Optical Properties and Response Mechanism Analysis of Multi-branched Fluorescent Probes Based on Intramolecular Charge Transfer

In this work, the optical properties of fluorescent probes used for detection of biothiol were studied by employing time-dependent density functional theory. By calculating the single photon absorption and emission properties of probe Mol.1, Mol.2 and Mol.3 before and after reaction with cysteine and homocysteine, we have investigated the effect of carboncarbon triple bond and benzene ring on the properties of fluorescent probes. It is found that the oscillator strength of probe molecules increases gradually with the improvement of the structure of the electron donor triphenylamine and the addition of carbon-carbon triple bonds, and better properties of fluorescence probes have also been demonstrated. At the same time, the effect of different number of side branches on the molecular properties of the probe was also studied. The results showed that compared with single-branched molecule Z1 and tribranched probe Mol.3, two side probe molecules Z2 had higher oscillator strength and better detection effect. In addition, the new single-branched probe Mol.4 with the addition of carbon-carbon triple bonds and benzene rings has better probe properties and simpler structure than the tribranched probe Mol.3.

Responsive mechanism and molecular design of di-2-picolylamine-based two-photon fluorescent probes for zinc ions

The properties of one-photon absorption（OPA）, emission and two-photon absorption（TPA） of a di-2-picolylaminebased zinc ion sensor are investigated by employing the density functional theory in combination with response functions.The responsive mechanism is explored. It is found that the calculated OPA and TPA properties are quite consistent with experimental data. Because the intra-molecular charge transfer（ICT） increases upon zinc ion binding, the TPA intensity is enhanced dramatically. According to the model sensor, we design a series of zinc ion probes which differ by conjugation center, acceptor and donor moieties. The properties of OPA, emission and TPA of the designed molecules are calculated at the same computational level. Our results demonstrate that the OPA and emission wavelengths of the designed probes have large red-shifts after zinc ions have been bound. Comparing with the model sensor, the TPA intensities of the designed probes are enhanced significantly and the absorption positions are red-shifted to longer wavelength range. Furthermore, the TPA intensity can be improved greatly upon zinc ion binding due to the increased ICT mechanism. These compounds are potential excellent candidates for two-photon fluorescent zinc ion probes.

A novel carbazole-based fluorescent probe:3,6-B is-[(N- ethylcarb azole- 3-yl)-propene- 1-keto]-N-ethylc arb azole

A novel carbazole-based compound 5,3,6-bis[(N-ethylcarbazole-3-yl)-propene-1-keto]-N-ethylcarbazole has been designed, synthesized and characterized.The absorption and fluorescence spectra in solvents of different polarities prove that the compound has a distinct intramolecular charge transfer character.Compound 5 can be used as a new class of fluorescent probe or biosensor due to its sensitivity to the local microenvironment such as solvent polarity.

A Highly Selective and Sensitive Ratiometric Fluorescent Probe for pH Measurement Based on Fluorescence Resonance Energy Transfer

Fluorescein-rhodamine 6G（Flu-Rh） was synthesized and used as the fluorescence probe for pH measurement based on fluorescence resonance energy transfer（FRET）. In the probe, fluorescein fluorophore and pH-sensitive rhodamine 6G hydrazide were used as FRET donor and acceptor, respectively. The values of acidity constant（pKa） and fluorescence quantum yield（Ф） of Flu-Rh were 3.71 and 0.72, respectively. The fluorescence efficiency of Flu-Rh remains almost constant when the pH value of the sample solution changed 10 times in a range of 4.78-7.03 continuously. The present probe is simple and easy-to-use for the pH measurement in acidic media.

Monitoring the in vivo siRNA release from lipid nanoparticles based on the fluorescence resonance energy transfer principle

The siRNA-loaded lipid nanoparticles have attracted much attention due to its significant gene silencing effect and successful marketization.However,the in vivo distribution and release of siRNA still cannot be effectively monitored.In this study,based on the fluorescence resonance energy transfer(FRET)principle,a fluorescence dye Cy5-modified survivin siRNA was conjugated to nanogolds(Au-DR-siRNA),which were then wrapped with lipid nanoparticles(LNPs)for monitoring the release behaviour of siRNA in vivo.The results showed that once Au-DR-siRNA was released from the LNPs and cleaved by the Dicer enzyme to produce free siRNA in cells,the fluorescence of Cy5 would change from quenched state to activated state,showing the location and time of siRNA release.Besides,the LNPs showed a significant antitumor effect by silencing the survivin gene and a CT imaging function superior to iohexol by nanogolds.Therefore,this work provided not only an effective method for monitoring the pharmacokinetic behaviour of LNP-based siRNA,but also a siRNA delivery system for treating and diagnosing tumors.

A mini review and hypothesis for coronavirus detection using photonics: surface enhanced Raman scattering and fluorescence resonance energy transfer

COVID-19 has devastated numerous nations around the world and has overburdened numerous healthcare systems,which has also caused the loss of livelihoods due to prolonged shutdowns and further led to a cascading effect on the global economy.COVID-19 infections have an incubation period of 2–7 days,but 40 to 45%of cases are asymptomatic or show mild to moderate respiratory symptoms after the period due to subclinical lung abnormalities,making it more likely to spread the pandemic disease.To restrict the spread of the virus,on-site diagnosis methods that are quicker,more precise,and easily accessible are required.Rapid Antigen Detection Tests and Polymerase Chain Reaction tests are currently the primary methods used to determine the presence of COVID-19 viruses.These tests are typically time-consuming,not accurate,and,more importantly,not available to everyone.Hence,in this review and hypothesis,we proposed equipment that employs the properties of photonics to improve the detection of COVID-19 viruses by taking the advantage of typical binding of coronavirus with angiotensin-converting enzyme 2(ACE2)receptors.This hypothetical model would combine Surface-Enhanced Raman Scattering(SERS)and Fluorescence Resonance Energy Transfer(FRET)to provide great flexibility,high sensitivities,and enhanced accessibility.

Ultrafast Energy Transfer in Artificial Antenna Molecule Measured by Transient Fluorescence Spectroscopy

We have reported previously the ultrafast energy transfer process with a time constant of 0.8 ps from a monomeric to a dimeric subunit within a perylenetetracarboxylic diimide trimer, which was derived indirectly from a model fitting into the transient absorption experimental data. Here we present a direct ultrafast fluorescence quenching measurement by employing fs time-resolved transient fluorescence spectroscopy based on noncollinear optical parametric amplification technique. The rapid decay of the monomer＇s emission due to energy transfer was observed directly with a time constant of about 0.82 ps, in good agreement with the previous result.

Fluorescence spectrum characteristic of ethanol-water excimer and mechanism of resonance energy transfer

The steady-state fluorescence spectrum characteristic of ethanol-water excimer has been studied in this paper. By analysing the features of the sharp emission spectrum with fine structures in a shortwave band and the characteristics of the broad and featureless fluorescence peaks in the longwave band, one can conclude that the excimers are formed between the new ethanol-water cluster molecules in the excited state and the ground state through the interaction among different chromophores. The excitation spectra in the two fluorescence bands have been studied, and their emission mechanisms have been ascertained based on the energy transfer theory. Furthermore, the critical distance of the resonance energy transfer has been calculated.

Screening and identification of bioactive compounds from citrus against non-structural protein 3 protease of hepatitis C virus genotype 3a by fluorescence resonance energy transfer assay and mass spectrometry

BACKGROUND Hepatitis C virus genotype 3a(HCV G3a)is highly prevalent in Pakistan.Due to the elevated cost of available Food and Drug Administration-approved drugs against HCV,medicinal natural products of potent antiviral activity should be screened for the cost-effective treatment of the disease.Furthermore,from natural products,active compounds against vital HCV proteins like non-structural protein 3(NS3)protease could be identified to prevent viral proliferation in the host.AIM To develop cost-effective HCV genotype 3a NS3 protease inhibitors from citrus fruit extracts.METHODS Full-length NS3 without co-factor non-structural protein 4A(NS4A)and codon optimized NS3 protease in fusion with NS4A were expressed in Escherichia coli.The expressed protein was purified by metal ion affinity chromatography and gel filtration.Citrus fruit extracts were screened using fluorescence resonance energy transfer(FRET)assay against the protease and polyphenols were identified as potential inhibitors using electrospray ionization-mass spectrometry(MS)/MS technique.Among different polyphenols,highly potent compounds were screened using molecular modeling approaches and consequently the most active compound was further evaluated against HCV NS4A-NS3 protease domain using FRET assay.RESULTS NS4A fused with NS3 protease domain gene was overexpressed and the purified protein yield was high in comparison to the lower yield of the full-length NS3 protein.Furthermore,in enzyme kinetic studies,NS4A fused with NS3 protease proved to be functionally active compared to full-length NS3.So it was concluded that co-factor NS4A fusion is essential for the purification of functionally active protease.FRET assay was developed and validated by the half maximal inhibitory concentration(IC50)values of commercially available inhibitors.Screening of citrus fruit extracts against the native purified fused NS4A-NS3 protease domain showed that the grapefruit mesocarp extract exhibits the highest percentage inhibition 91%of protease activity.Among the compounds identified by LCMS analysis,hesperidin showed strong binding affinity with the protease catalytic triad having S-score value of-10.98.CONCLUSION Fused NS4A-NS3 protease is functionally more active,which is effectively inhibited by hesperidin from the grapefruit mesocarp extract with an IC50 value of 23.32μmol/L.

Highly-efficient quantitative fluorescence resonance energy transfer measurements based on deep learning

Intensity-based quantitative fluorescence resonance energy transfer(FRET)is a technique to measure the distance of molecules in scale of a few nanometers which is far beyond optical diffraction limit.This widely used technique needs complicated experimental process and manual image analyses to obtain precise results,which take a long time and restrict the application of quantitative FRET especially in living cells.In this paper,a simplified and automatic quanti-tative FRET(saqFRET)method with high efficiency is presented.In saqFRET,photo-activatable acceptor PA-mCherry and optimized excitation wavelength of donor enhanced green fluorescent protein(EGFP)are used to simplify FRET crosstalk elimination.Traditional manual image analyses are time consuming when the dataset is large.The proposed automatic image analyses based on deep learning can analyze 100 samples within 30 s and demonstrate the same precision as manual image analyses.

Investigation of fluorescence resonance energy transfer ultrafast dynamics in electrostatically repulsed and attracted exciton-plasmon systems

Following the gradual maturation of synthetic techniques for nanomaterials,exciton-plasmon composites have become a research hot-spot due to their controllable energy transfer through electromagnetic fields on the nanoscale.However,most reports ignore fluorescence resonance energy transfer(FRET)under electrostatic repulsion conditions.In this study,the FRET process is investigated in both electrostatic attraction and electrostatic repulsion systems.By changing the Au:quantum dot ratio,local-field induced FRET can be observed with a lifetime of ns and a fast component of hundreds of ps.These results indicate that the intrinsic transfer process can only elucidated by considering both steady and transient state information.

Retraction Note:Screening and identification of bioactive compounds from citrus against non-structural protein 3 protease of hepatitis C virus genotype 3a by fluorescence resonance energy transfer assay and mass spectrometry

Retraction note:Khan M,Rauf W,Habib F,Rahman M,Iqbal M.Screening and identification of bioactive compounds from citrus against non-structural protein 3 protease of hepatitis C virus genotype 3a by fluorescence resonance energy transfer assay and mass spectrometry.World J Hepatol 2020;12(11):976-992 PMID:33312423 DOI:10.4254/wjh.v12.i11.976.The online version of the original article can be found at https://www.wjgnet.com/1948-5182/full/v12/i11/976.htm.

Vinyl Groups Containing Tetraphenylethylene Derivatives as Fluorescent Probes Specific for Palladium and the Quenching Mechanism

We previously reported that a series of tetraphenylethylene(TPE)-containing all-hydrocarbon conjugated polymers exhibited a specific fluorescence quenching by palladium ions(Pd^(2+)).To understand the quenching mechanism,herein we investigate the quenching behaviors of three TPE derivatives in the presence of Pd^(2+).Each TPE derivative,consisting of TPE unit and terminal vinyl groups,shows an aggregation-induced emission(AIE)and its fluorescence turns off specifically to Pd^(2+).The sensitivity is enhanced with increasing numbers of vinyl groups in the molecules.By time-resolved fluorescence measurement,a dynamic quenching is observed where the fluorescence lifetime is reduced with Pd^(2+).Specifically,the quenching occurs via the electron transfer in the excited states,as suggested by the disappearance of the stimulated emission band in transient absorption spectra.A theoretical calculation on the excited states identifies intermolecular electron transfer from TPE derivatives to Pd,especially for electron-rich TPE derivative.The mechanism can be general for the design of novel AIE active chemosensors.

Naphthalimide-rhodamine based fluorescent probe for ratiometric sensing of cellular pH

The pH values of lysosomes in cancer cells is slightly lower than that in normal cells, which can be used to distinguish cancer cells from normal cells. According to this, a naphthalimide-rhodamine based fluorescent probe（hereafter referred to as RBN） with a pK_a of 4.20 was designed and synthesized for ratiometric sensing of cellular pH via fluorescence resonance energy transfer（FRET）, which can respond to different pH precisely through ratiometric fluorescence intensity（Ⅰ_（577）/Ⅰ_（540））. RBN can be employed to distinguish cancer cells from normal cells on the basis of different fluorescent response, in particular, RBN showed excellent water solubility and low cell toxicity, all these are quite significant for potential application in cancer diagnose and therapy.

Fabricating UCNPs-AuNPs Fluorescent Probe for Sensitive Sensing Thiamphenicol

A novel fluorescent probe has been constructed based on fluorescence resonance energy transfer(FRET)between upconversion nanomaterials(UCNPs)NaYF4:Yb,Er and gold nanoparticles(AuNPs).The fluorescent“off-on”switching was formed for the detection of thiamphenicol(TAP)in egg samples.The fluorescence of UCNPs can be quenched to a certain degree by AuNPs.After adding TAP,the AuNPs generated aggregation and the fluorescence of UCNPs was recovered.The synthesized amination UCNPs and AuNPs were characterized by Fourier transform infrared spectroscopy(FTIR),UV-Vis,X-ray diffraction(XRD),energy dispersive spectrometer(EDS),and transmission electron microscope(TEM)techniques for observation and confirmation.As a model target,the detection of TAP has two linear ranges in the buffer solution within 0.01–0.1µmol/L and 0.1–1µmol/L using this fluorescent probe.The detection limit was obtained to be 0.003µmol/L(S/N=3),which is favorable for trace analysis.The recovery of TAP from 98.2%to 105.3%was obtained,and the relative standard deviation(RSD)was from 2.5%to 4.3%.Furthermore,the method established in this study based on the UCNPs auto-low background fluorescence has high selectivity and strong ability to eliminate interference,which is beneficial to analyzing complex samples.

Photoluminescence properties and energy transfer in Y_2O_3:Eu^(3+) nanophosphors

The photoluminescence （PL） properties of Y203 ：Eu^3＋ nanophosphors were systematically investigated with the goal of improving the color quality and quantum efficiency of Y2O3 ：Eu^3＋ nanophosphors for potential applications in nano-scale devices. The emission spectra, excitation spectra and fluorescence decay curves were employed to trace the energy transfer process from Eu^3＋ at C3i site to Eu^3＋ at C2 site. The experimental results show that the energy transfer process becomes more and more efficient with the increase in the Eu^3＋ concentration. The emission of Eu^3＋ at C2 site is favorable because it has high radiative efficiency and better color quality. The successful suppress of the emission Eu^3＋ at C3i is especially important for its applications in general illumination or display technology. The quantum efficiency and color quality of Y203 ：Eu^3＋ can be improved by controlling the energy transfer between the Eu^3＋ at S6 site and Eu^3＋ at C2 site.

Rational Design of Ratiometric Fe^(3+) Fluorescent Probes Based on FRET Mechanism

As the most abundant transition metal element in mammals, iron(Fe) plays a vital role in life activities. It is of great significance to study the variation of Fe3+ level in living organisms. In virtue of the advantages of high sensitivity, good selectivity and low damage to living systems, the fluorescence detection of Fe3+ has attracted much attention. Compared with the intensity-based fluorescent probe, the ratiometric fluorescent probe has less interference of environmental and can realize quantitative detection. In this study, four ratiometric Fe3+ fluorescent probes, R1, R2, R3 and R4, were designed and synthesized using fluorescence resonance energy transfer(FRET) mechanism to achieve quantitative detection of Fe3+. In the FRET systems, 1,8-naphthalimide fluorophore derivatives were adopted as donors while rhodamine B derivatives were selected as receptors. The connection sites of the donor and acceptor in R3 and R4 are different from those in R1 and R2. All the four probes showed good response and selectivity to Fe3+. The energy transfer efficiencies of R3 and R4 were obviously higher than those of R1 and R2. This work provided a promising strategy for the development of fluorescent ratiometic Fe3+sensors.

Computational design of ratiometric two-photon fluorescent Zn2+probes based on quinoline and di-2-picolylamine moieties

To improve two-photon absorption(TPA)response of a newly synthesized probe,a series of ratiometric two-photon fluorescent Zn^(2+) sensors based on quinoline and DPA moieties have been designed.The one-photon absorption,TPA,and emission properties of the experimental and designed probes before and after coordination with Zn^(2+) are investigated employing the density functional theory in combination with response functions.The design consists of two levels.In the first level of design,five probes are constructed through using several electron acceptors or donors to increase accepting or donating ability of the fluorophores.It shows that all the designed probes have stronger TPA intensities at longer wavelengths with respect to the experimental probe because of the increased intra-molecular charge transfer.Moreover,it is found that the probe 4 built by adding an acyl unit has the largest TPA cross section among the designed structures due to the form of longer conjugated length and more linear backbone.One dimethylamino terminal attached along the skeleton can improve TPA intensity more efficiently than two side amino groups.Therefore,in the second level of design,a new probe 7 is formed by both an acyl unit and a dimethylamino terminal.It exhibits that the TPA cross sections of probe 7 and its zinc complex increase dramatically.Furthermore,the fluorescence quantum yields of the designed probes4 and 7 are calculated in a new way,which makes use of the relation between the computed difference of dipole moment and the measured fluorescence quantum yield.The result shows that our design also improves the fluorescence quantum yield considerably.All in all,the designed probes 4 and 7 not only possess enhanced TPA intensities but also have large differences of emission wavelength upon Zn^(2+) coordination and strong fluorescence intensity,which demonstrates that they are potential ratiometric two-photon fluorescent probes.

A microenvironment sensitive pillar[5]arene-based fluorescent probe for cell imaging and drug delivery

Dansylamide(DNSA) is a typical ICT probe that has a favorable serum albumin sensitivity. Inspired by this, we designed a microenvironment sensitive fluorescent probe 4 C-G through introducing DNSA into pillar[5]arene. Unlike DNSA, 4 C-G displayed differentiated sensitivity to multiple proteins, which was benefit from pillar[5]arene assisted the probe to form complexes with proteins. 4 C-G could not only be applied in imaging of Hep G2, but also act as a favorable drug carrier for regorafenib(REG) encapsulation.The 4 C-G-REG complex would aggregate into high drug-loading fluorescent nanoparticles in a physiological environment(pH 7.4). Such nanoparticles exhibited p H-triggered enrichment ability, which rapidly enriched REG in the acidic environment(pH 6.0). Furthermore, the complexation between 4 C-G and REG maintained the imaging property of the probe and the excellent anticancer activity of the drug on Hep G2.