The fabrication of a hybrid fluorescent nanosensing system and its practical applications via film kits for the selective determination of mercury ions.

Heavy metal ions especially mercury exposure have severe toxic effects on living organisms and human health. Therefore, easy, accessible, and accurate determination strategies for the selective specification of mercury ions are essential for numerous disciplines. In the presented paper, new hybrid fluorescent iron oxide nanoparticles labeled with carbazole and triazole units (CT-IONP) were prepared via surface modification for the spectrofluorimetric determination of Hg2+ in environmental samples. The structure of the new sensing system is characterized via various spectroscopic, thermal, and microscopic techniques. Under optimized conditions, the hybrid system is not only used in fully water media but also highly fluorescent which led to the "turn-off" response towards Hg2+ ion in the presence of various competitive species. The presented sensing system was successfully used for the determination of Hg2+ ions in the wide linear working range (0.02-10.00 µmol.L-1) at nanomolar levels, where the limit of detection and quantification were calculated as 7.38 and 22.14 nmol.L-1. Importantly, the practical application of hybrid material was applied by CT-IONP embedded polycaprolactone (PCL) polymer film kits. The bluish color of fabricated film kits was instantly and dramatically turned colorless-dark patterns after the addition of Hg2+ ions, which resulted in convenient and rapid film test kits for selective detection.

Investigation of organic micropollutant pollution in Izmit Bay: a comparative study of passive sampling and instantaneous sampling techniques.

In this study, we used a comprehensive array of sampling techniques to examine the pollution caused by organic micropollutants in Izmit Bay for the first time. Our methodology contains spot seawater sampling, semi-permeable membrane devices (SPMDs) passive samplers for time-weighted average (TWA), and sediment sampling for long-term pollution detection in Izmit Bay, together. Additionally, the analysis results obtained with these three sampling methods were compared in this study. Over the course of two seasons in 2020 and 2021, we deployed SPMDs for 21 days in the first season and for 30 days in the second season. This innovative approach allowed us to gather sea water samples and analyze them for the presence of polycyclic aromatic hydrocarbons (Σ15 PAHs), polychlorinated biphenyls (Σ7 PCBs), and organochlorine pesticides (Σ11 OCPs). Using SPMD-based passive sampling, we measured micropollutant concentrations: PAHs ranged from 1963 to 10342 pg/L in 2020 and 1338 to 6373 pg/L in 2021; PCBs from 17.46 to 61.90 pg/L in 2020 and 8.37 to 78.10 pg/L in 2021; and OCPs from 269.2 to 8868 pg/L in 2020 and 141.7 to 1662 pg/L in 2021. Our findings revealed parallels between the concentrations of PAHs, PCBs, and OCPs in both SPMDs and sediment samples, providing insights into the distribution patterns of these pollutants in the marine ecosystem. However, it is worth noting that due to limited data acquisition, the suitability of spot sampling in comparison to instantaneous sampling remains inconclusive, highlighting the need for further investigation and data collection.

A water-soluble small molecular fluorescent sensor based on phosphazene platform for selective detection of nitroaromatic compounds.

Nitro-aromatic compounds have a deleterious effect on the environment and they are extremely explosive. Therefore, societal concern about exposure to nitro-aromatic compounds encourages researchers to develop selective and sensitive detection platforms for nitro-aromatic compounds in recent years. In this paper, a new 100% water-soluble cyclotriphosphazene-based bridged naphthalene material (4) was prepared as a small molecule fluorescent sensor for ultra-selective detection of nitro-aromatic compounds. The chemical structure of 4 was extensively characterized by mass spectrometry and nuclear magnetic resonance spectroscopies (31P, 13C, 1H). The photo-physical properties of the newly developed sensing system were investigated by steady-state fluorescence and UV-Vis absorption spectroscopies. The fluorescence sensor behaviors were extensively evaluated after treatment with the most commonly used metal cations, anions, competitive aromatic compounds, saccharides, and organic acids. The developed fluorescent sensing system (4) demonstrated ultra-selective fluorescence "turn-off" signal change toward nitro-aromatic compounds while other tested competitive species caused negligible changes. To evaluate selectivity, time-resolved, steady-state 3D-fluorescence and UV-Vis absorption spectroscopies were used in fully aqueous media. Moreover, theoretical calculations (density functional theory and time-dependent density functional theory) were applied and discussed to identify fluorescence sensing mechanisms toward nitroaromatic compounds for the presented sensing system.

Synthesis, characterization, and photophysical and fluorescence sensor behaviors of a new water-soluble double-bridged naphthalene diimide appended cyclotriphosphazene.

A new water-soluble template of double-bridged naphthalene diimide appended cyclotriphosphazene was prepared, and its photophysical and sensor behaviors were evaluated. The characterization of novel double-bridged naphthalene diimide appended cyclotriphosphazene (6) was carried out by NMR (1H, 13C, 31P) and mass spectroscopies. The photophysical behaviors of compound 6 were evaluated by UV-Vis absorption and fluorescence spectroscopies in various solvent systems and different concentrations. As an application for usability of the obtained water-soluble template in different applications, the fluorescence sensor property of compound 6 was investigated in the presence of many different competing species (organic acids, saccharides, nitroaromatic compounds, anions, and metal cations). The results obtained showed that compound 6 had selectivity against only the nitroaromatic species among the competing species tested.

Hexa-BODIPY-cyclotriphosphazene based nanoparticle for NIR fluorescence/photoacoustic dual-modal imaging and photothermal cancer therapy.

Theranostic, which integrates the diagnosis and tumor treatment in tandem, is an emerging strategy in cancer treatment. Here, we report a novel and unique theranostic nanoparticle, HBCP NP, based on hexa-BODIPY cyclophosphazene (HBCP). Due to the unique bulky molecular structure of HBCP, this nanoparticle can simultaneously perform near-infrared (NIR) fluorescence imaging and photoacoustic imaging (PAI). Interestingly, since reactive oxygen species (ROS) generation of HBCP NPs is completely inhibited, 'safe' fluorescence imaging is possible without the risk of cell damage even under laser irradiation. Finally, NIR fluorescence imaging and PAI in 4T1 tumor-bearing mice demonstrated selective accumulation of HBCP NPs at tumor sites. In addition, HBCP NPs exhibited excellent photothermal effects under high-power laser irradiation, achieving effective tumor growth inhibition.

Recent advances in the supramolecular assembly of cyclophosphazene derivatives.

Cyclophosphazenes are a fascinating group of inorganic heterocyclic compounds whose rings are constituted by the repetition of phosphorus and nitrogen atoms. They have received particular attention due to their easy functionalization and thermal stability and as an excellent core for the preparation of advanced materials. Rigid trispirocyclic derivatives of cyclophosphazenes afford numerous supramolecular structures that are suitable for the formation of host-guest complexes with a variety of guest molecules such as gas molecules and molecular rotor compounds. Also, the donor nitrogen atoms of the cyclophosphazene ring can participate in non-covalent interactions such as hydrogen bonding and metal coordination. It can also be used in the construction of supramolecular dendrimeric or polymeric systems as either the starting compound or the carrier of supramolecular groups. Thus, cyclophosphazenes have been employed in the preparation of supramolecular systems for about past 30 years. This review focuses on the state of recent advances in the construction of cyclotriphosphazene-based supramolecular systems built by non-covalent interactions and their applications such as host-guest complexes, liquid crystals, coordination polymers and nanostructures. The future perspective of cyclophosphazene supramolecular assemblies is also discussed.

Pyrene-BODIPY-substituted novel water-soluble cyclotriphosphazenes: synthesis, characterization, and photophysical properties.

In the present work, pyrene-boron-dipyrromethene (BODIPY)-substituted novel water-soluble cyclotriphosphazene derivatives (6 and 7) were synthesized by click reactions between a cyclotriphosphazene derivative with a hydrophilic glycol side group (2) and BODIPYs (4 and 5). All of the new compounds (2, 6, and 7) were characterized by Fourier-transform infrared and nuclear magnetic resonance spectroscopy, as well as mass spectrometry and elemental analysis. The photophysical properties of the BODIPY-substituted cyclotriphosphazenes (6 and 7) were investigated by UV-Vis and fluorescence emission spectroscopy in water and water/solvent mixtures. It was found that the target compounds were soluble in water and could be potential candidates as water-soluble fluorescent dyes for the desired applications.

Synthesis of new cyclotriphosphazene derivatives bearing Schiff bases and their thermal and absorbance properties.

In this study, a series of cyclotriphosphazene derivatives containing a Schiff base (3a-3d) were synthesized by the reactions of hexachlorocyclotriphosphazene (1) with bis-aryl Schiff bases ( 2a - 2d ) having different terminal groups (H, F, Cl, and Br). The products ( 3a - 3d ) were characterized by elemental and mass analyses, FT-IR, and 1 H, 13 C, and 31 P NMR spectroscopies. Furthermore, the structure of compound 3a was also determined by X-ray crystallography. The thermal behaviors and the spectral properties of the new cyclotriphosphazene compounds ( 3a - 3d ) were investigated and the results were compared in the series.

Synthesis, optical, and structural properties of bisphenol-bridged aromatic cyclic phosphazenes.

Phenoxy- and naphthoxy-substituted bisphenol-bridged cyclic phosphazenes were synthesized in 2 steps and their thermal, photophysical, and electrochemical properties were investigated. The structures of the cyclic phosphazene compounds were determined by ESI-MS mass spectrometry and 1 H, 13 C, and 31 P NMR spectroscopies. The photophysical studies of phenoxy- and naphthoxy-substituted bridged cyclophosphazenes were investigated by means of absorption and fluorescence spectroscopies in different solvents. Thermal and electrochemical properties of the target compounds were also studied. Furthermore, the excimer emissions through intramolecular interactions in solution and in solid state were investigated by fluorescence spectroscopy and the theoretical calculations were performed in detail using DFT.

Novel Water-Soluble Cyclotriphosphazene-Bodipy Conjugates: Synthesis, Characterization and Photophysical Properties.

In the present work, novel water-soluble cyclotriphosphazene derivatives (3b and 4b) were synthesized by 'click' reactions between cyclotriphosphazene derivative with hydrophilic glycol side groups (2) and Bodipy's (3a and 4a). All newly synthesized compounds (2, 3b and 4b) were characterized by fourier-transform infrared (FTIR), mass and NMR spectroscopy techniques and elemental analysis (EA). The photophysical properties of Bodipy substituted novel cyclotriphosphazenes (3a and 4a) were examined via UV-Vis absorption and fluorescence emission spectroscopy inside water and many organic solvents such as acetone, tetrahydrofuran, dichloromethane, dimethyl sulfoxide, etc., and the results were compared with the each other. Graphical Abstract.

The novel anthracene decorated dendrimeric cyclophosphazenes for highly selective sensing of 2,4,6-trinitrotoluene (TNT).

Novel fluorescent anthracene-decorated cyclotri- and cyclotetraphosphazenes (5 and 6) are designed and synthesized, and their chemosensor behaviors against nitroaromatic compounds are examined by UV/Vis and fluorescence spectroscopies for addressing the sensors with cyclophosphazenes for 2,4,6-trinitrotoluene detection. The fluorescence intensities of (5 and 6) are found to be selectively quenched by only 2,4,6-trinitrotoluene through the non-covalent π⋯π stacking interactions between anthracene-substituted cyclophosphazenes and 2,4,6-trinitrotoluene. In addition, cyclic voltammetry and theoretical calculation of novel sensor systems are studied. The proposed fluorescent sensor systems are critical in terms of practical detection of 2,4,6-trinitrotoluene.

Imidazole/benzimidazole-modified cyclotriphosphazenes as highly selective fluorescent probes for Cu2+: synthesis, configurational isomers, and crystal structures.

Configurational isomers (cis and trans) of imidazole- or benzimidazole-modified cyclotriphosphazenes (3a, 4a or 3b, 4b) were designed, synthesized and investigated as fluorescent probes for metal ions. The newly synthesized compounds were characterized by 1H and 31P NMR, and MALDI MS spectrometry. The configurations of geometric isomers were analyzed by X-ray crystallography and 31P NMR spectroscopy on addition of CSA. The photophysical behaviour and metal ion selectivity of the compounds were investigated by UV/vis and fluorescence spectroscopy. Among the examined 20 metal ions, the fluorescence emissions of the isomer mixtures were quenched by Cu2+ together with Fe2+, Fe3+, Zn2+ and Ni2+ ions, but each individual isomer (3a,b and 4a,b) exhibited an on-off-type fluorescence response with high selectivity towards only Cu2+ with a low limit of detection ranging from 1.27 µM to 2.04 µM. The complex stoichiometries of 3a,b and 4a,b with Cu2+ were determined as 1 : 1 (L/M) using the method of continuous variation (Job's plot) and density functional theory (DFT) calculations; moreover the complex formation of 4a with Cu2+ was unambiguously determined by X-ray crystallographic analysis that is consistent with the results obtained by the Job's plots as well as DFT.

Colorimetric Fluorescent Sensors for Hemoglobin Based on BODIPY Dyes.

Colorimetric fluorescent chemosensors 4 and 5 based on mono- and di- styryl borondipyrromethenes (BODIPY) linked methyl malonyl were designed for detection of hemoglobin (HgB). Their sensing behavior toward various analytes (Br-, EDTA, Glucose, CO32-, Fe2+, Fe3+, I-, NO3-, PO43-, SO42-,Cl-, Urea, K+, Mg2+, Na+, NH4+, Zn2+,Ca2+,Cd2+, Li+, Pb2+, Cs2+, Ag+, Mn2+, Cr2+, Ni2+, Hg2+, Al3+) were investigated by fluorescence spectroscopies. Addition of HgB to acetone: water (4:1) solutions of BODIPYs 4 and 5 solutions gave visual color changes, as well as significantly quenched fluorescence emissions, while other analytes induced no or much smaller spectral changes. The sensing method for both BODIPYs 4 and 5 was successfully applied to measure the HgB in human blood with satisfactory results. Spike and recovery tests in human blood samples exhibit good recovery rates for the spiked concentrations close to the limit of detection. It was found that BODIPYs 4 and 5 constituted the HgB selective fluorescent chemosensor (ON-OFF) and the detection limits were calculated to be 1.773 µg. mL-1 and 1. 295 µg.mL-1 respectively.

Hexa-BODIPY Linked-Triazole Based on a Cyclotriphosphazene Core as a Highly Selective and Sensitive Fluorescent Sensor for Fe(2+) Ions.

A new type of fluorescent chemosensor based on tethered hexa-borondipyrromethene cyclotriphosphazene platform (HBTC) linked via triazole groups was designed and synthesized. Its sensing behavior toward metal ions was investigated by ultraviolet-visible and fluorescence spectroscopies. Addition of a Fe(2+) ion to a tetrahydrofuran solution of HBTC gave a visual color change as well as a significantly quenched fluorescence emission, while other tested 19 metal ions induced no color or spectral changes. This compound was found to be highly selective and sensitive for Fe(2+) with a low limit of detection (2.03 µM) which is, to the best of our knowledge, the superior than the previously studied chemosensors for Fe(2+). Graphical Abstract ᅟ.

Novel hexapodal triazole linked to a cyclophosphazene core rhodamine-based chemosensor for selective determination of Hg(2+) ions.

The hexapodal Rhodamine B derivative compound 3 containing a cyclotriphosphazene core was synthesized and characterized by spectroscopic techniques such as FT-IR, (1)H, (13)C and (31)P NMR, HR-MS, MALDI MS and microanalysis. Compound 3 is a naked eye selective sensor with colorimetric and fluorescent properties for Hg(2+) ions in the presence of other metal ions such as Na(+), K(+), Ca(2+), Ba(2+), Mg(2+), Ag(+), Mn(2+), Cu(2+), Ni(2+), Co(2+), Pb(2+), Cd(2+), Zn(2+), Fe(2+), Fe(3+), and Cr(3+). The optical sensor properties of compound 3 were investigated using UV-vis and fluorescence spectroscopy. The lowest detection limit of compound 3 was determined as 3.76 × 10(-9) M (0.75 ppb) for Hg(2+) ions. The stoichiometry of compound 3-Hg(2+) complex was found to be 1:3 (ligand/metal ion). The reusable test strip was improved by the immobilization of compound 3 into a hydrogel network. The reusability of the sensor and test strip was tested with S(2-) ion solutions.

A first archetype of boron dipyrromethene-phthalocyanine pentad dye: design, synthesis, and photophysical and photochemical properties.

A novel type of phthalocyanine pentad containing four boron dipyrromethene (BODIPY) units at peripheral positions of the phthalocyanine framework has been designed and synthesized for the first time. The Sonogashira coupling reaction between 4,4'-difluoro-8-(4-ethynyl)-phenyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (Ethynyl-BODIPY) and 2(3),9(10),16(17),23(24)-tetrakis(iodo) zinc(ii) phthalocyanine (Iodo-Pc) has been used for the synthesis of the target compound. The BODIPY-phthalocyanine pentad dye (BODIPY-Pc) has been fully characterized by (1)H NMR, MALDI-TOF mass, FT-IR and UV-Vis spectroscopic techniques and elemental analysis as well. The photoinduced energy transfer process for this dye system was explored in tetrahydrofuran solution. The singlet oxygen generation capability and photodegradation behaviours of this BODIPY-Pc pentad dye were also investigated in DMSO for the determination of the usability of this new type of dye system as a photosensitizer in PDT applications.

Phosphazene based multicentered naked-eye fluorescent sensor with high selectivity for Fe3+ ions.

A novel on/off fluorescent rhodamine-based hexapodal Fe(3+) probe (L) containing a cyclotriphosphazene core was synthesized by an azide-alkyne "click-reaction". The synthesized compounds (1-5 and L) were characterized by FT-IR; (1)H, (13)C, and (31)P NMR; and MALDI MS spectrometry. The optical sensor features for the Fe(3+) complex of L were investigated by UV-vis and fluorescence spectroscopy. The stoichiometry of L-Fe(3+) complex was found to be 1:3 (ligand/metal ion), and the detection limit of L was determined as 4.8 µM (0.27 mg L(-1)) for Fe(3+) ions. The reusability of the sensor was tested by the addition of ethylenediamine to L-Fe(3+) complex solutions followed by the addition of Fe(3+) solution.

Intramolecular excimer formation in hexakis(pyrenyloxy)cyclotriphosphazene: photophysical properties, crystal structure, and theoretical investigation.

A hexakis(pyrenyloxy)cyclotriphosphazene is synthesized by the reaction of N3P3Cl6 with 2-hydroxypyrene, and its excimer emission through intramolecular interactions in solution and in the solid state has been investigated by fluorescence spectroscopy and X-ray crystallography. Thermal and electrochemical properties were investigated. A DFT benchmark study has been performed to evaluate the intramolecular interactions and molecular orbital levels by comparing with the experimental results.

Phosphorus-nitrogen compounds. 21. Syntheses, structural investigations, biological activities, and DNA interactions of new N/O spirocyclic phosphazene derivatives. The NMR behaviors of chiral phosphazenes with stereogenic centers upon the addition of chiral solvating agents.

The reactions of hexachlorocyclotriphosphazatriene, N(3)P(3)Cl(6), with N/O-donor-type N-alkyl (or aryl)-o-hydroxybenzylamines (1a-1e) produce mono- (2a-2e), di- (3a-3d), and tri- (4a and 4b) spirocyclic phosphazenes. The tetrapyrrolidino monospirocyclic phosphazenes (2f-2i) are prepared from the reactions of partly substituted compounds (2a-2d) with excess pyrrolidine. The dispirodipyrrolidinophosphazenes (3e-3h) and trispirophosphazenes (3i-3k) are obtained from the reactions of trans-dispirophosphazenes with excess pyrrolidine and sodium (3-amino-1-propanoxide), respectively. Compounds 3a-3d have cis and trans geometric isomers. Only the trans isomers of these compounds are isolated. Compounds 3a-3h have two stereogenic P atoms. They are expected to be in cis (meso) and trans (racemic) geometric isomers. In the trans trispiro compounds (3i-3k), there are three stereogenic P atoms. They are expected to be in racemic mixtures. The stereogenic properties of 3a-3k are confirmed by (31)P NMR spectroscopy upon the addition of the chiral solvating agent; (S)-(+)-2,2,2-trifluoro-1-(9'-anthryl)ethanol. The molecular structures of 3i-3k, 4a, and 4b look similar to a propeller, where the chemical environment of one P atom is different from that of others. Additionally, 4a and 4b are also expected to exist as cis-trans-trans and cis-cis-cis geometric isomers, but both of them are found to be in cis-trans-trans geometries. The solid-state structures of 2a, 2e, 2f, 3e, and 3f are determined by X-ray crystallography. The compounds 2f-2i, 3e-3i, and 3k are screened for antibacterial activity against gram-positive and gram-negative bacteria and for antifungal activity against yeast strains. These compounds (except 3f) have shown a strong affinity against most of the bacteria. Minimum inhibitory concentrations (MIC) are determined for 2f-2i, 3e-3i, and 3k. DNA binding and the nature of interaction with pUC18 plasmid DNA are studied. The compounds 2f-2i, 3e-3i, and 3k induce changes on the DNA mobility. The prevention of BamHI and HindIII digestion (except 2g) with compounds indicates that the compounds bind with nucleotides in DNA.

Absolute structure determination as a reference for the enantiomeric resolution of racemic mixtures of cyclophosphazenes via chiral high-performance liquid chromatography.

Reversed-phase chiral high-performance liquid chromatography (HPLC) is a potentially powerful technique for the enantiomeric resolution of racemic mixtures, although the elution order of enantiomers is only relative and it is necessary to fully characterize reference systems for this method to provide absolute configurational information. The enantiomeric resolution of a series of racemic di-spiro cyclotriphosphazene derivatives, N3P3X2[O(CH2)(3)NH]2 (X = Cl, Ph, SPh, NHPh, OPh) [(1)-(5), respectively] was carried out by reversed-phase chiral HPLC on a commercially available Pirkle-type chiral stationary phase (R,R)-Whelk-01 using 85:15 (v/v) hexane-thf as the mobile phase. The absolute configurations of the resulting enantiomers of compounds (3) (X = SPh) and (5) (X = OPh) were determined unambiguously by X-ray crystallography. For both (3) and (5) it was found that the SS enantiomer eluted before the RR enantiomer, indicating a convenient method to determine the absolute configurations of enantiomers of this series of cyclophosphazene derivatives and providing the first set of enantiomeric reference compounds for cyclophosphazene derivatives. These structures demonstrate an interesting anomaly in that the pair of enantiomers of (3) crystallize in enantiomorphically paired space groups whilst, under the same conditions, the solid-state forms of the enantiomers of (5) form structures in Sohncke space groups that are not enantiomorphous.