Blue Fluorescence Research Articles

Considerable Piezochromism in All‐Inorganic Zero‐Dimensional Perovskite Nanocrystals via Pressure‐Modulated Self‐Trapped Exciton Emission

AbstractPiezochromic materials refer to a class of matters that alter their photoluminescence (PL) colors in response to the external stimuli, which exhibit promising smart applications in anti‐counterfeiting, optoelectronic memory and pressure‐sensing. However, so far, most reported piezochromic materials have been confined to organic materials or hybrid materials containing organic moieties with limited piezochromic range of less than 100 nm in visible region. Here, we achieved an intriguing piezochromism in all‐inorganic zero‐dimensional (0D) Cs3Cu2Cl5 nanocrystals (NCs) with a considerable piezochromic range of 232 nm because of their unique inorganic rigid structure. The PL energy shifted from the lowest‐energy red fluorescence (1.85 eV) to the highest‐energy blue fluorescence (2.83 eV), covering almost the entire visible wavelength range. Pressure‐modulated self‐trapped exciton emission between different energy levels of self‐trapped states within Cs3Cu2Cl5 NCs was the main reason for this piezochromism property. Note that the quenched emission, which is over five times more intense than that in the initial state, is retained under ambient conditions upon decompression. This work provides a promising pressure indicating material, particularly used in pressure stability monitoring for equipment working at extreme environments.

Water-Soluble Luminescent Polymers with Room-Temperature Phosphorescence Based on the α-Amino Acids.

Nonconventional luminophores have received increasing attention, owing to their fundamental importance, advantages in outstanding biocompatibility, easy preparation, environmental friendliness, and potential applications in sensing, imaging, and encryption. Purely organic molecules with outstanding fluorescence and room-temperature phosphorescence (RTP) have emerged as a new library of benign afterglow agents. However, the cost, toxicity, high reactivity, and poor stability of materials also limit their practical applications. Therefore, some natural products, synthetic compounds, and biomolecules have entered horizons of people. The as-designed exhibits sky blue and green fluorescence emission and green RTP emission (a lifetime of 343ms and phosphorescence quantum of 15.3%) under air condition. This study presents an organic fluorescence for biological imaging and RTP for anti-counterfeiting and encryption based on amino acids, maleic anhydride and 4-vinylbenzenesulfonic acid sodium salt hydrate. This study provides a strategy for nonconventional luminophores in designing and synthesizing pure organic RTP materials.

Considerable Piezochromism in All-Inorganic Zero-Dimensional Perovskite Nanocrystals via Pressure-Modulated Self-Trapped Exciton Emission.

Piezochromic materials refer to a class of matters that alter their photoluminescence (PL) colors in response to the external stimuli, which exhibit promising smart applications in anti-counterfeiting, optoelectronic memory and pressure-sensing. However, so far, most reported piezochromic materials have been confined to organic materials or hybrid materials containing organic moieties with limited piezochromic range of less than 100 nm in visible region. Here, we achieved an intriguing piezochromism in all-inorganic zero-dimensional (0D) Cs3Cu2Cl5 nanocrystals (NCs) with a considerable piezochromic range of 232 nm because of their unique inorganic rigid structure. The PL energy shifted from the lowest-energy red fluorescence (1.85 eV) to the highest-energy blue fluorescence (2.83 eV), covering almost the entire visible wavelength range. Pressure-modulated self-trapped exciton emission between different energy levels of self-trapped states within Cs3Cu2Cl5 NCs was the main reason for this piezochromism property. Note that the quenched emission, which is over five times more intense than that in the initial state, is retained under ambient conditions upon decompression. This work provides a promising pressure indicating material, particularly used in pressure stability monitoring for equipment working at extreme environments.

Blue emitting fluorescent Cs2ZnCl4 perovskite nanoprobe for the sensing and visual detection of bilirubin-a jaundice biomarker

Lead halide perovskites are an advanced class of materials with high photoluminescence and optoelectronic properties. However their instability towards moisture and lead toxicity hinders their applications especially in biological sensing. Hence the need for novel lead free perovskite nanocrystals are of utmost important. Herein we synthesized a lead free, highly efficient, stable, cost effective Cs2ZnCl4 perovskite nanocrystals (PNCs) and extends its application in biosensing. The PNCs exhibits bright blue fluorescence upon UV irradiation and was able to selectively detect bilirubin (BR) - a clinically important jaundice biomarker. The intense fluorescence emission of the sensor was completely quenched upon the addition of bilirubin. The sensor could detect bilirubin even in the presence of other interfering biomolecules with a good limit of detection of 26.10 nM. The sensor could successively detect BR in human serum samples. Furthermore, for the visual detection of bilirubin, a paper strip sensor was also designed making the sensor more economical and adaptable.

Tripeptide-Assisted Gold Nanocluster Formation for Fe3+ and Cu2+ Sensing.

Fluorescent gold nanoclusters (AuNCs) have shown promise as metal ion sensors. Further research into surface ligands is crucial for developing sensors that are both selective and sensitive. Here, we designed simple tripeptides to form fluorescent AuNCs, capitalizing on tyrosine's reduction capability under alkaline conditions. We investigated tyrosine's role in both forming AuNCs and sensing metal ions. Two tripeptides, tyrosine-cysteine-tyrosine (YCY) and serine-cysteine-tyrosine (SCY), were used to form AuNCs. YCY peptides produced AuNCs with blue and red fluorescence, while SCY peptides produced blue-emitting AuNCs. The blue fluorescence of YCY- and SCY-AuNCs was selectively quenched by Fe3+ and Cu2+, whereas red-emitting YCY-AuNC fluorescence remained stable with 13 different metal ions. The number of tyrosine residues influenced the sensor response. DLS measurements revealed different aggregation propensities in the presence of various metal ions, indicating that chelation between the peptide and target ions led to aggregation and fluorescence quenching. Highlighting the innovation of our approach, our study demonstrates the feasibility of the rational design of peptides for the formation of fluorescent AuNCs that serve as highly selective and sensitive surface ligands for metal ion sensing. This method marks an advancement over existing methods due to its dual capability in both synthesizing gold nanoclusters and detecting analytes, specifically Fe3+ and Cu2+.

Electronic Effect Driven Specific and Sensitive Recognition toward GHB.

Precise detection of a trace substance that intrinsically possesses weak chemical activity and less-distinctive spatial structure is of great significance, but full of challenges, as it could not be effectively recognized via either an active covalent reaction process or multiple noncovalent interactions toward its simple structure. Here, the electronic-effect-driven recognition strategy was proposed to visually sense an illicit drug, γ-hydroxybutyric acid (GHB), which was treated as an analyte model due to its inherent simple structure. In particular, a sensing system composed of two probes substituted by the nitro (-NO2) and the hydrogen (-H), was constructed with the characteristic yellow coloring and blue fluorescence, as well as high sensitivity (0.586 ng/mL), fast response (0.2 s), and specific recognition, even in the presence of 22 interferents. In addition, a portable eyeshadow box-like sensing chip was fabricated and proven to be reliable and feasible in sensing GHB disguised in liquors for self-protection in a covert manner. Hence, this work developed an electronic-effect-driven modulation strategy of the recognition interaction between the probe and the analyte and, thus, would open up a new thought for detecting the analyte with weak activity and a simple structure, as well as propel the relevant application in real scenarios.

Self-assembled dipeptide grafted nanohybrid material strips for reliable spectroscopic and electrochemical recognition of tryptamine

According to the World Health Organization (WHO), foods high in tryptamine may cause foodborne diseases and abnormal activity in the central nervous system (CNS). The real-time monitoring of tryptamine levels is an emphasized topic among scientific community. In the present work, we report a cost-effective fluorescent paper strips-based methodology impregnated with self-assembled dipeptide-modified (DM1) zinc oxide (ZnO) i.e.DM1@ZnO for the real-time monitoring of tryptamine levels. It is based on an organic-inorganic nanohybrid material of self-assembled N-functionalised dipeptide molecule coated over the surface of ZnO thus tailoring its properties for the detection of tryptamine employing spectroscopic and electrochemical methods. The designed material exhibited a noteworthy response towards tryptamine irrespective of the presence of other biogenic amines (BAs). It selectively displayed blue fluorescence under the 365 nm UV light. On top of that, the detection of tryptamine was also corroborated by its transition to 2-oxytryptamine, as deduced from its electrochemical route. Thus, the proposed paper strip-based methodology unbolts a realistic platform for the efficient recognition of varying levels of tryptamine thus tackling the prima facie reasons for foodborne diseases.

Visual detection and discrimination of nerve and blood agents using a dual-site fluorescent probe in living cells and mice

Of all chemical warfare agents (CWAs), only nerve and blood agents cause massive mortality at low concentrations. To better detect and discriminate nerve and blood agents, a reliable detection method is desirable. We report a series of fluorescent probes for nerve and blood agent detection. Among the tested probes, SR-Pip detected nerve and blood agents quickly (within 10 s for nerve agents and 1 min for blood agents). SR-Pip coupled with nerve agent produced a weak orange fluorescence with good sensitivity [limit of detection (LOD)= 5.5 μM]. Upon reaction with blood agent, the fluorescence of SR-Pip changed from orange fluorescence to blue fluorescence with detection limits as low as 9.6 nM. This probe effectively visualised different concentrations of nerve agents in living cells and mice. A portable test kit using SR-Pip instantly detected nerve and blood agents. To the best of our knowledge, SR-Pip is the first fluorescent probe for nerve and blood agent detection.

Intermolecular π-π interactions-induced aggregation based on bispyrene for ultrasensitive detection of picric acid (PA) and 2,4-dinitrophenol (DNP)

It was still important to explore excimer emission-based fluorescence probes for nitroaromatics detection by formation or destruction of pyrene excimer with strong emission change. In this work, we have synthesized a simple bis(pyrene) derivative (BisPyH) and studied its optical behavior by using UV–vis and fluorescent spectroscopy. In pure DMSO solution, it emitted a weak blue fluorescence due to the formation of excimer states, on the contrary, the BisPyH in the DMSO/H2O (v/v, 1:1) mixture solution was self-assembled to form aggregates via intermolecular π-π interactions among pyrene units, giving almost 10-fold fluorescence enhancement compared to that in pure DMSO solution. The formed aggregates just offered a perfect platform for the selective detection PA and DNP explosives by quenching the bright green intermolecular-excimer emission in competitive environment. BisPyH exhibited a limit of detection (LOD) towards PA, and DNP as low as 7.32 × 10−8, and 8.11 × 10−8 M, respectively. Subsequently, the fluorescence quenching mechanism was demonstrated by the density functional theory (DFT), UV–vis and fluorescence spectra, SEM, and the quenching constants. Furthermore, filter paper strips and thin-layer chromatography (TLC) plates coated with BisPyH were able to detect PA and DNP in the practical application.

Carbon quantum dots from hemicucur[6]bit and the application for the detection of Pb2+

A macrocyclic compound, hemicucurbit[6]uril (HemiQ[6]), is employed as the carbon source to produce a novel sort of carbon quantum dots (CQDs) with blue fluorescence in aqueous solution. The CQDs are fully identified by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Nuclear Magnetic Resonance (NMR), zeta potential, ultraviolet/visible (UV–vis) and photoluminescence spectroscopy (PL). The nanomaterial is developed for the analysis of Pb2+ in the light of the Resonance Rayleigh scattering (RRS) changes with the increasing Pb2+ concentration. The proposed probe emerges a high selectivity to Pb2+ and excellent sensitivity in the linear concentration range of 0–6 μM with a detection limit low to 0.42 μM, which is superior to the previous values of Pb2+ sensors, as well as the good anti-interference ability is confirmed by the specifical response to Pb2+ in the presence of other metal cations. Therefore, the proposed analysis of Pb2+ is explored for the application in real samples of tap water and lake water, in satisfied results of acceptable recoveries.

Carbon quantum dots as a turn-on fluorescent probe for the sensitive detection of Cd2+

In this study, fluorescent carbon dots were synthesized for the first time using ammonium citrate and glutamic acid as precursors via a one-pot hydrothermal method. The synthesized carbon dots emit blue fluorescence at 436 nm (excited at 320 nm) and demonstrate excellent photobleaching resistance and fluorescence stability in high salt environments. Within the range of 1–25 μM, the fluorescence of CDs gradually increases with the increasing concentration of Cd2+, reaching a limit of detection as low as 13 nM. This phenomenon could be ascribed to the chelation-enhanced fluorescence, a result of Cd2+ forming complexes with the abundant surface functional groups such as CN–, –COOH, –OH, –NH2 in CDs. Furthermore, this turn-on fluorescent probe has been successfully used for the detection of Cd2+ in tap water and lake water, providing an efficient and sensitive method for the analysis of environmental metals.

Customized carbon dots as a fluorescent sensor for detecting paraquat through enhanced excited state binding energy

A novel fluorescent sensor utilizing customized carbon dots (CDs) has been developed for the rapid and efficient detection of the herbicide paraquat. The 4,4′-diamino-2,2′-stilbenedisulfonic acid (DSD acid) functionalized CDs (DSD-CDs) were synthesized by a hydrothermal method using citric acid and L-cysteine as precursors, followed by amidation with DSD acid. The resultant DSD-CDs exhibited bright blue fluorescence upon UV excitation. The fluorescence of the functionalized carbon dots was effectively quenched by paraquat, following a static quenching mechanism as confirmed by fluorescence lifetime measurements. Interestingly, the mechanism study revealed that the excited-state of the DSD-CDs could interact effectively with paraquat, resulting in stronger fluorescence quenching compared to the ground-state. The sensor showed high sensitivity, selectivity, and stability, with a wide linear range of 0.01 ∼ 2 mg/L (R2 = 0.997) and a low detection limit of 0.003 mg/L. The developed fluorescent sensor demonstrated exceptional potential for paraquat detection in actual samples, encompassing blood, urine, soybean, and river water, with recovery rates exceeding 83 % and relative standard deviations (RSD) below 10 %. This underscores its practical utility in environmental protection and clinical testing applications.

Synthesis, Spectral Characteristics, Sensing Properties and Microbiological Activity of New Water-Soluble 4-Sulfo-1,8-naphthalimides

A new water-soluble polyamidoamine (PAMAM) dendrimer modified with 4-sulfo-1,8-naphthalimide (DSNI) and its monomeric structural analogue (MSDI) were synthesized. Their photophysical properties were investigated in organic solvents of different polarities and aqueous solutions. The effect of pH on fluorescence intensity was determined. It was found that the dendrimer emits blue fluorescence in an acidic medium, which is quenched in an alkaline environment. This phenomenon is due to the possibility of suppression of nonradiative photoinduced electron transfer in acidic media. The influence of different metal ions (Cu2+, Pb2+, Sn2+, Sr2+, Mg2+, Ba2+, Co2+, Hg2+, Zn2+, Ni2+, Fe3+, Al3+) and anions (CN−, S2−, S2O52−, HPO42−, H2PO4−, F−, CH3COO−, NO2−, CO32−, SO42−) on the intensity of the emitted fluorescence was studied. Quenching was only found in the presence of Cu2+. This makes the dendrimer suitable for determining copper ions in water solutions in the presence of other metal ions and anions. Additionally, DSNI was used as a ligand to obtain a stable copper complex, the structure of which was investigated by electron paramagnetic resonance (EPR), infrared spectrum, and elemental analysis. Two copper ions were found to form a complex with one dendrimer. The in vitro microbiological activity of the new compounds against bacteria Pseudomonas aeruginosa and two viruses HRSV-2 and HAdV-5 was investigated. With a view to obtaining antibacterial and anti-viral textiles, cotton fabrics were treated with the three compounds, and then their activity against the same microbial strains was investigated. It was found that the microbiological activity was preserved after the application of the new compounds to the cotton fabrics.

Development of a new series of thioacetal based fluorescence chemosensors for highly sensitive determination of Hg2+ in environmental samples and cell imaging

Mercury ion is one of the most harmful metal ions with significant hazards to the environment and human health. Thus, the development of innovative, sensitive, and selective sensors to help address the detrimental impacts of heavy metal contamination is necessary. In this work, we present three new chemosensors based on the deprotection reaction of the thioacetal group for distinguishing Hg2+ in environmental samples. These chemosensors show good photophysical properties with high quantum yield in aqueous medium. These prepared chemosensors were employed as fluorometric sensors for the determination of Hg2+ through the quenching of fluorescence emission due to the Hg2+-induced hydrolysis of the thioacetal to the aldehyde group. In the presence of Hg2+, chemosensors showed an emissive color transformation from blue fluorescence to non-fluorescence under UV light, which was readily seen by the visual eye. These chemosensors also exhibited highly distinctive selectivity toward Hg2+ over other interfering metal ions, with detection limits of 1.1 ppb, 13.4 ppb, and 12.7 ppb. Moreover, the practical applicability of chemosensor was successfully demonstrated in real water samples and herb extract samples.

Coumarin-hemicyanine-based ratiometric fluorescent probes for detection of strong acidity

Fluorescent probes for determination of strongly acidic pH values are urgently needed, especially the ones with ratiometric signal changes. Here, two fluorescent probes (CP and CyC) based on coumarin-hemicyanine were synthesized. Both probes emitted red fluorescence under weakly acidic to weakly alkaline conditions, whereas blue fluorescence under strongly acidic conditions. Notably, probe CP displayed good stability, water solubility, anti-interference ability, repeated utilization and instant response. Encouraged by the good performance, probe CP based test strips were used to indicate the pH of aqueous solutions, and to detect HCl or NH3 vapor in air reversibly.

Aluminium-doped Carbon Dots for the Simultaneous Selective Detection of Five Tetracycline Antibiotics.

In this paper, the aluminium-doped carbon dots (Al-CDs) were developed for simultaneous selective detection of five tetracycline antibiotics (TCs), including minocycline (MC), tetracycline (TC), oxytetracycline (OTC), doxycycline (DOC) and chlortetracycline (CTC). With the bright blue fluorescence, Al-CDs displayed excellent stability and showed no obvious fluorescence intensity changes under different ionic strength, acidic or alkaline environment, continuous ultraviolet light illumination, and even longtime storage at room temperature. As adding different antibiotics, the fluorescence of Al-CDs was strongly quenched by five TCs and showed no distinguished changes with the addition of other kinds of antibiotics. The presence of interferential metal ions, anions and small organic molecules imposed no effect on the simultaneous selective detection of five TCs. A good linear relationship was achieved for five TCs in the range of 0-100μM, and the limit of detection for MC, TC, OTC, DOC, and CTC were 13.91 (0-100μM), 15.54 (0-100μM), 14.26 (0-100μM), 13.48 (0-100μM) and 13.88nM (0-100μM), respectively. Moreover, Al-CDs was successfully used to the detection of five TCs in real samples with recovery ranging from 92.47% to 122.05%, confirming a bright future for the practical applications in the assays of foods, medicines, and environments.

Efficient porphyrin integrated UiO-66 probes for ratiometric fluorescence sensing of antibiotic residues in milk.

Dual-emissive fluorescence probes were designedby integrating porphyrin into the frameworks of UiO-66 for ratiometric fluorescence sensing of amoxicillin (AMX). Porphyrin integrated UiO-66 showed dual emission in the blue and red region. AMX resulted in the quenching of blue fluorescence component, attributable to the charge neutralization and hydrogen bonds induced energy transfer. AMX was detected using (F438/F654) as output signals. Two linear relationships were observed (from 10 to 1000nM and 1 to 100µM), with a limit of detection of 27nM. The porphyrin integrated UiO-66 probe was used to detect AMX in practical samples. This work widens the road for the development of dual/multiple emissive fluorescence sensors for analytical applications, providing materials and theoretical supporting for food, environmental, and human safety.

A visual and sensitive sensor for colorimetric and fluorescent recognition of Fe3+/2+, theoretical calculation and strip applications in wine

Total iron ions (Fe3+/2+) are a critical factor influencing wine quality and stability. A novel “turn-on” fluorescent probe (E)-2-((4-(5-methyl-1H-benzo[d]imidazol-2-yl)benzylidene)amino)phenol (probe MBBP) for monitoring Fe3+/2+ in wine was developed. It was designed with benzimidazole as the fluorophore and o-aminophenol as the Fe3+/2+ recognition site, simple and easy to prepare. The probe itself in EtOH/H2O (v: v, 49:1) emitted weak fluorescence and produced strong blue fluorescence after adding Fe3+/2+. The sensing of Fe3+/2+ was performed via the nucleophilic attack of Fe3+/2+ to imine groups of the probe with a 1:1 binding stoichiometry, and the fluorescence enhancement of the sensor was mainly due to the generation of compound 3 with the ICT effect. Results demonstrated that the probe exhibited high selectivity and sensitivity with a lower detection limit of 0.054 nM than previously reported Fe3+/2+ probes. In addition, based on the TD-DFT method and CAM-B3LYP and PBE0 functional theory, the significant changes in the dihedral angle stemmed from the isomerisation and rotation of the C = N bond. Probe MBBP was successfully applied to detect Fe2+/3+ in wine by intelligent software and the rapid detection of Fe3+/2+ using strips was also conducted.

Hydrothermal Synthesis of Tartaric Acid Functionalized Amino Acid CQD for Sensing of Hg2+ and Fe3+ Ions in Aqueous Medium

AbstractCarbon quantum dots (CQDs) are a type of carbon‐based nanoparticles that are typically smaller than 10 nanometres in size. In this study, L‐tryptophan‐mediated CQDs were synthesized using the hydrothermal carbonization (HTC) technique, which is known for its non‐toxic, environmentally friendly, and cost‐effective nature. The synthesized carbon quntum dot was successfully characterized. The HR‐TEM analysis clearly revealed the formation of specific aggregates with a size distribution ranging from 3.0 to 5.1 nm. These L‐tryptophan‐mediated CQDs exhibited remarkable emission behaviour, displaying strong and stable blue fluorescence. Moreover, they were utilized as a sensor for the sensitive detection of Fe3+ and Hg2+ ions in an aqueous solution, employing a fluorescence quenching mechanism. The limit of detection for Fe3+ sensing was determined to be 1.2×10−5 M, while for Hg2+ sensing, it was found to be 1.9×10−5 M. The sensing of Fe3+ and Hg2+ ions was also confirmed through visual eye detection, as a significant color change of the CQDs was observed. Additionally, a competitive study was conducted to verify the selectivity of the L‐tryptophan‐mediated CQDs towards Fe3+ and Hg2+ metal ions.

A new oligo(N,O-donor)-like ratiometric fluorescent probe with FRET effect for dual-channel recognition of B4O72- ions in practical water samples

B4O72- ions are widely found in various production and living environments, and can cause serious effects on human health. For this reason, it is necessary to develop a high-efficiency method for the detection of B4O72- ions. Here a oligo(N,O-donor)-like dual-channel ratiometric fluorescence probe H3L was designed and synthesized for the detection of B4O72- ions in environmental samples. The recognition of B4O72- is based on the FRET effect by the probe H3L, the naphthalene ring partially serves as an energy donor, benzene ring partially serves as an energy acceptor, and phenolic oxygen acts as a reaction site for B4O72-. The probe H3L mainly displays the blue fluorescence of the donor; the presence of the B4O72- ions turns on the FRET effect, which will lead to yellow fluorescence of the benzene ring acceptor, enabling a ratiometric fluorescence recognition process. The probe has a large Stokes red shift (Δλ = 123 nm), which makes the emission wavelength after red shift more than 500 nm, and the obvious colourless to yellow color change can be observed by naked eyes, which solves the background fluorescence interference problem of short-wavelength fluorescence probe. At the same time, the probe has high selectivity and high sensitivity (low detection limit of 17.3 nM). In addition, we have successfully used this probe to detect B4O72- ions in actual samples. These results showed that the probe has a broad application prospect.