A Novel Fluorescent Probe for Lead Ions

A new fluorescent probe for lead ions, p-nitrophenyl 3H-phenoxazin-3-one-7-yl phosphoric acid (NPPA), has been synthesized by linking resorufLn (serving as a fluorophore and electron acceptor) to p-nitrophenol (serving as a fluorescence quencher and electron donor) through phosphodiester bonds. When NPPA was irradiated with light, intramolecular fluorescence self-quenching took place due to the PET (photoinduced electron transfer) from the donor to the acceptor. However, upon addition of Pb^Ⅱ, the phosphate ester bonds in the probe were cleaved and the fluorophore was released, accompanying the retrievement of fluorescence.     

Heptamethine cyanines in bioorthogonal chemistry

Due to their excellent fluorescence properties and biological function, cyanine dyes have been widely applied in biological imaging. Heptamethine cyanine(Cy7) dyes, as a type of classic near-infrared(NIR) fluorescent dyes, are considered as one of the effective fluorescent tools in the living organisms due to their good biocompatibility and very low background interference. Bioorthogonal reactions performed in living cells and tissues have developed by leaps and bounds in recent years. The NIR f...     

过渡金属离子识别的1，8-萘二甲酰亚氨衍生物作为荧光传感器的研究

Two fluorosensor systems have been designed and synthesized with their photophysical properties and fluorescence responses toward the transition metal ions studied. The fluorosensor was composed of 1,8-naphthalimide and 4-chloro-1,8-naphthalimide as fluorophore respectively, an amino moiety as the receptor and a hydrocarbon chain as the spacer to link the fluorophore and receptor. Fluorescence intensity of these systems is very weak due to the process of the efficient intramolecular photoinduced electron transfer （PET） in the absence of metal ions. Titration of the transition metal ions can switch on the fluorescence immediately. The intensity of released fluorescence is even higher than the expected from the consideration of the PET in these systems. It may be rationalized that the receptor bound to transition metal ions and the solvation of the fluorophore by the water molecules from the hydrated transition metal salts, may significantly cause fluorescence enhancement.     

Metal Ion Enhanced Phosphorescence of 2,3—Naphtho—10—aza—15—crown—5：A Possible Molecular Photonic Operator

A novel crown ether,2,3-naphtho-10-aza-15-crown-5(NAC) was synthesized.This compound does not show strong fluorescence and phosphorescence due to photoinduced intramolecular electron transfer from the nitrogen lone pair of electrons to the singlet excited state of the naphthalene chromophore.Complexation with heavy-metal ions results in the quenching of the fluorescence and enhancement of the phosphorescence significantly.These observations were interpreted in terms of the binding interactions,between the nitrogen lone pair electrons and the metal cation,which prevent photoinduced intramolecular electron transfer,and the heavy-atom effects which induce quenching of the fluorescence and enhancement of the phosphorescence.These azacrown and heavy-metalbased systems could be useful as potential chemical sensors and molecular photonic devices.     

Photoinduced intramolecular charge transfer of sodium 4-(N,N-dimethylamino) benzenesulfonate

A new dual fluorescent N,N-dimethylaniline derivative, sodium 4-(N,N-dimethylamino)-benzenesulfonate (SDMAS), is reported. In SDMAS, the electron acceptor is linked to the phenyl ring via a sulfur atom at the para-position of the electron donor. It was found that SDMAS emits dual fluorescence only in highly polar solvent water but not in organic solvents such as formamide, methanol and acetonitrile. In organic solvents only a single-band emission at ca.360 nm was observed in the short wavelength region. The dual fluorescence of SDMAS in water was found at 365 and 475 nm, respectively. Introduction of organic solvent such as ethanol, acetonitrile, and 1,4-dioxane into aqueous solution of SDMAS leads to blue-shift and quenching of the long-wavelength emission. Measurements of steady-state and picosecond time-resolved fluorescence indicate that the long wavelength fluorescence is emitted from a charge transfer (CT) state that is populated from the locally excited (LE) state, with the latter giving off the     

CO2/NIR light dual-controlled nanoparticles for dsDNA unzipping

Both of carbon dioxide(CO2)and near-infrared(NIR)light as triggers for non-invasive remotely control are attracting wide attentions due to their good biocompatibility and easy operation.Here,CO2/NIR light dual controlled nanoparticles are proposed to remotely regulate the unzipping of dsDNA by using imidazole functionalized conjugated polymer nanoparticles(imidazole-CPNs).The dsDNA successfully coats on the shell of imidazole-CPNs to form imidazole-CPNs/dsDNA assembly due to intensively electrostatic interaction triggered by CO2.Furthermore,the unzipping process of dsDNA is remotely controlled by NIR light based on the photothermal effect,and it can be readily monitored by the fluorescence intensity of ethidium bromide(EB)and CD spectra of dsDNA.Thus,dual stimulation responsive imidazole-CPNs effectively control dsDNA unzipping under CO2 stimulus and NIR light,promising a new direction in the biological applications of DNA,such as the treatments of diseases caused by gene duplication abnormality.     

Fluorescence Quenching of Poly[2-methoxy-5-（2′-ethylhexoxy）-p-phenylene vinylene] （MEH-PPV） in Solutions

Fluorescence quenching processes of poly[2-methoxy-5-(2‘ethyl-hexoxy)-p-phenylene vinylene] (MEH-PPV) in solution by electron acceptors, O2 and acid, have been studied. Static quenching of the fluorescence from MEH-PPV by an electron acceptor (DDQ or TCNE) occurs due to electron transfer from MEH-PPV to the electron acceptor and this electron transfer quenching can be promoted by chloroform. Photooxidation takes place in the MEH-PPV solution and singlet oxygen is an intermediate in the photooxidation, according to the results of ESR spectroscopy. Acid also plays an important role in the fluorescence quenching process of MEH-PPV, by the protonation of the alkoxy groups in the molecular chain.     

Fluorescence enhancing by alkaline degradation of tetracycline antibiotics and its application

Tetracycline antibiotics could be degraded after being beated in boiling-water bath in alkaline solution (in KOH medium).The fluorescence excitation and emission wavelengths of the degradation products changed and the fluorescence intensity increased by 5-190 folds as compared with that of antibiotics themselves It was considered that there occurred a nucleophilic ring rupture reaction to form the degradation products with lactome structure The mteraction of the lone pair electrons of oxygen on the degradation products with the conjugated π electrons induced the in crease of the delocalization for the conjugated electron system in the molecule and thus enhanced the fluorescence intensity.     

A near-infrared fluorescent probe for monitoring fluvastatin-stimulated endogenous H2S production

Most reported fluorescent probes have limitations in practical applications in living systems due to the strong autofluorescence background,construction of probes with near-infrared(NIR) fluorescence emission is an accessible approach for addressing this challenge.We here designed a NIR fluorescent probe for monitoring the endogenous production of H_2S in living cells.The designed probe showed significant NIR fluorescence turn-on response to H_2S with high selectivity,enabling the sensitive detection H_2S.Importantly,the probe could be applied in monitoring the endogenous production of H_2S in raw 264.7 macrophages.This study showed that fluvastatin can promote the activity of cystathionineγ-lyase(CSE) for generation H_2S.     

1-萘甲酰苯胺和2-萘甲酰苯胺的分子内电荷转移研究

A series of 1-naphthanilides (1) and 2-naphthanilides (2) with varied substituents at the para- or meta-position of anilino phenyl ring were prepared and their absorption and fluorescence spectra in a nonpolar solvent cyclohexane were investigated. An abnormal long wavelength emission assigned to the charge transfer (CT) state was found for all of the prepared naphthanilides in cyclohexane. A linear free energy correlation between the CT emission energies and the Hammett constants of the substituent was found within series 1 and 2. The value of the linear slope with 1 (0.42 eV) was higher than that with 2 (0.32 eV) being close to that of the substituted benzanilides 3 (0.31 eV) The higher slope value suggested higher charge separation extent in the CT state of 1 than that of 2. It was found that the corresponding linear slope of anilino-substituted benzanilides remained unchanged when para-, meta-, ortho-, or ortho, ortho-methyls were introduced into the anilino moiety, which ruled out the possible contribution of the difference in the steric effect and the electron accepting ability of the naphthoyl acceptor in 1 and 2. Compared with the early reported N-substituted-benzoyl-aminonaphthalene derivatives 4 and 5, it was considered that 1-naphthoyl enhanced the charge transfer in 1 and the proximity of its ^1La and ^1Lb states was suggested to be responsible. It was shown that 1- and/or 2-substituted naphthalene cores acting as either electron acceptor (naphthoyl) or electron donor (aminonaphthalene) were different in not only electron accepting (donating) ability but also shaping the charge transfer pathway.     

Anaphthalimide-based fluorescent probe for mercaptocontaining compounds

A polarity-sensitive fluorescent probe MNP was rationally designed and synthesized with naphthalimide as the fluorophore and maleimide as the receptor for thiols. MNP is weakly fluorescent due to the photoinduced electron-transfer(PET) from the fluorophore to the receptor, and it displays evidently solvatochromic UV–vis and fluorescence spectra: the emission shifted from 495 nm in n-hexane to545 nm in phosphate buffer solution. Michael addition reaction between thiols and the maleimide in MNP inhibited the PET process, which led to about eight-fold fluorescence enhancement. In addition,MNP showed highly sensitivity to mercapto-containing proteins and it could detect as low as 20.4 mg/m L of BSA in PBS. MNP has potential in fluorescent imaging of thiols in living cells.     

Preparation and recognition performance of ratio-fluorescent probe based on sulfadiazine imprinted polymersEI北大核心CSCD

A novel ratio-fluorescent probe based on molecular imprinting polymer ( MIP) for the detection of sulfadiazine was prepared by using nitrogen-doped carbon quantum dots (N-CQDs) as the fluorescence response signal, silica-embedded cadmium telluride quantum dots ( CdTe QDs) as the fluorescence reference signal, sulfadiazine ( SDZ) as template molecule, acrylamide as functional monomer, N, N-methyl bisacrylamide as crosslinking agent and 2,2-Azobisisobutyronitrile as initiator. The results showed that the probe has a core-shell structure and fluorescence sensitive to SDZ, by the characterization of scanning electron microscopy, transmission electron microscopy, and fluorescence spectrophotometer. Under the wavelength of 360 nm, the ratio-fluorescent signal of probe showed a linear response with SDZ concentration in the range of 0-100 μmol / L with the detection limit of 11 nmol / L. Also, the ratio-fluorescent probe was applied to the detection of SDZ with a recovery of 92. 0%-95. 1% and relative standard deviation (RSD) of 3. 6% in real water samples. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

State-crossing from a Locally Excited to an Electron Transfer State(SLEET) Model Rationalizing the Aggregation-induced Emission Mechanism of (Bi)piperidylanthracenes

Luminogens with aggregation-induced emission(AIE)characteristics(or AIEgens)have been widely used in various applications due to their excellent luminescent properties in molecular aggregates and the solid state.A deep understanding of the AIE mechanism is critical for the rational development of AIEgens.In this work,the“state-crossing from a locally excited to an electron transfer state”(SLEET)model is employed to rationalize the AIE phenomenon of two(bi)piperidylanthracenes.According to the SLEET model,an electron transfer(ET)state is formed along with the rotation of the piperidyl group in the excited state of(bi)piperidylan-thracene monomers,leading to fluorescence quenching.In contrast,a bright state exists in the crystal and molecular aggregates of these compounds,as the intermolecular interactions restrict the formation of the dark ET state.This mechanistic understanding could inspire the deployment of the SLEET model in the rational designs of various functional AIEgens.     

Studies on photooxidation (VIII)——Electron transfer photooxygenation mechanism of acenaphthenone as electron donor

The photooxidation and its electron transfer (ET) mechanism of acenaphthenone (ANO) sensitized by 9,10-dicyanoanthracence (DCA) are investigated. It has been found that the reaction with a stepwise manner led to the formation of 1,8- (3'-hydroxy)-β-naphthalene lactone and 1,8-naphthalenedicarboxylic anhydride. By cyclic voltammetry, fluorescence quenching, exciplex emission, co-sensitbation of biphenyl/DCA as well as CIDNP studies, it is verified that ANO can behave as an electron donor to undergo ET reaction with singlet DCA which is a thermodynamically-favored process.     

基于对二烷基氨基苯甲酰苯胺分子内电荷转移的单糖比值法荧光受体

Two dual fluorescent receptors (1 and 2) for monosaccharides based on 4-dialky(alkyl=methyl and n-butyl) containing boronic acid group at the amido aniline were synthesized and their spectral properties were investigated. These receptors exhibited dual fluorescence with the long-wavelength band displaying strong solvent-polarity dependence, indicating the occurrence of the excited-state intramolecular charge transfer （ICT).With increasing pH value in aqueous solutions, the hybridization of the boron atom changed from sp^2 to sp^3, inducing a decrease in the total fluorescence quantum yield. The experimental results indicated that the anionic form of the boronate group acted as an electron donor and the benzanilide-like charge transfer was promoted upon hybridization change. In the presence of monosaccharides, the boronic acid in 1 and 2 changed from neutral to anionic form. The intensity of the locally excited (LE) state emission decreased in the presence of sugars while a slight increase in the intensity at the charge transfer (CT) emission occurred. Based on the change in the CT to LE intensity ratios of 1 and 2 due to sugar binding, ratiometric fluorescent assays for monosaccharide sensing were established.     

Crystal Structure,One-and Two-photon Excited Fluorescence and Bioimaging of a D-π-A Structural Triphenylamine Derivative

An electron donor-π-bridge-electron acceptor(D-π-A) optical functional organic compound comprising a triphenylamine moiety as the electron donor and pyridine moiety as the electron acceptor was synthesized. The structure of the compound was solved by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21, with a = 9.753(5), b = 8.815(5), c = 25.554(5) ?, β = 96.315(5)°, V = 2184(2) ?~3, Z = 2, D_c = 1.136 g/m~3, F(000) = 792, Μr = 746.92, μ = 0.069 mm~(-1), the final R = 0.0658 and wR = 0.1730 for 6790 observed reflections with I 2(I). Study of nonlinear optical properties shows that the compound exhibits excellent two-photon excited fluorescence with the two-photon absorption cross-section value of 116 GM. The structure-property relationship was researched in detail through X-ray crystallography and quantum chemical calculation. Result of living cell imaging experiment shows its potential in fluorescence microscopy bioimaging.     

Determination of Sparfloxacin in Human Urine by Reversed-Phase High Performance Liquid Chromatography With Nitrous Acid and Hydroiodic Pre-Column Derivatization

Quinolone drugs, due to the aromatic systems with benzoheterocycle in their molecules, can usually emit strong fluorescence. However, contrary to this, sparfloxacin (SPFX) as the fourth generation quinolone products, can only emit weak fluorescence, although it possesses a similar structure to quinolones. At present, the majority of SPFX determinations have been carried out using techniques such as colorimetry1 and spectrophotometry2-3. For the high performance liquid chromatography (HP…     

Molecularly near-infrared fluorescent theranostics for in vivo tracking tumor-specific chemotherapy

Molecularly near-infrared(NIR) theranostics, combining in vivo sensing and tumor-specific therapeutic capability within one molecular system, have received considerable attention in recent years. Compared with the visible fluorescence imaging, NIR imaging(emission wavelength at 650–900 nm) possesses unique advantages including the minimum photodamage to biological samples, deep penetration, and low interference from auto-fluorescence. In over past decades, there has been an explosive development in the design of molecular imaging contrasts and imaging-guided therapeutics. In this review, we have sumarried the strategies of the NIR theranostics for imaging and tumor-specific chemotherapy applications in living systems. It is noted that the molecularly NIR theranostic design strategy could address current challenges of real-time in vivo sense-and-release for the intelligent biosensing and personalized treatment.     

Polymer Vesicles with Upper Critical Solution Temperature for Near-infrared Light-triggered Transdermal Delivery of Metformin in Diabetic Rats

Near-infrared light(NIR)triggered transdermal drug delivery systems are of great interest due to their on-demand drug release,which enable to enhance drug treatment efficiency as well as reduce side effect.Herein,a NIR-triggered microneedle(MN)patch array has been fabricated through depositing the photothermal conversion agent and anti-diabetic drug-loaded polymer vesicles with upper critical solution temperature(UCST)into dissolvable polymer matrix.The UCST-type polymer has a clearing point temperature of 41℃ and the drug-loaded polymer vesicles present excellent NIR-triggered and temperature responsive drug release behavior in vitro due to the disassociation of polymer vesicles upon NIR irradiation.After applying MNs to diabetic rats,significant hypoglycemic effect is achieved upon interval NIR irradiation and the blood glucose concentration can decrease to normal state for several hours,which enables to achieve the goal of on-demand drug release.This work suggests that the NIR-triggered MN drug release device has a potential application in the treatment of diabetes,especially for those requiring an active drug release manner.     

Mitochondria-targeting NIR fluorescent probe for rapid,highly sensitive and selective visualization of nitroxyl in live cells,tissues and mice

Nitroxyl(HNO)has been reported to possess unique biological and pharmacological performances,and emerged as a novel therapy for congestive heart failure.Recent studies also suggest that HNO may be produced and involved in important metabolisms in mitochondria.However,due to its high reactivity and short life properties,fast,sensitive and selective observation and monitoring of HNO related dynamic changes in mitochondria still remains a great challenge.Herein,we synthesized a mitochondria-targeting near-infrared(NIR)fluorescent probe(DCMHNO)for rapid detection of HNO with remarkably high sensitivity,selectivity and photostability.DCMHNO shows fast response(about 4 min)towards HNO via 2-(diphenylphosphino)benzoyl group through the Staudinger reaction to boost the bright NIR emission(700 nm)with excellent sensitivity(detection limit of 13 nM),high p H stability and very low interference from other species.DCMHNO can selectively locate in mitochondria and visualize exogenous and endogenous HNO in live He La cells with high biocompatibility and photostability.The probe could also monitor the interaction between NO and H2 S that gives rise to the generation of HNO in live He La cells.In addition,DCMHNO was further utilized in ex vivo NIR imaging of HNO in live mouse liver tissues at the depth of about 50μm.In vivo imaging of HNO with high signal-to-noise ratio in live mice was also realized by using DCMHNO.These remarkable imaging performances could render NIR DCMNHNO as a useful tool to reveal HNO related dynamic changes in live samples.