We report here our results on the investigation of the chain dynamics of poly(acrylic acid) in aqueous solution. The concentration of poly(acrylic acid) was approximately 3.8×10^(-4) mol/L, two orders of magnitude higher than that reported in the literature. The p H value of the solution was 3.9, and the hydrogen bonds between the intrinsic and ionized carboxylic acid groups formed dynamic networks, which captured aggregation-induced emission-active molecules(a tetra-quaternary ammonium modified tetraphenylethene derivative) inside the polymer coils and induced fluorescence emission. The hydrogen bonds can be classified as intra- or intermolecular; both can be probed based on the emission change of the tetra-quaternary ammonium modified tetraphenylethene probes. The effects of different external stimuli on the polymer chain dynamics were investigated using different metal cations(including Na^+, Li^+, Zn^(2+), Ni^(2+), Ca^(2+), and Co^(2+)), different cation concentrations(1×10^(-6) to 4×10^(-4) mol/L), different poly(acrylic acid) molecular weights(5, 240, and 450 k Da), and different copolymers. The experimental results indicate that the long poly(acrylic acid) chains(high molecular weight) tend to form dense globular coils and exclude the probe molecules outside, which are robust and unsusceptible to water-soluble metal cations. However, the shorter poly(acrylic acid) chains tend to form intermolecular hydrogen bonds, which are helpful in capturing more probe molecules inside the networks, thus inducing stronger emission. Because of the dual functions of forming hydrogen bonds with carboxylic groups and acting as an acceptor of protons from the carboxylic acid group to form cationic species, copolymerization with acrylate amide [poly(acrylic acid)-co-poly(acrylamide)] can greatly affect the chain dynamics of poly(acrylic acid) segments, which is reflected by the drastically decreased emission intensity from the fluorescent probes.
Rodents are popular biological models for physiological and behavioral research in neuroscience and rats are better models than mice due to their higher genome similarity to human and more accessible surgical procedures.However,rat brain is larger than mice brain and it needs powerful imaging tools to implement better penetration against the scattering of the thicker brain tissue.Three-photon fluorescence microscopy(3PFM)combined with near-infrared(NIR)excitation has great potentials for brain circuits imaging beause of its abilities of anti scattering,deep-tissue imaging,and high signal-to-noise ratio(SNR).In this work,a type of AIE lumninogen with red fuorescence was synthesized and encapsulated with Pluronic F-127 to make up form nano-particles(NPs).Bright DCDPP-2TPA NPs were employed for in trino three-photon fuorescent laser scanning microscopy of blood vessels in rats brain under 1550 nm femtosecond laser exci-tation.A fine three-dimensional(3D)reconstruction up to the deepness of 600 pm was achieved and the blood flow velocity of a selected vessel was measured in vrito as well.Our 3PFM deep brain imaging method simultaneously recorded the morphology and function of the brain blood vessels in vivo in the rat model.Using this angiography combined with the arsenal of rodent's brain disease,models can accelerate the neuroscience research and clinical diagnosis of brain disease in the future.
Cu（Ⅱ） detection is important because it plays crucial role in several biological processes and ecological systems.Fluorescent techniques have attracted more and more attention in Cu（Ⅱ） detection.In this report,we contribute a novel strategy to use fluorescence spectroscopy for Cu（Ⅱ） specific detection.The specificity relies on the fact that,of the many metal cations,only Cu（Ⅱ） can catalyze the hydrolyzation of a-amino acid ester.The novelty originates from the unique aggregation-induced emission（AIE） property of the fluorescent label.We designed a model a-amino acid ester（TPE-Ala） constructed with alanine and tetraphenylethene-functionalized methanol（TPE-methanol）.In comparison with the precursor TPE-Ala, TPE-methanol has lower solubility and is easy to form aggregates in water,thereby displaying a higher fluorescent response.Thus,the Cu（Ⅱ） catalyzed hydrolyzation can be monitored by recording the fluorescence enhancement and fluorescent detection Cu（Ⅱ） is rationally achieved.
A highly stable Zn, Ni-bimetallic porous nanocomposite was synthesized via a one-step pyrolysis of a metal-organic framework as an efficient anode material for Lithium-ion batteries. Remarkably the obtained composite shows 1105.2 m Ah/g at a current density of 5000 m A/g after 400 cycles which makes it a promising candidate to improve the volumetric energy density.
A novel luminogen, CZ2TPAN, with typical D-A architecture was obtained. It shows intramolecular charge transfer and aggregation-induced emission characteristics with high solid-state efficiency of 65.3%. Moreover, it exhibits reversible mechanochromic behavior between crystalline and amorphous states with remarkable emission color change from green (504 nm) to yellow (545nm).
LU YaWeiTAN YeQiangGONG YongYangLI HongYUAN WangZhangZHANG YongMingTANG Ben Zhong
Two derivatives of tetraphenylethene (TPE) were synthesized through one step cross McMurry coupling reaction. Both luminogens exhibit aggregation-induced emission (AIE) and crystallization induced emission enhancement (CIEE). The emissions of both luminogens could be switched between blue and green through reversible modulation of morphology with thermal, organic solvent fuming and mechanical stimuli. Thus we provide a possible design strategy for emission switching materials.
SHI JunQingZHAO WeiJunLI CuiHongLIU ZhengPingBO ZhiShanDONG YuPingDONG YongQiangTANG Ben Zhong
Tetraphenylethylene (TPE) derivatives have been proved to be typical aggregation-induced emission (AIE) luminogens when they were aggregated in the free three-dimensional space. In order to reveal the effect of the dimensional degree on AIE property of TPEs, we utilized tetra(4-hydroxyphenyl)ethylene (TPE-4OH) and 1,4-benzenediamine diazonium salt (BD) to fabricate the ultrathin films (TPE-4OH/BD LBL SA film) through layer-by-layer self-assembled technique. The interaction between TPE-4OH and BD in the films was converted from electrostatic force and hydrogen-bond to covalent bonds through photodecomposition of diazonium groups under UV irradiation. Fluorescence emission spectroscopy, UV-Vis absorption spectroscopy and atomic force microscope were carried out to evaluate the relationship between bilayer number and photoluminescence of the TPE-based self-assembled films. The experimental results showed that the TPE-based film with three bilayers only displayed AIE character, whereas the fluorescence of the film became randomly changed if the bilayer number was above three. It is supposed that the fluorescence property of the TPE-4OH/BD LBL SA film with limited molecular length in z-axis and infinite aggregation space in x-and y-axis is dominated by two competitive effects, one is the partial restriction of intramolecular rotation through short inter-molecular interactions in cross-linked structure of TPE-4OH/BD, and the other is deactivation of its excited state through unrestricted intramolecular rotations or π-π interactions.
Luminescent materials exhibiting emission switching in the solid state have drawn much attention though there is still no clear design strategy for such materials. In this letter, we reported the crystallization induced emission enhancement (CIEE) of di(4-ethoxyphenyl)dibenzofulvene (1), and achieved switching its emission among four different colors through modulation of its molecular packing patterns. We have investigated its potential application as optical recording materials. The twisted conformations of CIEE compounds afford morphology dependent emission and facilitate tuning their emission through modulation of molecular packing patterns. Thus we provide a possible design strategy for solid stimulus responsive luminescent materials.
LI ChenYuLUO XiaoLiangZHAO WeiJunHUANG ZheLIU ZhengPingTONG BinDONG YongQiang
2,3-Bis(4-(phenyl(4-(1,2,2-triphenylvinyl)phenyl)amino)phenyl) fumaronitrile (TPE-TPA-FN or TTF), which possesses aggregation-induced emission (AIE) characteristic, is doped in organically modified silica (ORMOSIL) nanoparticles. By increasing the weight ratio of TTF to the precursor of silica nanoparticles (the quantities of the precursors were kept the same), the fluorescence intensity of nanoparticles increased correspondingly, due to the formation of larger AIE dots in the cores of ORMOSIL nanoparticles. The fluorescent and biocompatible nanoprobes were then utilized for in vitro imaging of HeLa cells. Two-photon fluorescence microscopy clearly illustrated that the nanoparticles have the capacity of nucleus permeability, as well as cytoplasm staining towards tumor cells. Our experimental results may offer a promising method for fast and bright fluorescence imaging, as well as bio-molecule/drug delivery to cell nucleus.
