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Biomedical subjects

Yuliang Li

Publications and source records attributed to Yuliang Li.

At least 19 recordsLinked to original sources

Amination of [60]fullerene by ammonia and by primary and secondary aliphatic amines--preparation of amino[60]fullerene peroxides.

Ammonia and aliphatic amines react readily in the oxygen-rich regions of the Cs symmetric fullerene peroxides C60(O)(OOtBu)4 (1) and C60(OH)(Br)(OOtBu)4 (2 c). Michael addition-type hydroamination of the 1,4-diene moiety on the central skew-pentagon was observed when 1 was treated with ammonia or with nonbulky primary amines, while sterically demanding primary amines opened the epoxy moiety to form vicinal aminohydroxy fullerene compounds with the amino group on the central pentagon. In 2 c the bromo group was replaced under similar conditions by ammonia and primary amines. Cyclic secondary amines showed different reaction patterns, forming hydrogenation products or aminoketal-fullerenes when treated with 1 and 2 c, respectively. Single-electron transfer (SET) is the key step in all the proposed mechanisms. The compounds were characterized by their spectroscopic data, and in addition, three single-crystal X-ray structures were obtained.

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Direct visualization of enzymatic cleavage and oxidative damage by hydroxyl radicals of single-stranded DNA with a cationic polythiophene derivative.

A new method has been developed for the label-free, convenient, and real-time monitoring of the cleavage of single-stranded DNA by single-strand-specific S1 nuclease and hydroxyl radical based on cationic water-soluble poly[3-(3'-N,N,N-triethylamino-1'-propyloxy)-4-methyl-2,5-thiophene hydrochloride](PMNT). The PMNT can form an interpolyelectrolyte complex with ssDNA (duplex) through electrostatic interactions, in which PMNT takes a highly conjugated and planar conformation, and thus PMNT exhibits a relatively red-shifted absorption wavelength. When ssDNA is hydrolyzed by S1 nuclease or hydroxyl radical into small fragments, the PMNT/ssDNA duplex cannot form. In this case, the PMNT remains in random-coil conformation and exhibits a relatively short absorption wavelength. The nuclease digestion or oxidative damage by hydroxyl radical of DNA can be monitored by absorption spectra or just visualized by the "naked-eye" in view of the observed PMNT color changes in aqueous solutions. This assay is simple and rapid, and there is no need to label DNA substrates. The most important characteristic of the assay is direct visualization of the DNA cleavage by the "naked-eye", which makes it more convenient than other methods that rely on instrumentation. The assay also provides a promising application in drug screening based on the inhibition of oxidative damage of DNA.

Base Sequence↗

Synthesis, characterization, and self-assembly of nitrogen-containing heterocoronenetetracarboxylic acid diimide analogues: photocyclization of N-heterocycle-substituted perylene bisimides.

Novel dibenzocoronenetetracarboxylic acid diimide analogues and naphthoperylenetetracarboxylic acid diimide analogues containing imidazole, 1,2,4-triazole, and pyrazole rings embedded as functional constituents within the parent hydrocarbon backbone have been synthesized. The pi-rich and pi-poor heterocycles have different influences on the physical properties of the parent benzocoronenetetracarboxylic acid diimide and naphthoperylenetetracarboxylic acid diimide systems. The pi-rich 3 was able to self-assemble into one-dimensional nanostructures through strong pi-pi stacking, whereas the pi-poor 8 lacked the one-dimensional self-assembly capability, thus offering the potential to control the self-assembly capability of the pi-conjugated perylene core by decoration with N-heterocycles.

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Shape-specific detection based on fluorescence resonance energy transfer using a flexible water-soluble conjugated polymer.

We present the detection of the shape-specific conformation of DNA based on the fluorescence resonance energy transfer (FRET) by using a novel flexible water-soluble cationic conjugated polymer (CCP). The flexible backbone of CCP has more conformational freedom with the potential to be responsive to analyte shape by electrostatic interaction between flexible CCP and negatively charged DNA. The analyte shape dependent recognition is accomplished by structural changes that compressed or extended the flexible CCP. The morphology-dependent spectral properties of the novel flexible polymer related to the analyte shapes are investigated in detail, where two types of chromophores, referred to as "isolated" segment and "packed" segment aggregates, within the flexible polymer are identified by means of ensemble and single molecule measurements upon binding with different geometric DNA. The change in fluorescence intensity upon binding with shape-specific DNA without obvious color shifts makes this novel flexible polymer a suitable CCP donor for FRET measurements. The results provide insights for understanding the spectral properties of flexible water-soluble CCP and CCP/DNA interaction related to the geometry of target analyte.

Base Sequence↗

Quadruplex-to-duplex transition of G-rich oligonucleotides probed by cationic water-soluble conjugated polyelectrolytes.

G-quartet DNA converts to duplex form in the presence of its complementary strand. This conformational change can be detected in real time by a homogeneous assay method based on the signal amplification of conjugated polyelectrolytes and the specific interaction of intercalating dyes with double-stranded DNA (dsDNA). The probe solution contains a cationic, conjugated polymer (CCP), G-quadruplex labeled with a fluorescein at the 5'-terminus (G-quadruplex-Fl), and ethidium bromide (EB). The addition of a complementary target results in the transition from G-quadruplex to duplex (dsDNA-Fl) and EB intercalation within the duplex structure. Excitation of the CCP leads to energy transfer from CCP to dsDNA-Fl (FRET-1) and then energy transfer from dsDNA-Fl to EB (FRET-2). Increasing the number of mismatched bases discourages dsDNA formation, which is detected in the assay.

Cations↗

Synthesis and characterization of pyrrolidin-2-one fused N-confused calix[4]phyrins.

[reaction: see text] A facile method for the synthesis of pyrrolidin-2-one fused N-confused calix[4]phyrins is provided by reactions of 5,10,15,20-tetraaryl-2-aza-21-carbaporphyrin with acyl chlorides in the presence of triethylamine. The (1)H NMR and UV-vis spectra of products indicate their loss of macrocyclic aromaticity.

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Synthesis and characterization of 3,5-bis(2-hydroxyphenyl)-1,2,4-triazole functionalized tetraaryloxy perylene bisimide and metal-directed self-assembly.

[structure: see text] New perylene bisimide dyes bearing 3,5-bis(2-hydroxyphenyl)-1,2,4-triazole receptor units with different spacers have been synthesized and characterized. The fluorescence and electronic properties of these compounds have been studied. MALDI-TOF, UV-vis, and fluorescence titration experiments proved that monotopic perylene bisimide ligands could be assembled into dimmers by Fe(III) coordination. The coordination properties of the ditopic perylene bisimide ligands have also been studied preliminarily. Furthermore, the SEM images indicated that well-defined nanoscale structures could be fabricated by self-assembly due to metal ion coordination and pi-pi stacking interactions of perylene rings with the help of a proper spacer.

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Energy transfer switching in a bistable molecular machine.

[reaction: see text] A novel [2]rotaxane, containing pyrene and perylene bisimide as both stoppers and photoactive units, has been prepared. The shuttling of the protonated macrocycle switched the energy transfer (EN) from a pyrene moiety to a perylene moiety, which resulted in changes of fluorescence of the perylene moiety.

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Novel carboxylated oligothiophenes as sensitizers in photoelectric conversion systems.

Novel carboxylated oligothiophenes with different thiophene units were designed and synthesized as photosensitizers in dye-sensitized solar cells (DSSCs) for efficient opto-electric materials. The introduction of -COOH into thiophene molecules can lead to a red shift of UV-visible absorption, increase light-harvesting efficiency, and enhance photoinduced charge transport by forming efficient covalent bonds to the substrate surface. A red shift of the absorption spectrum of oligothiophene is also achieved by the increase in the number of thiophene units. The DSSCs based on the oligomers have excellent photovoltaic performances. Under 100 mW cm(-2) irradiation a short-circuit current of 10.57 mA cm(-2) and an overall energy conversion efficiency of 3.36 % is achieved when pentathiophene dicarboxylated acid was used as a sensitizer. The incident photo-to-current conversion efficiency (IPCE) has a maximum as high as 80 %. In addition, photovoltage and photocurrent transients show that slow charge recombination in DSSCs is important for efficient charge separation and excellent photoelectric conversion properties of the oligomers. These initial and promising results suggest that carboxylated oligothiophenes are efficient photosensitizers.

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Fabrication of polydiacetylene nanowires by associated self-polymerization and self-assembly processes for efficient field emission properties.

The paper described here concerns a challenge of general interest for producing a novel structure of a polymer aggregate, the achievement of nanowires with controlled diameters. We provide a strategy for fabricating a supramolecular polymer, in which ordered polydiacetylene nanowires can be obtained by associated self-polymerization and self-assembly processes. The polymer nanowire film shows excellent field emission properties with the turn-on field of 8.2 V/mum at 10 muA/cm2 and the maximum current density of 5 mA/cm2 at an applied field of 15 V/mum.

Acetylene↗

Fluorescent amplifying recognition for DNA G-quadruplex folding with a cationic conjugated polymer: a platform for homogeneous potassium detection.

Single-stranded DNA with G-rich sequences can fold into secondary structures, G-quadruplexes, via intramolecular hydrogen-bonding interactions. This conformational change can be detected by a homogeneous assay method based on fluorescence resonance energy transfer (FRET) from a water-soluble cationic conjugated polymer (CCP) to a fluorescein chromophore labeled at the terminus of the G-quadruplex DNA. The space charge density around the DNA controls the efficiency of FRET from the CCP to the fluorescein. The higher FRET efficiency for the CCP/G-quadruplex pair is correlated to the stronger electrostatic interactions between the more condensed G-quadruplex and the CCP in comparison to the CCP/ssDNA pair. Since the potassium ion can specifically bind to the G-quadruplex DNA, the G-quartet-DNA/CCPs assembly can also be used as a platform to sense the potassium ion in water with high selectivity and sensitivity.

Biosensing Techniques↗

Third-order nonlinear optical properties of an ultrathin film containing a porphyrin derivative.

An ultrathin nanoscopic multilayer film has been fabricated through the electrostatic layer-by-layer self-assembly of negatively charged 5,10,15,20-tetrakis(3,4,5-trihydroxyphenyl)porphyrin (DHP) and oppositely charged polyethylenimine (PEI). UV-vis spectra showed a continuous and uniform deposition process of PEI and DHP. The film structure was characterized by small-angle X-ray diffraction measurement and AFM images. The nonlinear optical properties of ultrathin film were studied by Z-scan technique with laser duration of 8 ns at a wavelength of 532 nm. The film sample exhibited strong nonlinear saturated absorption and a self-defocusing effect. The nonlinear absorption coefficient and refractive index of the self-assembly ultrathin film are -9.7 x 10(-5) m/W and -7.56 x 10(-12) m(2)/W, respectively.

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Dyads and triads containing perylenetetracarboxylic diimide and porphyrin: efficient photoinduced electron transfer elicited via both excited singlet states.

Synthesis, characterizations, and photophysical properties of new photoactive dyads and triads containing perylenetetracarboxylic diimide (PIm) and porphyrin (free-base porphyrin (H(2)P) and zinc porphyrin (ZnP)), in which both entities were connected with a short ether bond, were examined with the aim of using these systems for molecular photonics. The porphyrin(P)-PIm systems absorbed strongly across the visible region, which greatly matched the solar spectrum. The geometric and electronic structures of the dyads and triads were probed using density function theory method at the B3LYP/3-21G level. It was revealed that the majority of the highest-occupied molecular orbital was located on the porphyrin entity, while the lowest-unoccupied molecular orbitals were entirely on the PIm entity. The excited-state electron-transfer processes were monitored by both steady-state and time-resolved emission as well as transient-absorption techniques in polar solvent benzonitrile. Upon excitation of the P (H(2)P and ZnP) moieties, efficient fluorescence quenching of the P moiety was observed, suggesting that the main quenching paths involved charge separation from the excited singlet porphyrin ((1)P) to the PIm moiety. Upon excitation of the PIm moiety, fluorescence quenching of the (1)PIm moiety was also observed. The nanosecond transience of spectra in near-IR region revealed the charge separation process from the P moieties to the PIm moiety via their excited singlet states. The lifetimes of the charge-separated states were evaluated to be 7-14 ns, depending on the solvent polarity. Photosensitized electron mediation systems were also revealed in the presence of methyl viologen and sacrificial electron donor.

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Field emission properties of large-area nanowires of organic charge-transfer complexes.

In this contribution, large-area organic charge-transfer complex (AgTCNQ and CuTCNQ) nanowires were synthesized by organic vapor-solid-phase reaction at mild experimental conditions. These nanowires were facilitated on the surface of Cu and Ag foils or different kinds of substrates coated with a layer of silver and copper on a large scale. The excellent field emission properties were observed in the as-grown AgTCNQ and CuTCNQ nanowires. They should have great potential in vacuum device applications.

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Fabrication of ultrathin films with large third-order nonlinear optical properties.

An ultrathin composite film containing anionic Ag-His complexes (His: L-Histidine) and oppositely charged BH-PPV was fabricated by means of the electrostatic layer-by-layer self-assembly technique. UV/Vis spectra showed a continuous deposition process of Ag-His complexes and BH-PPV. The film structure was characterized by using small-angle X-ray diffraction, AFM, and SEM. The nonlinear optical properties of the ultrathin film were studied by using the Z-scan technique with a laser duration of 8 ns at a wavelength of 532 nm. The film sample exhibited a strong nonlinear saturated absorption, with an alpha2 value of -3.9 x 10(-5) mW(-1) and a self-defocusing effect with an n2 value of -4.78 x 10 (-12) m2W(-1).

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Assembly and characterization of novel hydrogen-bond-induced nanoscale rods.

A class of bis-urea compounds with perylene bisimide was synthesized and characterized successfully. (1)H NMR and fluorescence spectra confirmed that strong hydrogen-bonding interactions between neighboring urea groups were formed. Interestingly, the photocurrent measurement showed that the self-assembled films of bis-urea compounds could produce steady and rapid anodic photocurrent responses. The TEM images indicated that well-defined nanoscale rods with uniform diameter distribution could be fabricated by self-assembly of hydrogen-bonding interactions and pi-pi stacking interactions of perylene rings.

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