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.

An electrochemical sensor for detection of trace-level endocrine disruptor bisphenol A using Mo2Ti2AlC3 MAX phase/MWCNT composite modified electrode.

Bisphenol A (BPA) is an industrially preferred material for the production of plastic and polycarbonate as well as a used material for the interior of food and beverage cans. In this study, synthesis and electrochemical sensor application of Mo2Ti2AlC3/MWCNT (multi-walled carbon nanotube) nanocomposite for BPA sensing was evaluated. Mo2Ti2AlC3 was used as MAX phase material in the design of the sensor, and MWCNT was preferred to increase conductivity and sensitivity. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to determine Mo2Ti2AlC3/MWCNT nanocomposite's electrochemical sensor performances which had LOD of 2.7 nM and LOQ of 8.91 nM in the linear working range of 0.01-8.50 µM calculated from DPV. The composite showed a single oxidation step against BPA which is diffusion-controlled and irreversible. The sensor was successfully applied for the determination of BPA in milk pack, plastic bottle, and can with recoveries ranging from 95.67% to 100.60%. In addition, sensor performance was examined through selectivity, repeatability, and reusability studies. HPLC as a standard determination method was carried out for accuracy of the voltammetric determination method in the real samples. The developed sensor could be applied to different areas from industry quality control to clinical analysis for the detection of BPA.

A Hybrid Nanomaterial Based on Single Walled Carbon Nanotubes Cross-Linked via Axially Substituted Silicon (IV) Phthalocyanine for Chemiresistive Sensors.

In this work, the novel hybrid nanomaterial SWCNT/SiPc made of single walled carbon nanotubes (SWCNT) cross-linked via axially substituted silicon (IV) phthalocyanine (SiPc) was studied as the active layer of chemiresistive layers for the detection of ammonia and hydrogen. SWCNT/SiPc is the first example of a carbon-based nanomaterial in which an axially substituted phthalocyanine derivative is used as a linker. The prepared hybrid material was characterized by spectroscopic methods, thermogravimetry, scanning and transmission electron microscopies. The layers of the prepared hybrid were tested as sensors toward ammonia and hydrogen by a chemiresistive method at different temperatures and relative humidity as well as in the presence of interfering gases like carbon dioxide, hydrogen sulfide and volatile organic vapors. The hybrid layers exhibited the completely reversible sensor response to both gases at room temperature; the recovery time was 100-200 s for NH3 and 50-120 s in the case of H2 depending on the gas concentrations. At the relative humidity (RH) of 20%, the sensor response was almost the same as that measured at RH 5%, whereas the further increase of RH led to its 2-3 fold decrease. It was demonstrated that the SWCNT/SiPc layers can be successfully used for the detection of both NH3 and H2 in the presence of CO2. On the contrary, H2S was found to be an interfering gas for the NH3 detection.

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.

Sensing Volatile Pollutants with Spin-Coated Films Made of Pillar[5]arene Derivatives and Data Validation via Artificial Neural Networks.

Different types of solvents, aromatic and aliphatic, are used in many industrial sectors, and long-term exposure to these solvents can lead to many occupational diseases. Therefore, it is of great importance to detect volatile organic compounds (VOCs) using economic and ergonomic techniques. In this study, two macromolecules based on pillar[5]arene, named P[5]-1 and P[5]-2, were synthesized and applied to the detection of six different environmentally volatile pollutants in industry and laboratories. The thin films of the synthesized macrocycles were coated by using the spin coating technique on a suitable substrate under optimum conditions. All compounds and the prepared thin film surfaces were characterized by NMR, Fourier transform infrared (FT-IR), elemental analysis, atomic force microscopy (AFM), scanning electron microscopy (SEM), and contact angle measurements. All vapor sensing measurements were performed via the surface plasmon resonance (SPR) optical technique, and the responses of the P[5]-1 and P[5]-2 thin-film sensors were calculated with ΔI/Io × 100. The responses of the P[5]-1 and P[5]-2 thin-film sensors to dichloromethane vapor were determined to be 7.17 and 4.11, respectively, while the responses to chloroform vapor were calculated to be 5.24 and 2.8, respectively. As a result, these thin-film sensors showed a higher response to dichloromethane and chloroform vapors than to other harmful vapors. The SPR kinetic data for vapors validated that a nonlinear autoregressive neural network was performed with exogenous input for the best molecular modeling by using normalized reflected light intensity values. It can be clearly seen from the correlation coefficient values that the nonlinear autoregressive with exogenous input artificial neural network (NARX-ANN) model for dichloromethane converged more successfully to the experimental data compared to other gases. The correlation coefficient values of the dichloromethane modeling results were approximately 0.99 and 0.98 for P[5]-1 and P[5]-2 thin-film sensors, respectively.

A novel comparative study for electrochemical urea biosensor design: Effect of different ferrite nanoparticles (MFe2O4, M: Cu, Co, Ni, Zn) in urease immobilized composite system.

A new enzymatic electrochemical biosensor has been developed with the PANI/Nafion composite system containing ferrite nanoparticles with four different transition metals. The ferrite nanoparticles containing copper, cobalt, nickel, and zinc metals were synthesized by the co-precipitation method and their surfaces were modified with tetraethoxysilane and (3-aminopropyl) triethoxysilane to obtain -NH2 function in order to develop the purposed sensing system. The modified and unmodified ferrite nanoparticles were characterized by physically, chemically, and morphologically. Ferrite nanoparticles with suitable for enzyme immobilization were integrated on the GCE surface and covered with PANI/Nafion. According toelectrochemical measurements, it was determined that copper ferrite nanoparticles, which have the lowest bandgap value, significantly increased the biosensor performance. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to monitor biosensor production and evaluate its performance. A detection limit of 0.17 µM and a wide linear range of 0.5-45.0 µM were obtained for the urea detection with the DPV method with the sensing system (Nf/PANI/CuF/Urs). The biosensor has been successfully applied to soil and milk samples with high accuracy. In addition, it has been determined that the proposed method has good reproducibility, selectivity, and stability.

Direct and selective determination of p-coumaric acid in food samples via layered Nb4AlC3-MAX phase.

Phenolic compounds that are naturally found in food samples are not only an important part of the human diet but also useful bioactive substances for health. Among these, para-coumaric acid (p-CA) has antibacterial and antioxidant properties and is used in many industrial processes. In this study, the novel MAX-phase material, Nb4AlC3, was successfully prepared and characterized in detail with various spectroscopic, microscopic and thermal techniques. The sensor performance of Nb4AlC3 modified glassy carbon electrode (Nb4AlC3@GCE) was evaluated and analytical parameters were calculated. Experimental conditions such as pH and amount of modifier were optimized with differential pulse voltammetry (DPV) measurements. The real samples analyses of lemon, apple and pomegranate were applied for determination of p-CA with Nb4AlC3@GCE sensing system under the optimized conditions. The accuracy was evaluated by spike/recovery and high-performance liquid chromatography analysis, which accounted for high accuracy of the Nb4AlC3@GCE sensing system. The limit of detection, limit of quantification, linear working range and relative standard deviation (%) of the Nb4AlC3@GCE sensing system were determined as 0.28 and 0.85 µmol/L, 0.8-80.0 µmol/L, 3.17 %, respectively. The results showed that the proposed sensing system has the high precision at lower concentration of p-CA.

The chemical and electrochemical stimuli viologen substituted phthalocyanine with tunable optical features1.

In this study, viologen-tetrasubstituted Zn(II) phthalocyanines (PcV1 and PcV2) were designed and synthesized to achieve the tunable optical features via redox-active viologen groups. Several parameters relevant to the evaluation of the tunable optical features have been investigated: UV-Vis, cyclic voltammetry (CV), EPR, square wave voltammetry (SWV), and theoretical analyses. The results showed that upon reductions and oxidations of viologen groups either chemically or electrochemically, the optical features of PcV1 and PcV2 change drastically with switchable processes. These outcomes indicate that achieving control over optical features of large organic chromophores such as Pc with our rational design can be used for the design of new complex organic electronic materials.

Evaluation of the effectiveness of Ampicillin and Lactobacillus casei rhamnosus treatment in cases of preterm premature rupture of membranes remote from term.

OBJECTIVES: Preterm premature rupture of membranes (PPROM) remote from term is an important obstetric cause of maternal and fetal adverse outcomes. The aim of our study is to examine the efficacy of ampicillin and Lactobacillus casei rhamnosus treatment in cases of PPROM remote from term. MATERIAL AND METHODS: The study was carried out by examining the results of cases who were given Ampicillin and Lactobacillus casei rhamnosus treatment. The patients were divided into two groups. Group 1 who didn't develop clinical chorioamnionitis and Group 2 who developed clinical chorioamnionitis. Obstetric characteristics, neonatal outcomes, adverse events were recorded. RESULTS: A total of 46 pregnant women, 40 in Group 1 and six in Group 2, were included in the study. The frequency of clinical chorioamnionitis developing during the treatment was found to be 13.0%. Mean gestational age at diagnosis was 28.43 ± 2.38 and 28.17 ± 1.33 for Groups 1 and Group 2, respectively. Mean gestational age at the time of delivery was 32.38 ± 2.07 31.33 ± 1.63 for Group 1 and Group 2, respectively. The mean latency period for Group 1 and Group 2 was 27.45 ± 1.71 days, 23.66 ± 4.53, respectively. Sepsis developed in six newborns (15%) in Group 1, while it developed in three newborns (50%) in Group 2. While 90% of the babies in Group 1 were discharged from the hospital, this rate was 66.7% in Group 2. CONCLUSIONS: Ampicillin + Lactobacillus casei rhamnosus is an effective treatment method in PPROM cases and positively affects perinatal outcomes.

Ultrasensitive electrochemical sensor for detection of rutin antioxidant by layered Ti3Al0.5Cu0.5C2 MAX phase.

MAX phases have attracted great attention due to unique features such as thermal and electrical conductivity, easy fabrication, heat resistant, and lightweight. In this study, an easy and green method was employed to successfully develop a Ti3Al0.5Cu0.5C2 MAX phase structure, and a Ti3Al0.5Cu0.5C2 based glassy carbon electrode (GCE) was applied for the electrochemical determination of rutin antioxidants in mandarin and kiwi samples. The developed Ti3Al0.5Cu0.5C2 MAX phase was characterized by different techniques such as X-ray photoelectron spectroscopy (XPS), thermogravimetry and differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) to obtain information on the structural and morphological properties. Electrochemical methods such as cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were employed for the determination of rutin using Ti3Al0.5Cu0.5C2/GCE. The GCE modified with Ti3Al0.5Cu0.5C2 demonstrated amplified electrochemical response (ca. 4.25 times) in comparison to the bare GCE towards rutin, and exhibited ultra-sensitivity and selectivity in the presence of other interfering antioxidants. Under the optimum conditions, good linearity in the range of 0.02-50.00 µmol L-1 was obtained for rutin analysis by the Ti3Al0.5Cu0.5C2-based sensor with a limit of detection (LOD, 3σ/K) as low as 0.015 µmol L-1. The fabricated Ti3Al0.5Cu0.5C2 MAX phase was applied to determine trace levels of rutin in mandarin and kiwi samples with validation by high-performance liquid chromatography (HPLC), thus highlighting its potential for the electrochemical determination of small molecules in the agricultural field.

Sensitive, simple and fast voltammetric determination of pesticides in juice samples by novel BODIPY-phthalocyanine-SWCNT hybrid platform.

The present work describes the first synthesis of novel asymmetric zinc (II) phthalocyanine (ZnPc) including three boron dipyrromethene (BODIPY) and one ethyloxy azido moieties. Moreover, single walled carbon nanotube (SWCNT) surface was functionalized by this ZnPc containing BODIPY; using the azide-alkyne Huisgen cycloaddition (Click) reaction to obtain SWCNT-ZnPc hybrid material. Structural, thermal and morphological characterizations of both ZnPc and SWCNT-ZnPc hybrid were carried out in-depth by spectroscopic, thermal and microscopic techniques. In this study, the synthesized SWCNT-ZnPc material was decorated on composite glassy carbon electrode (GCE) by means of an easy and a practical drop cast method. The modified electrode was tested as a non-enzymatic electrochemical sensor in various common pesticides such as methyl parathion, deltamethrin, chlorpyrifos and spinosad. Electrochemical behavior of non-enzymatic electrode (GCE/SWCNT-ZnPc) was determined via cyclic voltammetry and differential pulse voltammetry. The non-enzymatic sensor demonstrated high selectivity for methyl parathion in a wide linear range (2.45 nM-4.0 × 10-8 M), low limit of detection value (1.49 nM) and high sensitivity (0.1847 µA nM-1). Also, the developing non-enzymatic sensor exhibited good repeatability (RSD = 2.3% for 10 electrodes) and stability (85.30% for 30 days). Validation guidelines by HPLC and statistical analysis showed that the proposed voltammetric method were precise, accurate, sensitive, and can be used for the routine quality control of methyl parathion determination in juice samples.

A synergetic and sensitive physostigmine pesticide sensor using copper complex of 3D zinc (II) phthalocyanine-SWCNT hybrid material.

2,3,9,10,16,17,23,24-Octakis (4-methyl-2,6-bis((prop-2-yn-1-yloxy)methyl)phenoxy) phthalocyaninato zinc(II) (Pc) bearing sixteen terminal ethynyl groups was synthesized and attached to SWCNT (Single-walled carbon nanotube) covalently to obtain three dimensional porous hybrid material (SWCNT-Pc 3D) and its copper complex (Cu-SWCNT-Pc 3D). The structural characterization and electrochemical sensor features of the Cu-SWCNT-Pc hybrid towards to physostigmine pesticide were performed. A fast, direct and suitable determination method for physostigmine detection was offered. The designed sensor, Cu-SWCNT-Pc 3D/GCE (glassy carbon electrode) shows sensitivity ca 1.8, 4.3 and 2.8 times more than that of SWCNT/GCE, SWCNT-Pc-noncovalent/GCE and SWCNT-Pc 3D/GCE in terms of peak heights while bare and Pc/GCE had almost no voltammetric response to 2 µM physostigmine in PBS at a pH of 7.0. The limit of detection and quantification of physostigmine determination with Cu-SWCNT-Pc 3D/GCE were found to be 53 and 177 nM in the range of 0.1-4.8 µM, respectively. This study demonstrated that the modification of the GCE with Cu-SWCNT-Pc 3D as an electrochemical sensor was acted as catalytic role toward physostigmine presence of other interfering pesticides as high sensitivity and selectivity. The electrochemical determination of physostigmine in real samples was performed under the optimized conditions, also accuracy of the electrochemical determination method was evaluated with HPLC as a standard determination method.

Fluorescence determination of trace level of cadmium with pyrene modified nanocrystalline cellulose in food and soil samples.

Cadmium is one of the most toxic metal that accumulates in the human body via food chain, industrial/agricultural activites. It also has negative effects in organs such as the brain, liver and central nervous system. Therefore, International Agency for Research on Cancer is classified cadmium as "carcinogenic to humans" (group 1). In this work, novel pyrene modified nanocrystalline cellulose (NP-1) was designed as a fluorescence sensor for selective determination of Cd2+ in food and soil samples. FTIR, UV-Vis, SEM, TEM and TGA were used for structural, morphological characterizations and thermal properties of NP-1. The experimental conditions such as selectivity, pH, sensor concentration, photostability, time and interaction mechanism were examined and optimized. The LOD was determined as 0.09 µM (10.70 µg/L) which was lower than WHO's permissible limit of cadmium in plant with 0.10-60.00 µM linear working range. Validation of the present method was performed by spike/recovery test and ICP-MS, then fluorescence determination of Cd2+ in food and soil samples was succesfully applied. The results indicated that the proposed method based on "turn-on" fluorescence of NP-1 was a simple, sensitive and reliable for rapid determination of Cd2+ in real samples with high applicability and stability.

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.

Highly selective and ultra-sensitive electrochemical sensor behavior of 3D SWCNT-BODIPY hybrid material for eserine detection.

In this work, 4,4-difluoro-8-(4-hydroxyphenyl)- 2,6-diethynly-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (BODIPY) having double terminal ethynyl groups was synthesized. Three dimensional single walled carbon nanotube (SWCNT)-BODIPY hybrid material (3D SWCNT-BODIPY) was synthesized by the reaction of BODIPY bearing double terminal ethynyl groups with azido containing SWCNTs via "Click" reaction. The structural properties and electrochemical detection of eserine (a pesticide) on BODIPY functionalized SWCNTs as a three dimensional (3D) material were investigated. A glassy carbon electrode (GCE) was modified by 3D SWCNT-BODIPY hybrid material for the determination of eserine in the range of 0.25-2.25 µM. In the study by the square wave voltammetry (SWV), the bare GCE showed no response, while the new peak at - 0.6 V appeared in the case of the modified electrode. The detection limit and quantification were determined as 160 nM and 528 nM for eserine on the 3D SWCNT-BODIPY modified electrode, respectively. Eserine was also determined with a standard addition method in different brands of orange juices, and the recovery of eserine was obtained to be in the range of 102.09% and 103.22%. This study clearly indicates that the 3D SWCNT-BODIPY modified electrode tested as an electrochemical sensor was found to be highly selective and sensitive to eserine.

Synthesis and organic solar cell performance of BODIPY and coumarin functionalized SWCNTs or graphene oxide nanomaterials.

The synthesis and characterization of new hybrid materials based on reduced graphene oxide (rGO) or single walled carbon nanotubes (SWCNTs) covalently functionalized by 4,4'-difluoro-8-(4-propynyloxy)-phenyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (BODIPY) (2) or 7-(prop-2-yn-1-yloxy)-3-(3',4',5'-trimethoxyphenyl)-coumarin (4) as light harvesting groups have been described. The organic solar cell performances of these novel nanomaterials in P3HT:PCBM blends were investigated. These covalently bonded hybrid materials (reduced graphene oxide:BODIPY (GB), reduced graphene oxide:Coumarin (GC), SWCNTs:BODIPY (CB) and SWCNTs:Coumarin (CC)) were prepared by an azide-alkyne Huisgen cycloaddition (click) reaction between the azide bearing SWCNTs or rGO and terminal ethynyl functionalized BODIPY (2) or coumarin (4) derivatives. The formation of novel nanomaterials was confirmed by FT-IR, UV-Vis and Raman spectroscopies and thermogravimetric analysis. The best performance on P3HT:PCBM organic solar cells was produced by SWCNTs:Coumarin (CC) hybrids which were coated on an indium tin oxide coated polyethylene terephthalate film (ITO-PET). The reference device based on the P3HT:PCBM blend without CC showed a power conversion efficiency (PCE) of 1.16%, an FF of 35% and a short-circuit current density (Jsc) of 5.51 mA cm-2. The reference device with CC hybrids within the P3HT:PCBM blend increased the values significantly to 1.62% for PCE, 40% for FF and 6.8 mA cm-2 for Jsc.

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.