Photoinduced Electron Transfer Mechanism Research Articles

Selective dual sensing strategy for free and vitamin D3 micelles in food samples based on S,N-GQDs photoinduced electron transfer.

A reliable nanotechnological sensing strategy, based on anS,N-co-doped graphene quantum dot (GQD) platform, has been developed to distinctly detect two key variants of vitamin D3, specifically the free (VD3) and the nanoencapsulated form (VD3Ms). For this purpose, food-grade vitamin D3 micelles were self-assembled using a low-energy procedure (droplet size: 49.6 nm, polydispersity index: 0.34, ζ-potential: -33 mV, encapsulation efficiency: 90 %) with an innovative surfactant mixture (Tween 60 and quillaja saponin). Herein, four fluorescent nanoprobes were also synthesized and thoroughly characterized: S,N-co-doped GQDs, α-cyclodextrin-GQDs, β-cyclodextrin-GQDs, and γ-cyclodextrin-GQDs. The goal was to achieve a selective dual sensing strategy for free VD3 and VD3Ms by exploiting their distinctive quenching behaviors. Thus, the four nanosensors allowed the individual sensing of both targetsto be performed (except α-CD-GQD for VD3Ms), but S,N-GQDs were finally selected due to selectivity and sensitivity (quantum yield, QY= 0.76) criteria. This choice led to a photoinduced electron transfer (PET) mechanism associated with static quenching, where differentiation was evidenced through a displayed 13-nm hypsochromic (blue) shift when interacting with VD3Ms. The reliability of this dual approach was demonstrated through an extensive evaluation of analytical performance characteristics. The feasibility and accuracy were proven in commercial food preparations and nutritional supplements containing declared nanoencapsulated and raw VD3, whose results were validated by a paired Student's t-test comparison with a UV-Vis method. To the best of our knowledge, this represents the first non-destructive analytical approach addressing the groundbreaking foodomic trend to distinctly detect different bioactive forms of vitamin D3, while also preserving their native nanostructures as achemical challenge, thus providing reliable information about their final stability and bioavailability.

Design and Construction of the Uranyl Coordination Polymer with Multifunction Stimulus Response: Fluorescent Sensors for Halide Ions and Photochromism.

It can provide ideas for the use of uranium elements in the treatment of spent fuel from nuclear wastewater to explore the application potential of uranium element. Thus, it is necessary to research the structure and properties of a novel uranyl coordination polymer (CP) for uranium recovery and reuse. Herein, we designed and prepared a new uranyl CP U-CMNDI based on UO22+ and H2CMNDI (H2CMNDI = N, N'-bis(carboxymethyl)-1,4,5,8-naphthalenediimide). Structural analysis shows that two uranyl ions are connected by two parallel deprotonated CMNDI ligands to form a discrete uranyl dimer structure. U-CMNDI can act as a potential stimulus-responsive halide ion sensor by a fluorescence "turn on" response in water. The limit of detection for fluoride (F-), bromide (Br-), iodide (I-), and chloride (Cl-) is 5.00, 5.32, 5.49, and 5.73 μM, respectively. The fluorescence "turn on" behavior is based on the photoinduced electron transfer (PET) mechanism between halide ions and electron-deficient NDI cores. In addition, U-CMNDI demonstrates a color response to ultraviolet light, exhibiting reversible photochromic behavior with a notable color change. The color change mechanism can contribute to the PET process and the radical process.

Design, synthesis, and spectrofluorimetric analysis of a novel fluorene-based chemosensor for the selective detection of picric acid

Fluorene-based probes are efficient candidates for sensing nitroaromatics and toxins. A novel fluorophore based on fluorene and terephthalaldehyde 1,4-YBF (1,4-ylidene-bis-fluorene) has been designed and synthesized for the efficient sensing of 2,4,6-trinitrophenol (picric acid) in solution. X-ray crystallographic studies, NMR, and mass analyses revealed the molecular stacking and exact structure of 1,4-YBF, which was further structurally optimised using the DFT technique. The optical properties of the newly synthesized compound were studied using UV–Vis and spectrofluorimetric analyses. The fluorophore was subjected to detailed sensing studies of various nitroaromatics, among which it was identified that picric acid (PA) exhibited the maximum quenching efficiency. The excellent sensing ability of the fluorophore was probably attributed to the photoinduced electron transfer (PET) mechanism. Further, pH studies and interference studies, along with its high selectivity towards PA and an LOD of 0.314 µM, revealed 1,4-YBF to be efficient in the detection of picric acid at a micromolar level.

A captivating approach to elevate the detection of Al3+ ions incorporates the utilization of a tripodal receptor intricately embellishing the surface of zinc oxide

The FDA (Food and Drug Administration, (USA)) lists ZnO as a material that is widely acknowledged to be safe. ZnO NPs with a range of tiny particle sizes were made using the precipitation process. ZnO nanoparticles' surface is embellished with a tripodal sensor containing naphthol units. The assembly with the same receptor decorated on ZnO NPs is contrasted with the cation detection capabilities of the purified tripodal receptor. The UV–visible spectrophotometric analysis was conducted to study the state transitions of the receptor and the decorated ZnO receptor. A positive selectivity to Al3+ cations is determined by the fluorescence study under ideal circumstances. The particle size and surface morphologies are determined by DLS and SEM analysis for the same receptor − TP1 and embellished with a tripodal receptor TP2. Using a fluorescence switch-on Photoinduced Electron Transfer (PET) mechanism, the receptor coated on ZnO detects the presence of Al3+ ions with specificity. The binding constant value was determined using the B-H plot equation. Binding stoichiometry for [TP1-Al3+, TP2-Al3+] showed a 1:1 ratio. The fluorescence switches ON-OFF process of the ZnO surface adorned − TP2 with Tripodal receptor- TP1 was used to create molecular logic gates, which can function as a module for sensors and molecular switches. The addition of Na2EDTA in the solution of the [TP1; TP2 − Al3+] complex resulted in a noticeable reduction in the emission of fluorescence. This finding offers compelling support for the reversibility of the chemosensor. To enable the practical application of this sensor, we have developed a cassette containing receptors TP1 and TP2. Successfully, it can detect Al3+ metal ions. We performed a comprehensive assessment of the dependability and appropriateness of our approach in measuring the concentration of Al3+ ions in wastewater produced by important industrial procedures.

Facile Layer Diffusion Technique for Synthesis of Terbium-Based Metal Organic Framework for Fluorometric Sensing of Hydroquinone.

A photoluminescent terbium (III)-based Metal Organic Framework (MOF) was synthesized at room temperature by layer diffusion method utilizing mixed carboxylate linkers (4,4'-oxybis(benzoic acid) and benzene-1,3,5 tricarboxylic acid). Synthesized MOF has crystalline nature and rod-shaped morphology and is thermally stable up to 455°C. The fluorescence emission spectra and theoretical results revealed that carboxylate linkers functioned as sensitizers for Tb(III) photoluminescence which resulted in four distinct emission peaks at 495, 547, 584, and 621nm corresponding to the transitions 5D4 → 7F6, 5D4 → 7F5, 5D4 → 7F4, and 5D4 → 7F3. Using synthesized MOF as fluorescent probe, hydroquinone was detected in aqueous medium with a detection limit of 0.048μM, remarkable recovery (95.6-101.1%), and relative standard deviation less than 2.25%. The quenching phenomenon may be ascribed to electron transfer from synthesized probe to oxidized hydroquinone via carboxylic groups on thesurface of MOF, which is further supported by photo-induced electron transfer mechanism. This study introduces a cheaper, faster, and more accurate method for hydroquinone detection.

Ultrafast and nanomolar detection of Al3+: Furazan based fluorescent chemosensor and its practices in Smartphone, test kit, water samples and living–cell

A new fluorescent chemoprobe (SDAF) was successfully synthesized and utilized as a sensor for the recognition of Al3+ in EtOH:HEPES (3:2, v:v, pH: 7.0) media. The SDAF depicted a selective “turn–on” response at λem = 467 nm to Al3+ over competitive cations, and the SDAF–Al3+ complex had a reversible response with F−. The limit of detection (LOD) was found about at nano–molar level (28.0 nM), demonstrating the sensitivity of the chemoprobe toward Al3+. The binding stoichiometry of SDAF–Al3+ was investigated by TOF–MS, Job's plot, 1H NMR and 13C NMR methods and found as 1:1. The recognition mechanisms of SDAF for the detection of Al3+ were the –C = N isomerization and photoinduced electron transfer (PET) mechanisms, and they were confirmed by density functional theory (DFT) computation. Furthermore, the SDAF was successfully employed in living–cell bioimaging and cytotoxicity, it was also utilized in Smartphone, test–kit and natural spring water (recovery values; 89.01 %– 96.33 %)applications.

A facile nickel nanocluster-based fluorescent ‘‘turn-off” sensor to detect tetracycline antibiotics

Developing an effective method for monitoring of tetracycline (TC) concentrations is extremely crucial due to its adverse effects on both ecosystems and human health. In this study, we developed a novel glutathione-protected nickel nanoclusters (GSHNiNCs) fluorescent (FL) sensing platform to detect TC. The GSHNi NCs were synthesized by a facile one-pot route with GSH as a stabilizer and ascorbic acid (AA) as reducing agent. The experimental results confirmed that the FL of GSHNiNCs was quenched in the presence of TC based on both of the inner-filter effect (IFE) and photoinduced electron transfer (PET) mechanisms to achieve high sensitivity. Under the optimal conditions, excellent linear relationships existed between the FL intensities of GSHNiNCs and the logarithmic TC concentrations in the range of 0.5–120.0 and 120.0–300.0 μM. Even in the absence of surface modification or any complex signal amplification techniques, the proposed FL sensing platform for TC detection showed a low limit of detection of 58 nM (3σ/k). Thus, this approach provides considerable simplicity, low-cost, timesaving and flexibility for the construction of a TC sensor. Most remarkably, we could selectively analyze TC in milk samples without the need for tedious or time-consuming pretreatment processes. This work expands the FL analysis platform for TC detection, and facilitates the design and development of NiNC-based FL sensors for the monitoring of antibiotics.

TDDFT Study on the ESIPT Properties of 2-(2'-Hydroxyphenyl)-Benzothiazole and Sensing Mechanism of a Derived Fluorescent Probe for Fluoride Ion.

The level of fluoride ions (F-) in the human body is closely related to various pathological and physiological states, and the rapid detection of F- is important for studying physiological processes and the early diagnosis of diseases. In this study, the detailed sensing mechanism of a novel high-efficiency probe (PBT) based on 2-(2'-hydroxyphenyl)-benzothiazole derivatives towards F- has been fully investigated based on density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. F- attacks the O-P bond of PBT to cleavage the dimethylphosphinothionyl group, and the potential products were evaluated by Gibbs free energy and spectroscopic analyses, which ultimately identified the product as HBT-Enol1 with an intramolecular hydrogen bond. Bond parameters, infrared vibrational spectroscopy and charge analysis indicate that the hydrogen bond is enhanced at the excited state (S1), favoring excited state intramolecular proton transfer (ESIPT). The mild energy barrier further evidences the occurrence of ESIPT. Combined with frontier molecular orbital (FMO) analysis, the fluorescence quenching of PBT was attributed to the photoinduced electron transfer (PET) mechanism and the fluorescence turn-on mechanism of the product was attributed to the ESIPT process of HBT-Enol1.

Photoinduced electron transfer in Eu2+ and Sm3+ co-doped CaF2 nanocrystals prepared by co-precipitation

We report on the photoinduced electron transfer in Eu2+ and Sm3+ co-doped CaF2 nanocrystals prepared by a facile co-precipitation method using CaCl2, EuCl2, SmCl3 and NH4F. The doping of divalent Eu2+ was realized by employing granular zinc in the CaCl2/EuCl2 solution under nitrogen to reduce Eu3+→ Eu2+. The CaF2:xEu,0.2%Sm nanocrystals were prepared with different Eu concentrations of x = 0, 0.2, 0.5, 1.5, and 2.5%, resulting in an average crystallite size between 54 and 36 ± 1 nm. The maximum luminescence intensities of Eu2+ and Sm2+ were obtained for the x = 0.5% sample. Photoinduced electron transfer and back transfer in the CaF2:0.5%Eu,0.2%Sm nanocrystals were measured by detecting the Eu2+ and Sm2+ luminescence, upon exposure to 340 and 310 nm UV LED light. Interestingly, the photoionization of Eu2+ occurred 6 times faster for the sample co-doped with 0.2% Sm. Upon exposure to 340 nm light, a reduction and increase of the Eu2+ and the Sm2+ luminescence were observed, respectively. Subsequent exposure to 310 nm light decreased the Sm2+ luminescence, but the luminescence of Eu2+ kept on being bleached, albeit at a lower rate. Whilst the Sm valence state could be reversibly changed between the trivalent and divalent state by 340 and 310 nm light, the observation that the Eu2+ luminescence did not recover may indicate that a third centre is involved in the photoinduced electron transfer mechanisms.

Density Functional Theory Calculations on Fluorescence-Enhanced Mechanisms of the Optical Sensor for Zinc Ions, ADPA.

N-(9-anthracenylmethyl)-N-(2-pyridinylmethyl)-2-pyridinemethanamine (ADPA) as a specific ion sensor for Zn2+ has been widely applied. Although the photo-induced electron transfer (PET) mechanism was proposed previously, its fluorescence-enhanced effect still remains somewhat ambiguous, according to unknown influences of non-radiative energy decay pathways, such as intersystem crossing and internal conversion. Herein, a thorough study using density functional theory has been performed for low-lying electronic states of the ADPA monomer and hydrated ADPA-Zn2+ complex. Based on interfragment charge transfer analyses, we quantitatively calculated the amount of transferred electrons in the monomer and complex, providing solid evidences for the PET mechanism and in line with the conclusion of frontier molecular orbital analyses. Moreover, the ISC process of S1→T2 was confirmed to play a considerable role in the excitation energy relaxation process of the ADPA monomer, but this influence was significantly suppressed in the hydrated ADPA-Zn2+ complex. These results provide additional clues for the design of new metal ion-specific fluorescence probes.

Orientation and Membrane Partition Free Energy of PeT-Based Voltage-Sensitive Dyes from Molecular Simulations.

Voltage measurement via small-molecule fluorescent indicators is a valuable approach in deciphering complex dynamics in electrically excitable cells. However, our understanding of various physicochemical properties governing the performance of fluorescent voltage sensors based on the photoinduced electron transfer (PeT) mechanism remains incomplete. Here, through extensive molecular dynamics and free energy calculations, we systematically examine the orientation and membrane partition of three PeT-based voltage-sensing VoltageFluor (VF) dyes in different lipid environment. We show that the symmetry of the molecular scaffold and the net charge of the hydrophilic headgroup of a given VF dye dominate its orientation and membrane partition, respectively. Our work provides a mechanistic understanding of the physical properties contributing to the voltage sensitivity, signal-to-noise ratio, as well as membrane distribution of VF dyes and sheds light onto rational design principles of PeT-based fluorescent probes in general.

Investigating structural dynamics and sensing capabilities: Spectroscopic and DFT analysis of novel AIEE active deferasirox based organic sensor

A deferasirox based sensor DPA was rationally designed through single step amidation reaction. Sensor DPA exhibited aggregation induced emission enhancement (AIEE) property that was attributed to restriction in intramolecular rotation (RIR). Moreover, the sensor DPA displayed remarkable bathochromic shift (red-shift) of 110 nm in wavelength, ascribed to formation of J-aggregates. Furthermore, sensor DPA was employed for the selective and sensitive fluorescence based sensing of hazardous and carcinogenic nitrobenzene (NB). The sensor DPA successfully detected NB in solution through the quenching of emission intensity. The quenching of sensor fluorescence intensity was ascribed to photoinduced electron transfer (PET) mechanism. The sensing mechanism was investigated by 1H NMR titration experiment, Job's plot and density functional theory (DFT) calculations. Additionally, the existence of non-covalent interactions between sensor DPA and NB were examined by Bader's Quantum theory of atoms in molecules (QTAIM) and non-covalent interaction (NCI) analysis. Finally, sensor DPA was employed for the detection of volatile nitrobenzene in vapor phase.

On-Off Ratiometric Fluorescence Europium(III) Metal-Organic Framework for Quantitative Detection of the Inflammatory Marker Neopterin.

Benefiting from the unique photoluminescence behavior of the lanthanide(III) ions and organic ligands, a lanthanide(III) metal-organic framework (Ln-MOF) material can simultaneously demonstrate photoluminescence of lanthanide(III) cations and organic molecules and endow its superior applications of fluorescence sensing behaviors. Herein, we present a europium(III) MOF material {[Eu2(BPTA)·(CH3COO)2·3DMA]·0.5DMA·3H2O}n (1) (where H4BPTA is 3,3',5,5'-biphenyltetracarboxylic acid) for photoluminescence performance of quantitatively sensing the inflammatory marker neopterin (Neo). The obtained 1 comprises Eu2(COO)4 paddlewheel secondary building units, which could be bridged by BPTA4- ligands to extend a 2D framework. The fluorescence titration indicates 1 can achieve simultaneous fluorescence behavior of Eu3+ ions and Neo via on-off ratiometric effects and thus could be exploited as the ratiometric fluorescence sensor matrix. Such a fluorescence phenomenon of 1 as a ratiometric sensor for quantitative detection of Neo via an on-off ratiometric effect is never observed in MOF chemistry. Moreover, naked-eye visible color variations of the fluorescence for 1 could be observed from red to blue with increasing concentrations of Neo, confirmed by fluorescent test strips as well as portable fluorescent hydrogels. And 1 also shows a low detection limit of 15.11 nM. A synergetic contribution of the competitive absorption, fluorescence resonance energy-transfer, and photoinduced electron-transfer mechanisms between Neo and the framework of 1 realizes the on-off ratiometric fluorescence behavior for Neo detection, supported by the UV-vis spectral overlap experiment and DFT calculations.

Zinc(II)-MOF: A Versatile Luminescent Sensor for Selective Molecular Recognition of Flame Retardants and Antibiotics.

An exceptional Zinc(II)-organic framework with the formula [{Zn(L4-py)(bdc)}·DMF]n (Zn-MOF) has been constructed solvothermally using a novel linker L4-py {2,7-bis(3-(pyridin-4-ylethynyl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone}, coligand H2bdc (1,4-benzenedicarboxylic acid), and ZnBF4·xH2O. The ligand L4-py has been fabricated after functionalization of NDA (1,4,5,8-naphthalenetetracarboxylic dianhydride) core with 3-(pyridin-4-ylethynyl)phenyl group. The single-crystal X-ray analysis reveals that Zn-MOF exhibits a comprehensive three-dimensional (3D) framework architecture and features (4)-connected uninodal dia; 4/6/c1; sqc6 topology with point symbol {66} and two-dimensional (2D) + 2D, parallel polycatenation. Notably, Zn-MOF displayed excellent fluorescence phenomenon and stability in water as well as in methanol solvents and was harnessed as a versatile sensor, demonstrating selective and sensitive molecular recognition of flame retardants and antibiotics. Notably, Zn-MOF displayed 57 and 49.5% quenching efficiency for the flame-retardant pentabromophenol (PBP) and 3,3',5,5'-tetrabromobisphenol A (TBPA), respectively. Whereas an outstanding 90% quenching efficiency was observed for antibiotics, tetracycline (TC) and secnidazole (SD). The mechanistic investigations of this luminescence quenching suggest that this might be primarily occurring via the Fourier resonance energy transfer (FRET) and photoinduced electron transfer (PET) mechanisms, which might be assisted by the competitive absorption and host-guest interactions. The π-electron-rich framework structure of sensor Zn-MOF activates this mechanism.

Perylene diimide covalent organic frameworks super-reductant for visible light-driven reduction of aryl halides

In recent years, there has been a growing interest in the utilization of molecular photocatalysts in their radical ionic forms, especially as visible-light super-reductants. These catalysts exhibit remarkable capabilities in facilitating otherwise inert high-potential organic reactions, such as the reduction of aryl halides to aryl radicals. However, the development of heterogeneous super-reductants has lagged behind due to the deactivation effect caused by molecular aggregation. This study presents a novel approach to address this limitation by heterogenizing perylene diimides (PDIs) super-reductants with a consecutive photo-induced electron transfer mechanism into two-dimensional donor-acceptor (D-A) covalent organic frameworks (COFs). Both COFs, possessing D-A electronic structures and photothermal effects, demonstrated superior visible-light photocatalytic performance compared to their homogeneous counterparts. They achieved up to 99% conversion in the dehalogenation of aryl halides, primarily through a hydrogen atom trapping aryl radical mechanism. Additionally, we conducted a comparative investigation of the excited states of radical anionic D-A-type COFs and DPPDI using femtosecond transient absorption spectroscopy. Notably, the lifetimes of COFs were significantly prolonged, measuring 210 and 260 ps, respectively, compared to the 150 ps lifetime of (DPPDI•−). This study offers valuable insights into the design of efficient free radical ion-type photocatalysts, with potential applications in various chemical transformations.

Photoredox-Catalyzed Defluorinative Carboxylation of gem-Difluorostyrenes with Formate Salt.

Herein, we present a transition-metal-free, easy handling protocol for regioselective carboxylation of gem-difluorostyrenes with sodium formate as the C1 source. 30 examples of α-fluoracrylates were obtained in yields of 30 to 80% under these conditions. A defluorinative monofluorovinyl intermediate and consecutive photoinduced electron transfer mechanism were proposed after mechanism investigation.

Ethyl 3-aminobenzo[b]thiophene-2-carboxylate Derived Ratiometric Schiff Base Fluorescent Sensor for the Recognition of In3+ and Pb2.

An ethyl 3-aminobenzo[b]thiophene-2-carboxylate derived ratiometric Schiff base fluorescent sensor R was devised and synthesized. R exhibited a highly sensitive and selective ratiometric response to In3+ in DMF/H2O tris buffer solution. R exhibited a colorimetric/fluorescent dual-channel response to In3+. More importantly, R can distinguish In3+ from Ga3+ and Al3+ in less than 5min. R exhibited a good linear correlation with the concentration of In3+ in the 5-25μM range and the limit of detection for In3+ was found to be 8.36 × 10-9M. According to the job`s plot and MS spectra, R formed a complex with In3+ at 1:2 with a complexation constant of 8.24 × 109 M2. Based on Gaussian theory calculations, the response mechanism of R to In3+ can be explained by photo-induced electron transfer (PET) and intramolecular charge transfer (ICT) mechanisms. In addition, R can be used for the detection of indium in tap water with satisfactory recoveries. Meanwhile, R displayed a linear relationship to micromolar concentrations (0-50μM) of Pb2+ and recognized Pb2+ in a ratiometric response with a detection limit of 8.3 × 10-9M.

Programmable DNA barcode-encoded exponential amplification reaction for the multiplex detection of miRNAs.

Multiple analysis of miRNAs is essential for the early diagnosis and monitoring of diseases. Here, a programmable, multiplex, and sensitive approach was developed for one-pot detection of miRNAs by melting temperature encoded sequences and exponential isothermal amplification (E-EXPAR). In the presence of target miRNAs, the corresponding templates initiate the cycles of nicking and polymerization/displacement, generating numerous barcode strands with unique encoding sequences. Subsequently, generated barcode strands hybridize with fluorescent probes and quench the fluorophore by a triplet of G base through a photo-induced electron transfer mechanism. Finally, a melting curve analysis is performed to quantify miRNAs by calculating the rate of fluorescence change at the corresponding melting temperature. Based on this, miRNA-21, miRNA-9, and miRNA-122 were detected with the detection limits of 3.3 fM, 2.9 fM, and 1.7 fM, respectively. This E-EXPAR was also employed to simultaneously detect three miRNAs in biological samples, showing consistent results with RT-qPCR. Overall, this study provides a programmable and universal platform for multiplex analysis of miRNAs, and holds great promise as an alternative to the multiplex analysis in clinical diagnostics and prognostics for nucleic acid detection.

A benzoxazole-triphenylamine conjugated fluorogenic probe for specific detection of sarin gas mimic diethylchlorophosphate.

In this study, an excellent chromo-fluorogenic PMPA probe, (E)-4-(((4-(benzoxazole-2-yl)phenyl)imino)methyl)-N,N-diphenylamine, is introduced for the detection of sarin gas mimic diethyl chlorophosphate (DCP) in solution and gaseous phases. On adding DCP into PMPA solution in a pure DMSO and water-DMSO (4 : 1) medium, it exhibits a hypsochromic shift from yellow to colorless and from no fluorescence to highly intense blue-violet photoluminescence via the formation of a phosphorylated PMPA-DCP product due to the inhibition of intramolecular charge transfer (ICT) and photoinduced electron transfer (PET) mechanism. The sensor could detect DCP in the presence of several other notorious guest analytes with a detection limit in the μM range. Moreover, to accomplish the on-spot detection of DCP and explore the practical applicability of the probe, a paper strip-based test kit, "dip-stick" method, and, more interestingly, a real sample analysis was demonstrated in spiked soil samples.

Molecular two-point recognition of fructosyl valine and fructosyl glycyl histidine in water by fluorescent Zn(II)-terpyridine complexes bearing boronic acids.

Selective recognition of fructosyl amino acids in water by arylboronic acid-based receptors is a central field of modern supramolecular chemistry that impacts biological and medicinal chemistry. Fructosyl valine (FV) and fructosyl glycyl histidine (FGH) occur as N-terminal moieties of human glycated hemoglobin; therefore, the molecular design of biomimetic receptors is an attractive, but very challenging goal. Herein, we report three novel cationic Zn-terpyridine complexes bearing a fluorescent N-quinolinium nucleus covalently linked to three different isomers of strongly acidified phenylboronic acids (ortho-, 2Zn; meta-, 3Zn and para-, 4Zn) for the optical recognition of FV, FGH and comparative analytes (D-fructose, Gly, Val and His) in pure water at physiological pH. The complexes were designed to act as fluorescent receptors using a cooperative action of boric acid and a metal chelate. Complex 3Zn was found to display the most acidic -B(OH)2 group (pKa = 6.98) and exceptionally tight affinity for FV (K = 1.43 × 105 M-1) with a strong quenching analytical response in the micromolar concentration range. The addition of fructose and the other amino acids only induced moderate optical changes. On the basis of several spectroscopic tools (1H, 11B NMR, UV-Vis, and fluorescence titrations), ESI mass spectrometry, X-ray crystal structure, and DFT calculations, the interaction mode between 3Zn and FV is proposed in a 1 : 1 model through a cooperative two-point recognition involving a sp3 boronate-diol esterification with simultaneous coordination bonding of the carboxylate group of Val to the Zn atom. Fluorescence quenching is attributed to a static complexation photoinduced electron transfer mechanism as evidenced by lifetime experiments. The addition of FGH to 3Zn notably enhanced its emission intensity with micromolar affinity, but with a lower apparent binding constant than that observed for FV. FGH interacts with 3Zn through boronate-diol complexation and coordination of the imidazole ring of His. DFT-optimized structures of complexes 3Zn-FV and 3Zn-FGH show a picture of binding which shows that the Zn-complex has a suitable (B⋯Zn) distance to the two-point recognition with these analytes. Molecular recognition of fructosyl amino acids by transition-metal-based receptors has not been explored until now.