36, 32.20, 30.33, 29.90, 27.65, 27.12, 23.16, 14.29, 12. Preparation of L-1:C ompound S1 (100.0 mg, 0.31 mmol), UPy-SH [10] (289 mg, 0.93 mmol), and triethylamine (10 drops) were added to CH 2 Cl 2 (50 mL). This method produced powdered complexes (91 mg) that required no further purification.…”

Section: Synthesismentioning

confidence: 99%

“…The desired compound Pt-bisUPy was obtained by the Michael addition of S3 with UPy-SH in 60 %y ield. Pt(DMSO) 2 Cl 2 and UPy-SH weres ynthesized according to the literature procedures [9b] and our previous report, [10] respectively.T he Pt-bisUPy was characterizedb y 1 HNMR, 13 CNMR, and high-resolution ESI-MS spectra. Pt-1 without the bisUPy unit [11] and L-1 withoutp latinum, needed for control experiments, were also synthesized as described in the Experimental Section.…”

Section: Synthesismentioning

confidence: 99%

“…1 HNMR (400 MHz, CDCl 3 ,T MS): d = 9.27 (d, J = 5.7 Hz, 2H), 8.00 (s, 2H), 7.43 (d, J = 7.2 Hz, 4H), 7.33-7.21 (m, 6H), 7.17 (t, J = 7.4 Hz, 2H), 6.49 (dd, J = 17.3, 0.9 Hz, 2H), 6.16 (dd, J = 17.3, 10.5 Hz, 2H), 5.91 (d, J = 10.5 Hz, 2H), 5.22 ppm (s, 4H). Preparation of Pt-bisUPy: S3 (327.0 mg, 0.4532 mmol), UPy-SH [10] (353.0 mg, 1.13 mmol), and triethylamine (3 mL) were added to CH 2 Cl 2 (50 mL). The resulting mixture was stirred at room temperature for 2.5 h. The solvents were removed.…”

Section: Synthesismentioning

confidence: 99%

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A Phosphorescent Platinum(II) Bipyridyl Supramolecular Polymer Based on Quadruple Hydrogen Bonds

Liu

Niu

Chen

et al. 2016

Chemistry A European J

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A platinum(II) bipyridyl complex bearing bis-ureidopyrimidinone (Pt-bisUPy) has been designed and its self-assembling behavior has been thoroughly investigated by H NMR, DOSY NMR, Ubbelohde viscometry analysis, UV/Vis, and emission spectroscopies. Pt-bisUPy underwent concentration-dependent ring-chain polymerization in apolar solvents. Hydrogen-bonding interactions play an important role during the formation of the supramolecular polymers. Hydrogen-bonded supramolecular polymers were transformed to nanoparticles in water through the miniemulsion method. These nanoparticles showed strong π-π excimeric emission. Metal-metal-to-ligand charge transfer (MMLCT) from Pt-Pt interactions was not significant in the emission spectrum. The phosphorescence of the nanoparticle persisted even under aerobic conditions. The triplet state of these phosphorescent nanomaterials were long-lived and possessed moderate emission quantum yields. Furthermore, the low toxicity of these materials promises a place for them in in vitro and in vivo bioimaging.

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Supramolecular Polymeric Fluorescent Nanoparticles Based on Quadruple Hydrogen Bonds

Peng

Sun

Niu

et al. 2016

Adv Funct Materials

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113

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5483wileyonlinelibrary.com biocompatibility. Accordingly, there has been a surge in the exploitation of CPNs in numerous exciting studies. [ 9 ] Covalent polymers, however, suffer from the need for tedious chemical modifi cation to tune the emission color of their corresponding nanoparticles.Supramolecular polymers, which are formed from low-molecular-weight monomers by noncovalent interactions, provide a promising scaffold for the fabrication of fl uorescent nanoparticles with well fi ne-tuned emission properties. [ 10 ] On the one hand, the small building blocks of supramolecular polymers provide synthetic accessibility superior to that of covalent polymers. On the other hand, the excitation energy transfer from energy donor to acceptor fl uorophores of the monomers occurs effi ciently in supramolecular copolymers. Such a process can be used to adjust the emission properties of functional materials. [ 11 ] Recently, we have reported the synthesis of water-dispersible nanospheres of hydrogen-bonded supramolecular polymers by the miniemulsion method. [ 12 ] Bis-ureidopyrimidinone (Bis-UPy) monomers polymerized through the quadruple H-bonding of the ureidopyrimidinone (UPy) motif to form supramolecular polymers, [ 13 ] which further aggregated into nanospheres in the emulsifi ed organic droplets. Herein, we prepared FNPs based on fl uorophore-functionalized Bis-UPys by the miniemulsion method ( Scheme 1 ). The emission properties of the nanoparticles could be fi ne-tuned by effi cient excitation energy transfer in co-assemblies of the energy donor and acceptor fl uorophore-based monomers. The photoswitchable FNPs with high on-off fl uorescence contrast (85%) were prepared by copolymerization of Bis-UPys containing fl uorophore and photochromic dithienylethene. The FNPs have been successfully applied in cellular imaging and as fl uorescent inks. Results and Discussion Synthesis, Preparation, and Characterization of FNPsFour fl uorophore-functionalized Bis-UPys were synthesized for the preparation of supramolecular polymer-based fl uorescent nanoparticles: Based on their different emission colors, fl uorophore 9,10-diphenylanthracene, 1,3,5,7-tetramethyl boron dipyrromethene (BODIPY), 3,5-dithiolated BODIPY, and naphthalene bisimide were chosen as the functional groups A facile approach for the preparation of supramolecular polymer-based fl uorescent nanoparticles (FNPs) is reported. FNPs with homogeneous shape and size distribution are fabricated from low-molecular-weight molecules, and thus, different compositional constituents can be effi ciently incorporated via copolymerization. The emission color of the FNPs covers a wide region from blue to near infrared and can be easily tuned using effi cient excitation energy transfer. The photoswitchable fl uorescent nanoparticles with high on-off fl uorescence contrast are also simply prepared by copolymerization of monomers containing a fl uorophore and a photochromic unit. Our FNPs are successfully applied in living cell imaging and as fl uorescent inks.

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Convenient Synthesis of Functionalized Bis‐ureidopyrimidinones Based on Thiol‐yne Reaction

Cited by 18 publications

References 41 publications

A Hydrogen‐Bonded‐Supramolecular‐Polymer‐Based Nanoprobe for Ratiometric Oxygen Sensing in Living Cells

A Hydrogen‐Bonded‐Supramolecular‐Polymer‐Based Nanoprobe for Ratiometric Oxygen Sensing in Living Cells

A Phosphorescent Platinum(II) Bipyridyl Supramolecular Polymer Based on Quadruple Hydrogen Bonds

Supramolecular Polymeric Fluorescent Nanoparticles Based on Quadruple Hydrogen Bonds

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