Stokes Shift Research Articles

Rationally Designed G-Quadruplex Selective "Turn-On" NIR Fluorescent Probe with Large Stokes Shift for Nucleic Acid Research-Based Applications.

Guanine-rich DNA/RNA sequences can form Hoogsteen bonds to adopt noncanonical secondary structures called G-quadruplexes, and these have been associated with diverse cellular processes. There has been considerable research interest in the design of G4-interacting ligands for cellular probing of the G4 structure and understanding its associated biological function. Most of the fluorescent G4 ligands either do not have significant selectivity over other nucleic acid structures, have high Stokes shift, or are not in the near-infrared (NIR) region, which limits its cellular visualization. The current work involves the rational design and synthesis of NIR fluorescent probes comprising a (Z)-1-methyl-2-((3-methylbenzo[d]thiazol-2(3H)-ylidene)methyl)quinolin-1-ium scaffold. Among the designed molecules, 4a exhibited far-red fluorescence (λmax = 680 nm) with large Stokes shift (∼182 nm) upon selective binding to human telomeric G-quadruplexes. The dye 4a does not disturb the conformation and stability of G-quadruplexes, thereby making it suitable for nucleic acid research based applications. Interestingly, 4a showed remarkable selectivity over single- and double-stranded structures in contrast to a commercially available quadruplex binding probe, Thiazole orange (TO). The molecular docking studies indicate that 4a binds at the groove region of the telomeric DNA G-quadruplex through π-π stacking interactions with the quinoline and amine-substituted phenyl ring and with the phosphate backbone through anion-π interactions with the benzothiazole ring. The designed molecule 4a has interesting photophysical properties, cell permeability, and biocompatibility with minimal cytotoxicity. Fluorescence imaging studies in live HeLa cells showed that probe 4a binds to the transient population of the DNA G-quadruplex in the nucleus and RNA quadruplexes in the cytoplasm. In brief, G-quadruplex NIR fluorescent probe 4a with a higher signal/noise ratio has significant potential for cellular imaging studies and thus opens avenues to decipher the biological pathways for better understanding of G-quadruplex biology.

A Novel Near-Infrared Tricyanofuran-Based Fluorophore Probe for Polarity Detection and LD Imaging

In this paper, LD-TCF, a targeting probe for lipid droplets (LDs) with a near-infrared emission wavelength and large Stokes shift, was fabricated for polarity detection by assembling a donor–π–acceptor (D–π–A) molecule with typical twisted intramolecular charge transfer (TICT) characteristics. Surprisingly, the fluorescence emission wavelength of the newly constructed probe LD-TCF was stretched to 703 nm, and the Stokes shift was amplified to 126 nm. Furthermore, LD-TCF could specifically answer the change in polarity efficiently and did not experience interference from other biologically active materials. Importantly, LD-TCF exhibited the ability to target lipid droplets, providing valuable insights for the early diagnosis and tracking of pathophysiological processes underlying LD polarity.

A mitochondria-targeted nitric oxide probe with large Stokes shift for real-time imaging and evaluation of inflammatory bowel disease in situ

BackgroundInflammatory bowel disease (IBD) is a prevalent inflammatory disorder, and the abnormal expression of nitric oxide (NO) produced by biocatalysis of iNOS enzyme in mitochondria is directly associated with the occurrence and progression of IBD. Activatable fluorescent probes offer promising tools for early diagnosis of IBD, however, inadequate biodistribution and limited targeting properties of these probes in vivo severely impede accurate diagnosis of IBD and real-time evaluation of inflammatory levels in situ. Therefore, it is necessary to designed a highly efficient fluorescent probe towards NO to overcome inadequate biodistribution and achieve accurate diagnosis and evaluation of IBD in situ. ResultsWe designed a highly efficient mitochondria-targeted “turn-on” NIR fluorescent probe Cy-OMe which has excellent targeting properties and imaging ability. The response mechanism is probe Cy-OMe rapidly undergoes N-nitrosation reaction resulting in turn-on NIR fluorescence signal when exposed to NO. Cy-OMe exhibits high sensitivity and specificity in detecting NO content in vitro, owing to its large Stokes shift. Furthermore, the probe Cy-OMe not only efficiently targets mitochondria but also enables precise assessment of fluctuations in endogenous NO concertation across various cell types. Importantly, by virtue of large Stokes shift and excellent mitochondrial targeting ability, Cy-OMe has the capability to specifically evaluate dynamic fluctuations of NO in lipopolysaccharide (LPS)‐stimulated IBD mouse models in situ and Cy-OMe was achieved high-contrast imaging and precision diagnosis of intestinal inflammation diseases. SignificanceCy-OMe can accurately assess fluctuations in NO levels and show high signal fidelity in the diseased intestine region, which has prospects in the non-invasive diagnosis of intestinal inflammation in vivo. At the same time, it is expected to serve as a potential diagnose platform for investigating the physiological processes underlying NO-related inflammatory diseases and promoting understanding of the pathological functions of NO across diverse inflammatory diseases.

Metal‐Free Aminophosphonation: Eco‐Friendly Synthesis and Photophysical Properties of Fluorescent 3‐(Aminoimidazo[1,2‐a]Pyridin‐2‐yl)Phosphonates

AbstractWe report a novel, metal‐free procedure for the direct aminophosphonation of imidazo[1,2‐a]pyridines in green solvents under open air conditions. This method is characterized by its mild and sustainable conditions, ease of operation, scalability, and excellent functional group compatibility. The synthesized compounds exhibit promising photophysical properties, including significant Stokes shifts and quantum yields, making them potential candidates for innovative fluorescent probes.

Metal-Free Aminophosphonation: Eco-Friendly Synthesis and Photophysical Properties of Fluorescent 3-(Aminoimidazo[1,2-a]Pyridin-2-yl)Phosphonates.

We report a novel, metal-free procedure for the direct aminophosphonation of imidazo[1,2-a]pyridines in green solvents under open air conditions. This method is characterized by its mild and sustainable conditions, ease of operation, scalability, and excellent functional group compatibility. The synthesized compounds exhibit promising photophysical properties, including significant Stokes shifts and quantum yields, making them potential candidates for innovative fluorescent probes.

The Role of Spacers as a Probe in Variation of Photoluminescence Properties of Mono- and Bi-nuclear Boron Compounds.

A series of N,O donor-based mono- and binuclear four-coordinated boron complexes were synthesized. Depending on the substitution and spacer, these complexes exhibit intense blue, green and yellow emission in solution states. Notably, the fluorescence quantum yields (ФF) and fluorescence decay (lifetime, τ) of mononuclear boron complexes (2a-2e) were higher than the binuclear boron complexes (2f-2k). The lowest lifetime and quantum yield in binuclear boron complexes were due to intramolecular rotation induced non radiative processes. The disulphide spacer-based boron complexes2i-2kshowed aggregation-caused quenching in the THF/H2O mixture whereas no other complexes were ACQ responsive. These complexes show large Stokes shift, one of them i.e.2ehas the highest Stokes shift of 130 nm among them. Further, the electrochemical study suggests the presence of two redox incidences. Theoretical studies show close corroboration between the TD-DFT computed and experimentally measured absorption maxima as well as DFT (GIAO) calculated and experimentally measured11B NMR values. This complements the appropriate selection of the theoretical methods to shed light on the electronic transitions in the mono- and binuclear BF2complexes.

Double-Shell Encapsulation of Lead-Free Tin Halide Perovskite for Self-Powered Smart Windows.

Luminescent solar concentrators (LSC) have the potential application in building integrated photovoltaic (BIPV). 0D tin-based perovskites are a promising embedding phosphor in LSC due to the large Stokes shift and high photoluminescence quantum yield. But the instability and uncontrollable crystal growth are severe limiting their successful utilization in device fabrication. To tackle these issues, double-shell encapsulated configurations are presented, soft ligands of hypophosphorous acid and hard-shell of hollow mesoporous silica are simultaneously suppressing the oxidation of Sn2+ and restricting crystal growth within nano-matrix. The stable phosphor is subsequently embedded into LSC for harvesting solar energy and the resulting output power efficiently drives the combined electrochromic glass under natural light. These fabricated devices also offer the self-adaptable switch on/off functionality to regulate light absorption with variable solar irradiation intensity in real time. This approach is anticipated to open new avenues for utilizing lead-free perovskite nanomaterials in self-powered smart windows for BIPV.

Ultra-Narrowband Circularly Polarized Luminescence from Multiple 1,4-Azaborine-Embedded Helical Nanographenes.

In this manuscript we present a strategy to achieve ultranarrowband circularly polarized luminescence (CPL) from multiple 1,4-azaborine-embedded helical nanographenes. The impact of number and position of boron and nitrogen atoms in the rigid core of the molecule on optical properties─including absorption and emission maxima, photoluminescence quantum yield, Stokes shift, excited singlet-triplet energy gap and full width at half-maximum (fwhm) for CPL and fluorescence─was investigated. The molecules reported here exhibits ultranarrowband fluorescence (fwhm 16-17.5 nm in toluene) and CPL (fwhm 18-19 nm in toluene). To the best of our knowledge, this is among the narrowest CPL for any organic molecule reported to date. Quantum chemical calculations, including computed CPL spectra involving vibronic contributions, provide valuable insights for future molecular design aimed at achieving narrowband CPL.

Near-Infrared Room-Temperature Phosphorescence from Monocyclic Luminophores.

Compact luminophores with long emission wavelengths have aroused considerable theoretical and practical interest. Organics with room-temperature phosphorescence (RTP) are also desirable for their longer lifetimes and larger Stokes shifts than fluorescence. Utilizing the low electronic transition energy intrinsic to thiocarbonyl compounds, electron-withdrawing groups were attached to the 4H-pyran-4-thione core to further lower the excited state energies. The resulting mini-phosphors were doped into suitable polymer matrices. These purely organic, amorphous materials emitted near-infrared (NIR) RTP. Having a molar mass of only 162 g·mol-1, one of the phosphors emitted RTP that peaked at 750 nm, with a very large Stokes shift of 15485 cm-1 (403 nm). Thanks to the good processability of the polymer film, light-emitting diodes (LEDs) with NIR emission were easily fabricated by coating doped polymer on ultraviolet LEDs. This work provides an intriguing strategy to achieve NIR RTP using compact luminophores.

Near‐Infrared Room‐Temperature Phosphorescence from Monocyclic Luminophores

Compact luminophores with long emission wavelengths have aroused considerable theoretical and practical interest. Organics with room‐temperature phosphorescence (RTP) are also desirable for their longer lifetimes and larger Stokes shifts than fluorescence. Utilizing the low electronic transition energy intrinsic to thiocarbonyl compounds, electron‐withdrawing groups were attached to the 4H‐pyran‐4‐thione core to further lower the excited state energies. The resulting mini‐phosphors were doped into suitable polymer matrices. These purely organic, amorphous materials emitted near‐infrared (NIR) RTP. Having a molar mass of only 162 g·mol‐1, one of the phosphors emitted RTP that peaked at 750 nm, with a very large Stokes shift of 15485 cm‐1 (403 nm). Thanks to the good processability of the polymer film, light‐emitting diodes (LEDs) with NIR emission were easily fabricated by coating doped polymer on ultraviolet LEDs. This work provides an intriguing strategy to achieve NIR RTP using compact luminophores.

Organic Circularly Polarized Room‐Temperature Phosphorescence: Strategies, Applications and Challenges

Organic circularly polarized luminescence (CPL) plays crucial roles in chemistry and biology for the potential in chiral recognition, asymmetric catalysis, 3D displays, and biological probes. The long‐lived luminescence, large Stokes shift, and unique chiroptical properties make organic circularly polarized room‐temperature phosphorescence (CPP) a new research hotspot in recent years. Nevertheless, achieving high‐performance organic CPP is still challenging due to the sensitivity and complexity of integrating triplet excitons and polarization within organic materials. This review summarizes the latest advances in organic CPP, ranging from design strategies and photophysical properties to underlying luminescence mechanisms and potential applications. Specifically, the design strategies for generating CPP are systemically categorized and discussed according to the interactions between chiral units and chromophores. The applications of organic CPP in organic light‐emitting diodes, sensing, chiral recognition, afterglow displays, and information encryption are also illustrated. In addition, we present the current challenges and perspectives on developing organic CPP. We expect this review to provide some instructive design principles to fabricate high‐performance organic CPP materials, offering an in‐depth understanding of the luminescence mechanism and paving the way toward diverse practical applications.

Rational design and synthesis of pyrrolo-pyridine dinitrile dyes with strong dual-state emission

In recent years, there has been a growing focus on organic dual-state emission (DSE) materials that demonstrate robust luminescence in both solid and solution states. Nevertheless, in the solid state, π-π stacking between organic molecules often results in pronounced luminescence quenching, posing a significant challenge for the design and synthesis of organic DSE materials. In this work, a pyrrolo-pyridine dinitrile (PPDN) dye was synthesized from commercially available 2-heteroaryl acetonitriles and classical diketopyrrolopyrrole (DPP) dye via a two-step process. Due to its special "J"-shaped planar conjugate structure, the PPDN dye has strong DSE performance, high molar extinction coefficients (ε), large Stokes shifts, and excellent optical and thermal stability. It also has aniline vision detection capability, which is useful in the field of security displays and anti-counterfeiting.

A multifunctional Eu-organic framework for fluorescence sensing properties and the detection of pyrimethanil in real samples

Europium metal–organic frameworks (Eu-MOFs) have unique application prospects in the field of fluorescence sensing, due to the fluorescence characteristics of Eu3+ ion and organic ligands, and the advantages of obvious red luminescence, long emission lifetime, large Stokes shift, and high quantum yield. In this study, a novel Eu-MOF was synthesized hydrothermally using europium acetate hexahydrate (Eu(Ac)3·6H2O), 5-(4′-carboxybenzyloxy) isophthalic acid (5-H3CIA), and 4,4′-bipyridine (4,4′-bipy). Structural analysis revealed that the Eu-MOF exhibited a three-dimensional framework with 4,4′-bipyridine as the guest molecule. Fluorescence sensing experiments revealed that 2,4,6-trinitrophenol, ornidazole, pyrimethanil, and Cr2O72− effectively quenched the fluorescence of the Eu-MOF in aqueous solution, with corresponding limits of detection as low as 0.886, 0.732, 0.569, and 2.800 μM, respectively. Exploiting the ability of Cr2O72− to quench the fluorescence of the Eu-MOF, we devised a Cr2O72−@Eu-MOF fluorescence silencing system that, in the presence of ascorbic acid, gradually recovered its fluorescence to form a unique fluorescence “on–off-on” sensor. In addition, the fluorescence sensing mechanism of Eu-MOF was studied, the fluorescence test was prepared to detect Cr2O72− with an open eye, and the content of pyrimethanil was detected in real samples, including cucumber skin, tomato skin, grape skin, apple and kiwi.

Realizing Near-Unity Photoluminescence Efficiency in Antimony-Doped Indium-Based Halides Induced by Strong Electron-Phonon Coupling.

Exploring a zero-dimensional (0D) hybrid halide with a large Stokes shift and efficient broad-band emission is highly desirable due to its enormous potential for solid-state lighting (SSL) application. However, it is still challenging to develop a highly emissive 0D hybrid halide with low toxicity and remarkable stability. Herein, we developed a novel indium-based metal halide A5In2Cl16·4H2O (A = doubly protonated 1,4-diaminobutane) whose inorganic octahedrons are completely isolated by the organic cations to form the 0D structure. Experimental and theoretical studies confirmed that Sb-doped A5In2Cl16·4H2O exhibits broad yellow emission with a photoluminescence quantum yield (PLQY) of up to 98%. The intense yellow emission can be attributed to the radiative recombination of triplet self-trapped excitons (STEs) in [SbCl6]3- octahedrons caused by the strong electron-phonon coupling. Benefiting from the excellent stability and photoluminescence performance, A5In2Cl16·4H2O:15%Sb was used as the yellow phosphor to prepare a white-light-emitting diode (WLED) device with a color rendering index of 87.8 and a luminous efficiency of up to 36.18 lm/W, demonstrating its potential in SSL applications. This work provides a guidance for developing environmentally friendly, efficient, and stable ultraviolet (UV)-excited broad-band emission materials.

Detection of carboxylesterases by an activatable NIR fluorescence probe with high selectivity in living systems

Carboxylesterases (CEs) have attracted increasingly attention in the physiological and pathological processes of many diseases such as diabetes, hepatocellular carcinoma (HCC) and drug metabolism. Selective detection of CEs activity is imperative to evaluate the pathophysiological process of CEs-related disease. Herein, a selective near-infrared (NIR) fluorescent probe (DCM-CE) with high selectivity is reported. DCM-CE was composed of dicyanoisophorone-based fluorophore and carbamate unit which is a highly selective identification group for CEs. DCM-CE exhibited good sensitivity for CEs detection at physiological pH and temperature. Furthermore, DCM-CE featured large Stokes shift (175 nm) and good at tracking the drug-induced trace change of CEs activity in HepG2 cells with little effect on cell viability. Moreover, DCM-CE was applied to monitor the activity of CEs in living mice. Taken all together, DCM-CE had extensive potential application value in detecting CEs for evaluating related diseases.

Selective Recognition of the Dimeric NG16 Parallel G-Quadruplex Structure Using Synthetic Turn-On Red Fluorescent Protein Chromophore.

Red fluorescent protein (RFP)-based fluorescent probes that can selectively interact with specific nucleic acids are of great importance for therapeutic and bioimaging applications. Herein, we have reported the synthesis of RFP chromophores for selective recognition of G-quadruplex nucleic acids in vitro and ex vivo. We identified DFHBI-DM as a fluorescent turn-on probe that binds to the dimeric NG16 parallel quadruplex with superior selectivity and sensitivity over various parallel, antiparallel, and hybrid topologies. The binding of DFHBI-DM to NG16 exhibited excellent photophysical properties, including high binding affinity, large Stokes shift, high photostability, and quantum yield. The MD simulation study supports the 1:1 binding stoichiometry. It confirms the planar conformation of DFHBI-DM, which makes strong binding interactions with a flat quartet of NG16 compared to other antiparallel and hybrid topologies. The cell imaging and MTT assays revealed that DFHBI-DM is a biocompatible and efficient fluorescent probe for intracellular imaging of NG16. Overall, these results demonstrated that DFHBI-DM could be an effective fluorescent G4-stabilizing agent for the dimeric NG16 parallel quadruplex, and it could be a promising candidate for further exploration of bioimaging and therapeutic applications.

Monitoring of mercury ion in environmental media and biological systems using a red emissive fluorescent probe with a large Stokes shift

The development of practical fluorescent probe for detecting toxic mercury ions (Hg2+) is desirable for environmental assurance and public health. In this study, a new red emissive fluorescent probe (KJL) was designed and synthesized for monitoring trace Hg2+ both in vitro and in vivo with distinct features including ideal response rate (within 4 min), red emission (596 nm), large Stokes shift (162 nm), highly sensitivity (LOD = 4.79 nM) and excellent specificity. KJL also validated the good capability for accurately monitoring trace Hg2+ levels in actual samples (faucet water, drinking water, river water, lake water, urine and serum) and possessed the eye-catching ability in visualization of Hg2+ under environmental/biological conditions, which revealed the great potential of this red-emitting fluorescent probe for practical applications in complex environmental and biological systems.

Synthesis, photophysical properties, and in-silico nonlinear optics of 3-hydroxy-N-phenyl-2-naphthamide and its acetate, acrylate, and benzoate derivative

In this study, we report the successful growth of single crystals of 3-hydroxynaphthalene-2-carboxanilides (NAS) with a monoclinic structure in the P21/c space group and space group number of 14 for the first time. We have developed a yield and time-effective modified synthetic procedure using a synthetic reactor by replacing the traditional microwave method. Additionally, acylated derivatives of NAS, including novel acryloyl derivative (NAS AC), are synthesized with a modified procedure, replacing pyridine with triethylamine.We investigate the structural, photophysical, and quantum chemical properties of N-(4-acetylphenyl)-2-oxo-2H-chromene-3-carboxamide (NAS) and its acylated derivatives (NAS AC, NAS ACT, NAS BZ). Photophysical studies reveal significant Stokes shifts observed in different solvents, including time-enhanced fluorescence in DMSO, attributed to solvent relaxation processes. Natural bond orbital (NBO) analysis, molecular electrostatic potential (MEP) maps, and frontier molecular orbital (FMO) provide insights into electronic interactions and asymmetric charge distribution. Low-lying LUMO values of these compounds (-2.31 eV to -1.95 eV) support candidature for the electron acceptor applications. Nonlinear optical properties were thoroughly investigated, with NAS displaying the highest static first-order hyperpolarizability (17.89 × 10−30 esu) and NAS BZ exhibiting the highest second-order hyperpolarizability (113.09 × 10−36 esu), indicating significant nonlinear optical responses. Thermal stability (TGA and DTA) highlights the significant range of temperatures for the NLO applications.

Up-conversion materials for solid-state lighting

AbstractConventional phosphor-converted white LEDs (WLEDs), using (Stokes) down-conversion light emission, suffer from a red deficiency that increases the Color Temperature towards “cool white light” above 5000 K. The present work describes a phosphor-Up-converted WLED approach that wishes to overcome this issue by achieving white light generation (WLG) through Up-conversion photoluminescence (UCPL), without energy losses due to Stokes shift and excited by a 980 nm LED instead of the more expensive blue LEDs. The UC materials include thin films of lanthanide (Ln)-doped aluminosilicate glass multilayers, alternating (Ln)-doped aluminosilicate and titania films in the form of 1-D photonic crystals and Ln ion-implanted materials. Sol-gel (SG) processing has been used as a low-cost high purity processing method to prepare titania, as well as aluminosilicate films containing Er3+, Tm3+ and Yb3+, for WLG and possible application as WLED materials. The total Ln content varied from a high of 22 mol% to as low as 5.8 mol%. The materials prepared have been characterized by UV-Vis-NIR (using a variable angle specular reflection accessory), plus FTIR and UCPL spectroscopies. The UC light emission was analyzed with the help of CIE chromaticity diagrams. Graphical abstract

Near-infrared probes based on the phenanthridinium for dynamic monitoring of viscosity fluctuations during mitophagy

Abnormal changes in the mitochondrial microenvironment can cause a variety of diseases. Consequently, based on the twisted intramolecular charge transfer (TICT) theory, three hemicyanine fluorescent probes 1a-c were designed and developed by linking the phenanthridine group with different electron donor groups for the dynamic detection of mitochondrial viscosity in this paper. They have the advantages of near-infrared emission, excellent pH stability and viscosity sensitivity. Optical experiments showed that the maximum absorption and emission wavelengths of the probes in different solvents located at 411 − 529 nm and 623 − 684 nm with large Stokes shifts of 133 – 230 nm. In addition, when the viscosity increased from 0.89 cP to 856 cP, their fluorescence intensities in glycerol enhanced by 115-fold, 83-fold and 303-fold compared with water, respectively. The fluorescence intensities of probes showed excellent fit to the Forster Hoffmann equation, and exhibited nearly OFF-ON response to viscosity. Moreover, the probe 1a with good photostability and low cytotoxicity could target mitochondria. It was verified that 1a also could detect variation in mitochondrial viscosity during autophagy by modelling starvation and drug-induced (rapamycin and nystatin) in HeLa cells. Therefore, this study provides a useful probe for the analysis of mitophagy process in HeLa cells by the viscosity variation of mitochondria.