Construction of Cyan Blue Fluorescence Probe based on Nitrogen-Doped Carbon Dots for Detecting Nitrite Ion in Ham Sausage.

Nitrite ion is one of the materials widely used in human life, and the accurate, sensitive and stable detection of nitrite ions is of great significance to people's healthy life. In this study, nitrogen-doped fluorescent carbon dots (N-CDs) for detecting nitrite salt solutions were prepared using citric acid monohydrate and Chrysoidin as precursors through a one-pot hydrothermal method. Under the condition of pH = 3, a noticeable quenching phenomenon occurred in the carbon dot solution with the increase in nitrite ion concentration. This quenching effect might be attributed to the diazonium effect. N-CDs have been successfully used as fluorescence probes for NO2- detection. NO2- can effectively quench the fluorescence intensity of N-CDs, providing a linear response to fluorescence quenching efficiency with respect to NO2- concentration within the range of 0-10µM and 10-30µM, and a detection limit of 52nM, showing high sensitivity. In addition, the probe was applied to the determination of NO2- in ham sausage samples with a detection limit of 0.67µM and recoveries in the range of 99.5-102.3%, the fluorescent probe showed satisfactory reliability.

Polymer-Metal Bilayer with Alkoxy Groups for Antibacterial Improvement.

Many bio-applicable materials, medical devices, and prosthetics combine both polymer and metal components to benefit from their complementary properties. This goal is normally achieved by their mechanical bonding or casting only. Here, we report an alternative easy method for the chemical grafting of a polymer on the surfaces of a metal or metal alloys using alkoxy amine salt as a coupling agent. The surface morphology of the created composites was studied by various microscopy methods, and their surface area and porosity were determined by adsorption/desorption nitrogen isotherms. The surface chemical composition was also examined by various spectroscopy techniques and electrokinetic analysis. The distribution of elements on the surface was determined, and the successful bonding of the metal/alloys on one side with the polymer on the other by alkoxy amine was confirmed. The composites show significantly increased hydrophilicity, reliable chemical stability of the bonding, even interaction with solvent for thirty cycles, and up to 95% less bacterial adhesion for the modified samples in comparison with pristine samples, i.e., characteristics that are promising for their application in the biomedical field, such as for implants, prosthetics, etc. All this uses universal, two-step procedures with minimal use of energy and the possibility of production on a mass scale.

FIA- spectrophotometric method for the determination of amoxicillin in pharmaceuticals; application of AES, GAPI, and AGREE greenness assessment tools.

A new, simple, and sensitive FIA-spectrophotometric method has been developed for evaluating pure amoxicillin and pharmaceutical formulations. The FIA method involves the reaction of dapsone with sodium nitrite and hydrochloric acid. Subsequently, the diazotized dapsone is coupled with amoxicillin in an alkaline medium, resulting in a stable orange dye with a maximum wavelength of 440 nm. The developed method was validated according to the ICH guidelines and found to have a concentration range of 1-150 µg/mL, a correlation coefficient of 0.9994, a molar extinction coefficient of 0.273 × 104 L/mol.cm, and a detection limit of 0.074 µg/mL. The FIA method was then evaluated using AES, GAPI, and AGREES analytical greenness assessment tools. The FIA method uses dapsone as an eco-friendly reagent, in addition to the FIA method's advantages of reduced sample and reagent usage, reduced waste generation, and cheaper equipment. So, it has been proposed as an excellent eco-friendly method for the determination of AMX in pharmaceutical formulations.

A Highly Sensitive Electrochemical Sensor for Capsaicinoids and Its Application in the Identification of Illegal Cooking Oil.

Capsaicinoids, mostly from chili peppers, are widely used in daily life. Capsaicinoids are considered to be markers for the identification of illegal cooking oil (ICO), which is a serious threat to public health. The identification of capsaicinoids can help reveal food-related fraud, thereby safeguarding consumers' health. Here, a novel and ultrasensitive method was established with a signal amplification strategy for the detection of capsaicinoids. AuNPs@Fe3O4 nanocomposites were functionalized with 4-aminothiophenol (4-atp). After diazotization, 4-atp on AuNPs@Fe3O4 reacted with capsaicinoids and formed capsaicinoids-azo-atp-AuNPs@Fe3O4. Ultimately, capsaicinoids-azo-atp-AuNPs@Fe3O4 was dropped onto the surface of a screen-printed carbon electrode (SPCE) and detected via the differential pulse voltammetry (DPV) method. AuNPs@Fe3O4 nanocomposites increased the specific surface area of the electrode. Moreover, the diazotization-coupling reaction enriched the analytes on the electrode surface. Liquid-liquid extraction was used for sample pretreatment. Under a pH value of 9.0 and concentration of 0.20 mol/L for the supporting electrolyte, the linearity of capsaicinoids in ICO is from 0.10 to 10.00 ng/mL, and the limit of detection (S/N = 3) is 0.05 ng/mL. This method is ultra-sensitive, reliable, and cost-effective for the detection of capsaicinoids. Herein, this method provides a promising tool for the identification of ICO.

The target-induced redox and diazotized reaction for colorimetric ratio detection of nitrite using CoOOH nanosheets as mimetic oxidase.

Nitrite is a commonly used food additive and water contaminant that has received widespread attention due to its harmful effects on humans. Here, a colorimetric ratio sensing platform for the detection of nitrite in foods as well as aquatic systems was developed via the catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by CoOOH nanosheets (CoOOH NSs). Interestingly, in the presence of nitrite, TMB complexes in acidic environments can be oxidized and diazotized to produce yellow oxidized TMB (oxTMB) and diazotized TMB, resulting in the nitrite concentration-dependent ratio variation for the absorbance peaks at 655 and 450 nm (A655/A450). The colorimetric ratio sensing offers higher sensitivity and better selectivity compared to conventional detection methods because of the specific target-induced reduction-oxidation and diazotized reaction, as well as the excellent mimetic oxidase activity of CoOOH NSs. Based on this strategy, a smartphone-assisted portable approach was designed for the in-situ/visual detection of nitrite, which has good application prospects.

A turn-on fluorescent nano-probe base on methanobactin-AuNPs for simple and efficient detection of nitrite.

Nitrite ions are important markers threatening humans and environmental security. A highly selective method for rapid detection of nitrite needs to be developed. Herein, a novel and rapid fluorescence method for nitrite determination is established on the basis of diazotization-coupling reaction of methanobactin (Mb) extracted by Methylosinus trichosporium OB3b with nitrite on the fluorescence. In the presence of gold nanoparticles (AuNPs), the fluorescence of AuNPs was strongly quenched by the Mb because the sulfhydryl or amino structures on the surface of Mb could be bound to the surface of AuNPs by forming Au-S or Au-N bonds. Upon addition of nitrite, the Mb easily reacts with nitrite to form azo products in the acidic medium. Then, with the increase of nitrite concentration, the Mb-AuNPs fluorescence was gradually recovered, realizing the turn-on fluorescence sensing of nitrite. Under optimal conditions, the proposed method has a good linear relationship with nitrite concentration in the range of 0-8.0 µM and 8.0-50.0 µM, and the detection limit is 16.21 nM. In addition, satisfactory results were obtained for nitrite analysis using milk, ham sausage and leaf mustard as real samples, which demonstrated that the method as-developed would have great practical application prospects.

Extending the visible light absorption of NH2-UiO-66 through diazotization reaction for photocatalytic chromium (VI) reduction.

The optical properties of NH2-UiO-66 as a visible light-active metal organic framework was further enhanced through the diazotization reaction with π-conjugated 1-naphthol reagent. Diffuse reflectance UV-Vis spectrum of diazotized MOF, named as Azo-UiO-66, exhibited a significant red shift compared to unfunctionalized NH2-UiO-66 due to the formation of diazo compound. Also, Tauc calculations indicated considerable decrease in band gap energy from 2.68 to 1.7 eV, resulting in improvement of visible light harvesting. Furthermore, other physicochemical techniques, e.g., X-ray diffraction (XRD), N2 adsorption-desorption analysis, thermogravimetric analysis (TGA), energ-dispersive X-ray (EDX), and CHN elemental analyses demonstrated the successful MOF diazotization with 1-naphthol and preservation of NH2-UiO-66 framework upon post-modification process. The reduction of hexavalent chromium, Cr(VI), as a serious contaminant in wastewater to less toxic Cr(III) was performed over prepared photocatalyst, which demonstrated the positive role of ligand functionalization and enhancement of visible light absorption on overall photocatalytic performance of Azo-UiO-66.

Deamination of 1-Aminoalkylphosphonic Acids: Reaction Intermediates and Selectivity.

Deamination of 1-aminoalkylphosphonic acids in the reaction with HNO2 (generated "in situ" from NaNO2) yields a mixture of substitution products (1-hydroxyalkylphosphonic acids), elimination products (vinylphosphonic acid derivatives), rearrangement and substitution products (2-hydroxylkylphosphonic acids) as well as H3PO4. The variety of formed reaction products suggests that 1-phosphonoalkylium ions may be intermediates in such deamination reactions.

Covalent grafting diazotized black phosphorus with ferrocene oligomer towards smoke suppression and toxicity reduction.

In comparison with the thermal hazard of polymers, noxious smoke and gas produced by the combustion of polymers make the environment self-purification a huge challenge. As a new type of a highly effective flame retardant, black phosphorus (BP) can effectively decrease the thermal hazard of polymers, but its performances in smoke suppression and toxicity reduction are unsatisfactory. In this article, a method of covalently grafting diazotized BP with a ferrocene oligomer was applied to promote the smoke suppression and toxicity reduction efficiency of BP. In our work, the BP-NH nanomaterials with a mass of amino groups on the surface were acquired by diazotizing the BP. Then, the BP-Fe was obtained by covalently grafting the ferrocene chloride salt and nitrogen-containing heterocycles on the surface of BP. The smoke production rate (SPR) and total smoke production (TSP) values of the epoxy resin (EP) decreased by 49.8% and 52.5% with the addition of 2 wt% BP-Fe, respectively. In comparison with previous studies, this work was far more effective than the previous work in smoke suppression and flame retardant. The release of toxic gases (CO and HCN) and volatile organic compounds in the EP was also effectively inhibited at the same time. In addition, the storage modulus and tensile strength of nanocomposites increased by 35.1% and 27.2% with the addition of 1 wt% BP-Fe. This work also provides a new idea on how to simultaneously strengthen the toxic smoke suppression, mechanical properties, and flame retardant of polymer materials.

Designing an intriguingly fluorescent N, B-doped carbon dots based fluorescent probe for selective detection of NO2- ions.

Low-cost nitrogen and boron-doped carbon nanodots (CPAP-CDs) with a high quantum yield (64.07%) were synthesized through a facile hydrothermal treatment. The obtained CPAP-CDs exhibited wide absorption, strong fluorescence, and pH-dependent behavior. The high fluorescence of CPAP-CDs was quenching in the presence of the nitrite ion in a concentration-dependent manner. The detection limit was as low as 6.6 nM with a wide linear detection range of 2 µM - 1 mM. Diazotization between the NO2- ion and CPAP-CDs resulted in the aggregation of CPAP-CDs and aggregation-induced emission quenching. The as-designed method was tested further with different water samples, such as tap, drinking, and seawater.

An eco-friendly methodology for the synthesis of azocoumarin dye using cation exchange resins.

An azo dye bearing coumarin moieties were prepared by diazotization of 4-Nitro aniline using amberlyst-15 as an acid catalyst then coupling of the obtained diazonium salt with coumarin. The obtained dye were characterized via UV-Vis, FT-IR, and 1H, 13C NMR spectroscopy This eco-friendly procedure seeks to get ride of the restrictions of the diazotisation traditional method such as using of strong acids, harmful solvents, modest yields and difficult purification, In addition, the pluses of this procedure include moderate conditions with good conversions, avoidance of harmful acids, simple product isolation process, selective, reduce by-products and purification procedures, recyclability of the catalyst and inexpensive procedures.

Investigation of stable solid diazonium salt by molecular structure, Hirshfeld surface analysis, optical and electrochemical studies, and applications.

The title compound is a new pyrazolone derivative which was synthesized starting from p-sulphophenyl-3-methyl-5-pyrazolone (1) by nitrosation at low temperature to afford the corresponding p-sulphophenyl-3-methyl-4-nitroso-5-pyrazolone which can exist both in nitroso (2a) and oxime tautomeric forms (2b). Reduction of the latter using zinc with hydrochloric acid furnished the 4-amino-p-sulphophenyl-3-methyl-5-pyrazolone (3). The diazotization of (3) under careful control of temperature and pH afforded the p-sulphophenyl-3-methyl-5-pyrazolone diazonium salt (4) which was re-crystallized from acidified ethanol to afford crystal suitable for X-ray studies. UV-visible spectrum and cyclic voltammetric studies were also carried out indicating λmax at 420 nm and HOMO-LUMMO energy gap was also calculated (Eg) of 2.95 eV. The molecular and crystal structures of the compound were clarified by single crystal X-ray diffraction indicated that it crystallizes as the sodium salt in the triclinic space group P -1, with the 4-azo-pyrazolone and the sulphophenyl groups being nearly coplanar. To get an insight to the intermolecular interactions in the crystal, a Hirshfeld surface analysis was also carried out.

Ratiometric Colorimetric Detection of Nitrite Realized by Stringing Nanozyme Catalysis and Diazotization Together.

Due to the great threat posed by excessive nitrite in food and drinking water to human health, it calls for developing reliable, convenient, and low-cost methods for nitrite detection. Herein, we string nanozyme catalysis and diazotization together and develop a ratiometric colorimetric approach for sensing nitrite in food. First, hollow MnFeO (a mixture of Mn and Fe oxides with different oxidation states) derived from a Mn-Fe Prussian blue analogue is explored as an oxidase mimic with high efficiency in catalyzing the colorless 3,3',5,5'-tetramethylbenzidine (TMB) oxidation to blue TMBox, presenting a notable signal at 652 nm. Then, nitrite is able to trigger the diazotization of the product TMBox, not only decreasing the signal at 652 nm but also producing a new signal at 445 nm. Thus, the analyte-induced reverse changes of the two signals enable us to establish a ratiometric colorimetric assay for nitrite analysis. According to the above strategy, facile determination of nitrite in the range of 3.3-133.3 µM with good specificity was realized, providing a detection limit down to 0.2 µM. Compared with conventional single-signal analysis, our dual-signal ratiometric colorimetric mode was demonstrated to offer higher sensitivity, a lower detection limit, and better anti-interference ability against external detection environments. Practical applications of the approach in examining nitrite in food matrices were also verified.

Novel Ring Systems: Spiro[Cycloalkane] Derivatives of Triazolo- and Tetrazolo-Pyridazines.

In orderto synthesize new pyridazine derivatives anellated with different nitrogen heterocyclic moieties, spiro[cycloalkane]pyridazinones were transformed into the corresponding thioxo derivatives via a reaction with phosphorus pentasulfide. The reaction of the formed 2,3-diazaspiro[5.5] undec-3-ene-1-thiones with hydrazine provided the corresponding 1-hydrazono-2,3-diazaspiro[5.5] undec-3-ene, whose diazotization led to the desired spiro[cyclohexane-1,8'-tetrazolo[1,5-b]pyridazines. The reaction of dihydropyridazinethiones with benzhydrazide afforded the corresponding 7H-spiro[[1,2,4]triazolo[4,3-b]pyridazin-8,1'-cyclohexanes]. As a result of our work, seven new pyridazinethione intermediates were prepared, which served as starting materials for the synthesis of two kinds of new ring systems: tetrazolo-pyridazines and triazolo-pyridazines. The six new annulated derivatives were characterized by physicochemical parameters. The new N-heterocycles are valuable members of the large family of pyridazines.

Preparation of Functionalized Carbon-Coated Cobalt Nanoparticles with Sulfonated Arene Derivatives, a Study on Surface Functionalization and Stability.

The functionalization of magnetic nanoparticles has been an important field in the last decade due to the versatile applications in catalysis and biomedicine. Generally, a high degree of functionalities on the surface of the nanoparticles is desired. In this study, covalent functionalization of various aromatic sulfonic acids on carbon-coated cobalt nanoparticles are investigated on surface functionalization yield and stability. The nanoparticles are prepared via covalent linkage of an in situ generated diazonium on the graphene-like surface. Adsorption and wash experiments were performed to confirm a covalent bonding of the naphthalene derivatives on the nanoparticle surface. With an increased number of sulfonic acid groups on the aromatic compound a significantly lower loading is observed on the corresponding functionalized nanoparticles. This can be counteracted by a change of nitrite species. With this method, nanoparticles with a high number of sulfonic acid groups can be produced.

Ratiometric Fluorescent Probe Based on Diazotization-Coupling Reaction for Determination of Clenbuterol.

In view of the potential harm caused by illegal feeding of clenbuterol (CLB) in the livestock industry, herein, a novel ratiometric fluorescent probe based on graphene quantum dots (GQDs)@[Ru(bpy)3]2+ was elaborately constructed for CLB detection. In this probe, GQDs acted as response signals, and their fluorescence was remarkably quenched by CLB through the diazotization-coupling reaction. As for [Ru(bpy)3]2+ as a reference signal, its fluorescence was hardly affected. The intensity ratio of two fluorophores showed good linearity with CLB concentration in the range of 0.05-40 µM, accompanied by visualization of fluorescence variation from yellow to red. The detection limit was as low as 0.029 µM. Particularly, the probe was successfully used to detect CLB in pork and beef samples with satisfactory recoveries. To our knowledge, this is the first report on a ratiometric fluorescent probe for the detection of CLB, which possesses broad application prospects in food safety risk monitoring.

Arene diazonium saccharin intermediates: a greener and cost-effective alternative method for the preparation of aryl iodide.

In the current protocol, the arene diazonium saccharin derivatives were initially produced from various substituted aromatic amines; subsequently, these intermediates were treated with a greener organic iodide for the preparation of the aryl iodide. We tried to choose low-cost, commercially available, biodegradable, recoverable, ecofriendly, and safe reagents and solvents. The arene diazonium saccharin intermediates could be stored in the liquid phase into a refrigerator for a long time with no significant loss activity. The outstanding merits of the current protocol (a) included the partial recovering of saccharin and tetraethylammonium salt, (b) reduce the use of solvents and the reaction steps due to eliminating separation and purification of intermediates, (c) good yield of the sterically hindered substrates, and (d) avoid the generation of heavy metal or corrosive waste.

Covalent Bonding of Si Nanoparticles on Graphite Nanosheets as Anodes for Lithium-Ion Batteries Using Diazonium Chemistry.

Silicon/carbon (Si/C) composite has been proven to be an effective method of enhancing the electrochemical performance of Si-based anodes for lithium-ion batteries (LIBs). However, the practical application of Si/C materials in LIBs is difficult because of the weak interaction between Si and C. In this study, we applied two-step diazotization reactions to modify graphite nanosheets (GNs) and Si nanoparticles (Si NPs), yielding a stable Si-Ar-GNs composite. Owing to aryl (Ar) group bonding, Si NPs were dispersed well on the GNs. The as-prepared Si-Ar-GNs composite delivered an initial reversible capacity of 1174.7 mAh·g-1 at a current density of 100 mAh·g-1. Moreover, capacity remained at 727.3 mAh·g-1 after 100 cycles, showing improved cycling performance. This synthesis strategy can be extended to prepare other Si/C anode materials of LIBs.

tert-Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis.

The upsurge interest in the development of efficient methodologies for the construction of nitrogen-containing frameworks via the use of expedient reagents have been creating a renaissance in contemporary organic chemistry. In this perspective, tertbutyl nitrite (TBN) is an emerging building block. Due to its unique structural features, it shows differential reactivity under different reaction conditions. These diverse reactivities have resulted in the construction of a diverse array of complex N-containing molecules. The primary objective of the present review is to bring the latest findings of TBN in terms of its applications in reactions (oxidation, diazotization, nitrosation, nitration, oximation, N-synthon, and miscellaneous reactions) into the limelight. For simplicity and brevity, reactions in each section are explained with the mechanism of formation and selected examples are given.

Investigation of a New Spectrophotometric Method for the Analysis of Ciprofloxacin Based on Microwave Assisted Diazotization.

A microwave-assisted diazotization reaction of ciprofloxacin was used for the analysis of ciprofloxacin in pharmaceutical samples. The ciprofloxacin was diazotized with phenol using acidified sodium nitrite in a domestic microwave oven. Faster microwave heating and microwave effects were found to be very effective for the process of diazotization. The microwave-assisted reaction was initiated in an acidic media and the colored product was stabilized in a slightly basic medium using a NaOH solution as a neutralizer. The product was found to exhibit the maximum absorbance at 440 nm. All of the experimental conditions like the concentration of reagents, microwave power and reaction time were optimized. The optimum concentrations for phenol, sodium nitrite, HCl and NaOH were found to be 140 ppm, 300 ppm, 0.006 M and 0.006 M respectively. The optimum reaction time was found to be 2 min and a medium high power of the microwave was found to be most effective. The limit of detection (LOD) and the limit of quantification (LOQ) were found to be 1.08 and 3.61 mg L-1 respectively. The developed method was successfully applied for the determination of ciprofloxacin in pharmaceutical samples. This new spectrophotometric method for the analysis of ciprofloxacin is fast, sensitive, easy and cost effective.