Time-dependent Fluorescence Research Articles

Effect of load-resisting force on photoisomerization mechanism of a single second generation light-driven molecular rotary motor.

A pivotal aspect of molecular motors is their capability to generate load capacity from a single entity. However, few studies have directly characterized the load-resisting force of a single light-driven molecular motor. This research provides a simulation analysis of the load-resisting force for a highly efficient, second-generation molecular motor developed by Feringa et al. We investigate the M-to-P photoinduced nonadiabatic molecular dynamics of 9-(2,3-dihydro-2-methyl-1H-benz[e]inden-1-ylidene)-9H-fluorene utilizing Tully's surface hopping method at the semi-empirical OM2/MRCI level under varying load-resisting forces. The findings indicate that the quantum yield remains relatively stable under forces up to 0.003a.u., with the photoisomerization mechanism functioning typically. Beyond this threshold, the quantum yield declines, and an alternative photoisomerization mechanism emerges, characterized by an inversion of the central double bond's twisting direction. The photoisomerization process stalls when the force attains a critical value of 0.012a.u. Moreover, the average lifetime of the excited state oscillates around that of the unperturbed system. The quantum yield and mean lifetime of the S1 excited state in the absence of external force are recorded at 0.54 and 877.9fs, respectively. In addition, we analyze a time-dependent fluorescence radiation spectrum, confirming the presence of a dark state and significant vibrations, as previously observed experimentally by Conyard et al.

Light-Operated Diverse Logic Gates Enabled by Modulating Time-Dependent Fluorescence of Dissipative Self-Assemblies.

Light-fueled dissipative self-assembly possesses enormous potential in the field of optical information due to controllable time-dependent optical signals, but remains a great challenge for constructing intelligent light-operated logic circuits due to the limited availability of optical signal inputs and outputs. Herein, a series of light-fueled dissipative self-assembly systems with variable optical signals are reported to realize diverse logic gates by modulating time-dependent fluorescence variations of the loaded fluorophores. Three kinds of alkyl trimethylammonium homologs are employed to co-assemble with a merocyanine-based photoinduced amphiphile separately to construct a series of dissipative self-assemblies, showing unexpectedly different fluorescence control behaviors of loaded fluorophores during light irradiation and thermal relaxation processes. The opposite monotonicity of time-dependent emission intensity is achieved just by changing the excitation wavelength. Furthermore, by varying the types of trimethylammoniums and excitation wavelengths, a robust logic system is accomplished, integrating AND, XNOR, and XOR functions, which provides an effective pathway for advancing information transmission applications.

Reversible Multi-Color optical switch utilizing tetraphenylethylene and spiropyran Complexes: Applications in advanced information encryption

In this paper, we introduced a strategic methodology to obtain time-resolved encryption utilizing a new technique. This method utilizes a reversible supramolecular optical switch, which is based on complexes consisting of tetraphenylethylene and spiropyran. Notably, these components are separately attached at the focal point of the same cholesterol-based unit, wherein the cholesterol-based unit can provide the essential driving forces to form complexes. A series of complexes were prepared with varying molar ratios (TPE/SP), allowing for the tuning of fluorescence emission. The supramolecular system leverages hydrogen bonding, van der Waals forces, and other non-covalent interactions to orchestrate the collaboration between the fluorophores (tetraphenylethylene) and the photochromic molecule (spiropyran). This coordination results in exceptional photochromic attributes, including rapid response, high contrast, and the capability to regulate fluorescence. The system is capable of achieving tunable dynamic fluorescence emission that transitions from brilliant blue to light purple and finally to red through fluorescence resonance energy transfer (FRET) after successive irradiation periods. Additionally, by fine-tuning the ratio of tetraphenylethylene to spiropyran, different dynamic fluorescence emission can be precisely manipulated. It is rarely reported that complexes accomplish time-dependent fluorescence emission with high-contrast. We are confident that the complexes, grounded on cholesterol unit, hold promise for broader applicability in developing innovative time-dependent fluorescent materials. Such materials can be effectively utilized for time-dependent information encryption, thereby bolstering security measures against unauthorized access.

Hydrogen Bond-Associated Photofluorochromism for Time-Resolved Information Encryption and Anti-counterfeiting.

Time-resolved photofluorochromism constitutes a powerful approach to enhance information encryption security but remains challenging. Herein, we report a strategy of using hydrogen bonds to regulate the time for initiating photofluorochromism. In our strategy, copolymers containing negative photochromic spiropyran (NSP), naphthalimide, and multiple hydrogen-bonding (UPy) units are designed, which display photo-switchable fluorescence resonance energy transfer (FRET) process from naphthalimide donor to the NSP acceptor. Interestingly, the FRET is locked via the dynamic hydrogen-bonding interaction between ring-opened NSP and UPy moieties, resulting in time-dependent fluorescence. The change in fluorescence can be finely regulated via UPy fraction in the polymers. Besides the novel time-dependent fluorescence, the polymers also take advantage of visible-light triggerable, excellent photostability, photoreversibility, and processability. We demonstrate that these properties enable them many application opportunities such as fluorescent security labels and multilevel information encryption patterns.

“Double-locked” fluorescent probe based on a push-pull structure for detecting HClO/H2O2

Fluorophores with “push-pull” electronic structures can quench their fluorescence by shielding either part, and can be easily used to construct “double-locked” fluorescent probes. At present, research in this area is still rare. To demonstrate its feasibility, here we selected 6-acetyl-2-naphthol, a simple fluorophore with a characteristic “push-pull” structure (hydroxy-ketone) to construct a double-locked probe for the detection of HClO/H2O2. Specifically, 1,3-oxathiolane was employed as an HClO-responsive group to shield the ketone (pull group), while the hydroxy (push group) was protected by an H2O2-responsive boronate ester group, resulting in the HClO/H2O2-specific probe Sa1. In vitro experiments confirmed that Sa1 emits fluorescence only in the presence of both HClO and H2O2, exhibiting remarkable concentration- and time-dependent fluorescence responses. Additionally, Sa1 displayed excellent selectivity and low toxicity. Finally, through cell and zebrafish imaging experiments, the dual detection capability of Sa1 in biological systems was validated.

Unveiling the Influence of Glutathione in Suppressing the Conversion of Aspirin to Salicylic Acid: A Fluorescence and DFT Study.

Aspirin is a commonly used nonsteroidal anti-inflammatory drug, associated with many adverse effects. The adverse effects of aspirin such as tinnitus, Reye's syndrome and gastrointestinal bleeding are caused due to conversion of aspirin into its active metabolite salicylic acid after oral intake. Glutathione is a naturally occurring antioxidant produced by the liver and nerve cells in the central nervous system. It helps to metabolize toxins, break down free radicles, and support immune function. This study aims to investigate and explore the possibility of inhibiting aspirin to salicylic acid conversion in presence of glutathione at a molecular level using spectroscopic techniques such as UV-Visible absorption, time-Resolved and time-dependent fluorescence and theoretical DFT/ TD-DFT calculations. The results of steady state fluorescence spectroscopy and time-dependent fluorescence indicated that the aspirin to salicylic acid conversion is considerably inhibited in presence of glutathione. Further, the results presented here might have significant clinical implications for individuals with variations in glutathione level.

Ratiometric fluoroprobe based on Eu-MOF@Tb3+ for detecting tetracycline hydrochloride in freshwater fish and its application in rapid visual detection

Tetracycline hydrochloride (TCH), a prevalent antibiotic in aquaculture for treating bacterial infections, poses challenges for on-site detection. This study employed the reversed-phase microemulsion method to synthesize a uniform nano metal-organic framework (MOF) material, europium-benzene-p-dicarboxylic acid (Eu-BDC), doped with Tb3+ to form a dual-emission fluorescence probe. By leveraging the combined a-photoinduced electron-transfer (a-PET) and inner filter effect (IFE) mechanisms, high-sensitivity TCH detection in Carassius auratus and Ruditapes philippinarum was achieved. The detection range for TCH is 0.380–75 μM, with a low limit of detection (LOD) at 0.115 μM. Upon TCH binding, Eu-BDC fluorescence rapidly decreased, while Tb3+ fluorescence remained constant, establishing a ratiometric fluorescence change. Investigation into the TCH quenching mechanism on Eu-BDC was conducted using time-dependent density functional theory (TD-DFT) calculations and fluorescence quenching kinetic equations, suggesting a mixed quenching mechanism. Furthermore, a novel photoelectric conversion fluorescence detection device (FL-2) was developed and evaluated in conjunction with high-performance liquid chromatography-diode-array detection (HPLC-DAD). This is the first dedicated fluorescence device for TCH detection, showcasing superior photoelectric conversion performance and stability that reduces experimental errors associated with smartphone photography methods, presenting a promising avenue for on-site rapid TCH detection.

Dynamic Fluorescence Materials Based on Naphthalimide-Functionalized Silica Aerogels and Applications in Advanced Information Encryption.

With the progress of forgery and decryption, the traditional encryption technology is apparent not enough, which strongly requires the development of advanced multidimensional encryption strategies and technologies. Photo-stimuli responsive fluorescent materials are promising as candidate materials for advanced information encryption. Here, we have reported new photo-stimuli responsive materials by encapsulating photochromic molecules spiropyrans (SPs) into naphthalimide-functionalized silica aerogels. By introducing different modification groups (dimethylamino) into 1,8-naphthalimide, we obtained two kinds of silica aerogels that emit blue and green colors. The naphthalimide-functionalized silica aerogels/dye composite exhibits a blue (dimethylamino-modified naphthalimide-functionalized silica aerogel showing green) emission from naphthalimide of silica aerogels at 450 nm (520 nm) and a red emission around 650 nm of SP. Under exposure to ultraviolet light, SP gradually transformed into the merocyanine (MC) form, and a strong absorption band appeared near 540 nm. At that time, the fluorescence resonance energy-transfer (FRET) process occurred between naphthalimide and the MC isomer. As the irradiation time is extended, the fluorescence color changes continuously from blue (green) to red through the FRET process. Using the time dependence of fluorescence, dynamic encryption patterns and multiple codes were successfully developed based on these functionalized silica aerogels. This work has provided important guidance for designing advanced information encryption materials.

Transient cucurbit[7]uril-mediated host-guest complexes for time-dependent fluorescence and information-self-erasing hydrogel.

A non-equilibrium cucurbit[7]uril-mediated supramolecular host-guest system is fabricated by using urea/urease to control aqueous solution pH on time dimension, showing transient assembly behavior and time-dependent fluorescence. The dynamic assembly can be also achieved in hydrogel network, resulting in a time-dependent fluorescent hydrogel for information encryption.

Exploration of the impact of graphene oxide, acetylenic gemini, and CTAT on the photophysical and aggregation properties of dipolar coumarin 153.

Advanced spectroscopic techniques have been utilized to study the interaction between the laser dye coumarin 153 (C153) and graphene oxide (GO) nanoparticles. GO was synthesized using a modified Hummers' method and characterized by UV-vis spectroscopy, Raman laser spectroscopy, FTIR-ATR spectroscopy, FESEM, HR-TEM, and XRD techniques. The GO@C153 composite was formed by mixing two aqueous solutions of GO and C153 due to their strong interaction through stacking and hydrophobic interactions. In this case, GO acts as an effective fluorescence quencher for C153 molecules, which undergo H-type aggregation in the presence of GO. The Stern-Volmer equation and time-dependent fluorescence studies were utilized to analyse the mechanism of fluorescence quenching. According to the findings, both static and dynamic quenching processes are responsible for the reduction in fluorescence intensity. The effect of surfactants (both cetyltrimethylammonium p-toluenesulfonate (CTAT) and synthesized N,N'-dihexadecyl-N,N,N',N'-tetramethyl-N,N'-but-2-ynediyl-di-ammonium chloride (16-4-16)) on the aggregation and photophysical properties of the dye was investigated using surface tensiometry, conductometry, UV-vis absorption spectroscopy, steady-state fluorescence measurements, DLS, and time-dependent fluorescence spectroscopy. Surfactants change the microenvironment of the C153 dye, leading to spectrum shifting and a higher quantum yield, which causes a rapid rise in fluorescence intensity in the micellar medium. It has been noted that in a micellar medium rather than in an aqueous one, the luminous intramolecular charge transfer (ICT) state of C153 stabilises. Lastly, we investigated the photophysical behavior of the GO-C153-micelle ternary system and discovered that, in the presence of a micellar medium, the quenched and blue-shifted (H-type aggregation) fluorescence peak of C153 (in the presence of GO) began to intensify once more. The main goal of this work is to create an effective and fairly cost powerful fluorescence sensor. Additionally, the ternary system (GO-C153-micelle) analytical idea can be employed to identify the onset of micelle formation. In wastewater treatment analysis, the GO-C153-surfactant ternary system concept can also be used to regenerate the adsorbent (in this case, GO) from dye molecules by allowing the dye molecules to exit the adsorbent and enter the micellar medium.

Self-healing photoluminescent polymers with photosensitive behavior for information storage and multiple-level dynamic encryption.

Photo-responsive luminescent materials capable of responding to light stimuli are crucial in the realm of sophisticated encryption, anti-counterfeiting, and optical data storage. Yet, the development of such materials that also feature self-healing capabilities, swift reaction times, light weight, fatigue resistance, dynamic display abilities, and enhanced security measures is exceedingly rare and presents considerable challenges. Herein, a novel family of self-healing and photo-stimuli-responsive photoluminescent polymers are reported, which is achieved by interlinking terpyridine- and spiropyran-functionalized polymers through N-Ln coordination bonds and hydrogen bonding among the polymer chains. The resulting polymers exhibit good processability, superior tensile strength, fast self-healing ability, and photo-stimuli-responsive performance. The photo-stimuli-responsive properties include unique color shifts (colorless and purple) and light-controlled time-dependent fluorescence modulation (green-, red-, and yellow-emission), which stem from fine-tuning the isomerization of spiropyran and leveraging the fluorescence resonance energy transfer (FRET) from Ln-Tpy donors to spiropyran acceptors, respectively. Besides, these polymers have been successfully applied in dynamic multi-level information encryption applications. We are convinced that these smart materials, crafted through our innovative approach, hold vast potential for applications in information storage, cutting-edge anti-counterfeiting encryption, UV-sensing, and light-writing technologies, marking a novel strategy in the design of photosensitive luminescent smart materials.

Enhancing DNA-based nanodevices activation through cationic peptide acceleration of strand displacement.

Dynamic DNA-based nanodevices offer versatile molecular-level operations, but the majority of them suffer from sluggish kinetics, impeding the advancement of device complexity. In this work, we present the self-assembly of a cationic peptide with DNA to expedite toehold-mediated DNA strand displacement (TMSD) reactions, a fundamental mechanism enabling the dynamic control and actuation of DNA nanostructures. The target DNA is modified with a fluorophore and a quencher, so that the TMSD process can be monitored by recording the time-dependent fluorescence changes. The boosting effect of the peptides is found to be dependent on the peptide/DNA N/P ratio, the toehold/invader binding affinity, and the ionic strength with stronger effects observed at lower ionic strengths, suggesting that electrostatic interactions play a key role. Furthermore, we demonstrate that the cationic peptide enhances the responsiveness and robustness of DNA machinery tweezers or logic circuits (AND and OR) involving multiple strand displacement reactions in parallel and cascade, highlighting its broad utility across DNA-based systems of varying complexity. This work offers a versatile approach to enhance the efficiency of toehold-mediated DNA nanodevices, facilitating flexible design and broader applications.

Dynamic multicolor luminescent anti-counterfeiting based on spiropyran-engineered gold nanoclusters

Multicolor luminescent materials with time-dependent optical responses are attractive for developing advanced anti-counterfeiting techniques, but it still remains challenging to rationally design and fabricate these emerging materials. Herein, we report the design of novel dynamic luminescent materials based on spiropyran-engineered gold nanoclusters (AuNCs) for anti-counterfeiting applications. Encapsulating fluorescent AuNCs with spiropyran-labeled bovine serum albumin enables the construction of dynamic multicolor luminescent nanoparticles (DML NPs) based on fluorescence resonance energy transfer. These AuNCs-based DML NPs exhibit photochromism and dynamic fluorescence color change from green to yellow to orange-red with the extension of UV irradiation time. Moreover, the photochromism and dynamic fluorescent behavior is highly reversible when exposed to the irradiation of visible light. By taking advantage of photochromic and time-dependent dynamic fluorescence, potential application in optical information storage, dynamic anti-counterfeiting authentication and multi-mode anti-counterfeiting are successfully demonstrated based on DML NPs-deposited polyvinyl alcohol film. This study provides a new strategy of designing novel dynamic multicolor luminescent materials with promising optical properties, which can further advance the practical application of AuNCs-based luminescent materials in the field of information encryption and anti-counterfeiting.

A triphenylamine-based near-infrared fluorescence turn off probe for nitroreductase imaging

Nitroreductase (NTR) is an essential biomarker for various diseases and widely used to evaluate the hypoxia status in tumor cells. In this work, we developed a near-infrared (NIR) fluorescence “on-off” probe PTP based on a triphenylamine scaffold, with an intrinsic long wavelength emission more than 700 nm. This probe showed typical aggregation-induced emission (AIE) properties with the increase of PBS fraction (fw), which might be attributed to the restriction of intramolecular motions (RIM) effect in high aqueous solution. The frontiers molecular orbitals (FMO) of the probe PTP and the resulting reduction compounds (PT-OH and TPA-OH) were calculated to determine their structure differences. The two nitro groups were reduced in response to NTR and then released the substance TPA-OH through the 1,6-rearrangement-elimination, resulting in simultaneous fluorescence decrease. This process was also demonstrated by the DFT/TD-DFT and docking calculations, indicating a favorable structural and spatial match between the probe and NTR. More importantly, the probe was successfully used to visualize the NTR distribution in living A431 cells with nontoxicity. It exhibited a time-dependent fluorescence quenching behavior at the cellular level, making it of great potential in NTR detection for other biosystems.

Time dependent fluorescence spectrum of a three-level Λ system under electromagnetically induced transparency and coherent population trapping

We investigate theoretically the time dependent fluorescence spectra (TDFS) of a three-level system in electromagnetically induced transparency (EIT) and coherent population trapping (CPT) configurations. Time dependent fluorescence intensities of Rayleigh and Stokes transitions are studied as a function of the ground state coherence relaxation rate and initial state preparation, and their correlation with the temporal evolution of dark and bright states is established. Linewidths of fluorescence and absorption are compared in different regimes of relaxation rates. The results are used to discuss the characteristic features of EIT and CPT in the domain of fluorescence spectroscopy.

Controlling molecular assembly on time scale: Time-dependent multicolor fluorescence for information encryption

Dynamic assembly on time scale is common in biological systems but rare for artificial materials, especially for smart luminescent materials. Programming molecular assembly in a spatio-temporal manner and resulting in white-light-including multicolor fluorescence with time-dynamic features remains challenging. Herein, controlling molecular assembly on time scale is achieved by integrating a pH-responsive motif to a transient alkaline solution which is fabricated by activators (NaOH) and deactivators (esters), leading to automatic assembly on time scale and time-dependent multicolor fluorescence changing from blue to white and yellow. The kinetics of the assembly process is dependent on the ester hydrolysis process, which can be controlled by varying ester concentrations, temperature, initial pH, stirring rate and ester structures. This dynamic fluorescent system can be further developed for intelligent fluorescent materials such as fluorescent ink, three-dimension (3D) codes and even four-dimension (4D) codes, exhibiting a promising potential for information encryption.

A novel nitroreductase-responsive turn-off fluorescent probe based on AIEgen and its bioimaging application

Nitroreductase (NTR) is frequently employed as a biomarker to assess the level of hypoxia in tumor tissues. To date, the majority of NTR-reactive probes have focused on the luminescence "turn on" characteristic, which has been plagued by background interferences. In this study, we present the first report of an NTR-responsive "turn-off" fluorescent probe, TPEDCH-PBN, based on AIEgen. This probe exhibits typical aggregation-induced emission (AIE) properties in high PBS fraction, which may be attributed to the restriction of intramolecular motions (RIM) effect. DFT/TD-DFT calculations were employed to determine the discrepancies in structure and electron density distribution among TPEDCH, TPEDCH-PBNOH and TPEDCH-PBN. Additionally, docking calculations were utilized to elucidate the structure-function relationship between the probe and NTR, revealing a favorable structural and spatial match. Photophysical investigations demonstrated the probe's high selectivity towards NTR with the detection limit of 0.68 μg/mL. The dynamic quenching process of TPEDCH-PBN upon NTR was examined, and the quenching constant Ksv was determined to be 53.6 g−1.L. In addition, the NTR detection ability of probe TPEDCH-PBN as well as its time-dependent fluorescence quenching behaviors were confirmed by cell imaging of probe in A549 cells. Overall, this study proposed a novel molecular design approach for the biomarker detection probe, which may prove to be more extensively applicable.

Screening Enzymatic Degradation of Polyester Polyurethane with Fluorescent Single-walled Carbon Nanotube and Polymer Nanoparticle Conjugates.

Enzymatic biodegradation is a promising method to reclaim plastic materials. However, to date, a high-throughput method for screening potential enzyme candidates for biodegradation is still lacking. Here, we propose a single-walled carbon nanotube (SWCNT) fluorescence sensor for screening the enzymatic degradation of polyester polyurethane nanoparticles. Through wrapping the SWCNT with cationic chitosan, an electrostatic bond is formed between the SWCNT and Impranil, a widely applied model substrate of polyester polyurethane. As Impranil is being degraded by the enzymes, a characteristic quenching at a short reaction time followed by a brightening at a longer reaction time in the fluorescence signal is observed. The time-dependent fluorescence response is compared with turbidity measurement, and we conclude that the brightening in fluorescence results from the binding of the degradation product with the SWCNT. The proposed SWCNT sensor design has the potential to screen enzyme candidates for selective degradation of other plastic particles.

Spectroscopic studies on the supramolecular interactions of methyl benzoate derivatives with p-sulfocalix[6]arene macrocycles

This paper is a continuation of our previous research and aims to further investigate and elucidate the nature and mechanisms of noncovalent supramolecular interactions between four methyl benzoate derivatives (I-IV), which are capable of exhibiting Twisted Intramolecular Charge Transfer (TICT) and/or Excited State Intramolecular Proton Transfer (ESIPT)‐type behavior, and chemical and biological nanocavities. Photophysical and photochemical properties of molecules I-IV in aqueous solution in the presence of well-recognized macrocyclic host p-sulfocalix[6]arenes (SCA[6]) have been studied using steady-state, time-resolved and 1H NMR spectroscopic techniques. The changes in the ground- and excited-state spectroscopic characteristics (absorption and fluorescence spectra, time-resolved fluorescence spectra, fluorescence decay times and 1H NMR spectra) undergo significant modifications upon encapsulation of the investigated methyl benzoate derivative in the macromolecular cavity. For the two compounds (I and II), the interactions with the macrocycles with a hydrophobic SCA[6] cavity lead to the formation of stable inclusion complexes with 1:1 stoichiometry, both in the ground and excited state, while the stoichiometry of the III-SCA[6] and IV-SCA[6] complexes in the ground and excited states is 1:2. The values of the equilibrium constants have been determined from the spectroscopic data using Benesi-Hildebrand and nonlinear regression procedures. The location of the organic molecule inside the SCA[6] has been investigated by 1H NMR experiments. The changes in macrocyclic compound-induced NMR chemical shifts clearly indicate that the chemical structure of inclusion complexes is very different for methyl benzoate derivative-SCA[6] and methyl benzoate derivative-CB[7] systems. Finally, we have shown, using time-dependent fluorescence Stokes shift, that very fast solvation dynamics of pure water is markedly different from that of the confined water molecule in SCA[6] system.

From cell membrane to mitochondria: Time-dependent AIE photosensitizer for fluorescence imaging and photodynamic anticancer therapy

Aggregation-induced emission photosensitizers (AIE-PSs) targeting different subcellular organelles with time-dependent manner are highly promising for clinical applications but rarely reported. Herein, we designed and synthesized the near-infrared (NIR) emission AIE-PS (CTQ-S) with broad absorption and excellent type I reactive oxygen species (ROS) generation efficiency that was superior to the widely used PS (Rose Bengal and Chlorine 6). With short-term incubation, CTQ-S anchored on the cell membrane (Rr: 0.843, Rr is for Pearson correlation coefficient) and gradually entered the mitochondria (Rr: 0.937) of cancer cells, showing excellent time-dependent fluorescence fluorescent imaging effect. Furthermore, CTQ-S realized the selective photodynamic therapy (PDT) effect in a time-dependent manner under white light irradiation. This work provided a new way for cancer cells fluorescence imaging and PDT.