Chameleon-like Response Mechanism of Gold-Silver Bimetallic Nanoclusters Stimulated by Sulfur Ions and Their Application in Visual Fluorescence Sensing.

Herein, 2-mercapto-5-benzimidazolesulfonate acid sodium salt dihydrate (MBZS)-protected gold-silver bimetallic nanoclusters, named MBZS-AuAg NCs, were synthesized. Interestingly, we found that MBZS-AuAg NCs solutions can exhibit different fluorescence color changes under sulfide stimulation. A series of modern analytical testing techniques were used to explore the interaction mechanism between MBZS-AuAg NCs and sulfide. Sulfide ions can not only cause MBZS-AuAg NCs to exhibit rich fluorescence color changes similar to those of a chameleon but also have four linear relationships between the response intensity and sulfide concentration. A wide-range sulfide fluorescence sensing platform was constructed based on four linear segments with different fluorescence color responses. This sensing platform can be directly used for the determination of S2- with a detection limit as low as 11 nM. The portable test paper based on MBZS-AuAg NCs can realize the visual and rapid detection of gaseous hydrogen sulfide with a detection limit of 100 ppb (v/v). The wide detection range of the proposed method not only allows it to be used as an alternative method for sulfide detection in environmental samples but also has potential applications in the rapid detection and early warning of hydrogen sulfide gas in industrial and mining scenarios.

Ratiometric fluorescence sensor based on europium-organic frameworks for selective and quantitative detection of cerium ions.

BACKGROUND: Due to the unavoidable use of cerium in daily life, the accumulation of cerium in the environment increases health risks for humans. Therefore, it is crucial to develop a chemical sensing technology for the rapid, sensitive, and selective detection of cerium ions. RESULTS: In this research work, a novel two-dimensional chain structure of a europium-based metal organic framework (Eu-MOF) [Eu2(tcpa)(Htcpa)2] was synthesized by using 3,4,5,6-tetrachloro-1,2-benzenedicarboxylic acid (H2TCPA) as the ligand and europium nitrate as the metal source. The results of powder X-ray diffraction and thermogravimetric analysis show that the synthesized Eu-MOF has excellent chemical and thermal stability. When the Eu-MOF suspension was excited by ultraviolet light at 292 nm, four fluorescence emissions were observed at 420, 595, 620 and 705 nm. It was particularly interesting that when cerium ions (Ce3+/Ce4+) were added to the Eu-MOF suspension, the fluorescence intensity at 420 nm was enhanced, while the fluorescence at 620 nm was quenched. On this basis, a ratiometric fluorescent sensor for detecting cerium ions was constructed, which has a good linear relationship in the range of 0.05-15 µM and a detection limit of 16 nM. The plausible mechanism of the change in the fluorescence characteristics of Eu-MOF caused by cerium ions was discussed in detail. Through the study of fluorescence lifetime and ultraviolet absorption, it was proven that the mechanism of Ce3+-quenching Eu-MOF fluorescence is the inner filter effect. Photoinduced electron transfer and internal filtering effects lead to fluorescence quenching at 620 nm, while redox reactions lead to fluorescence enhancement of the ligand at 420 nm. SIGNIFICANCE: The proposed ratiometric fluorescence sensor was successfully employed for the detection of cerium ions in real water samples, confirming that it can be used as an alternative method for the detection of Ce3+ and Ce4+ in environmental samples.

Recent Advancement on the Indirect or Combined Alternative Thiocyanate Sources for the Construction of S-CN Bonds.

The process of thiocyanation is a notable chemical conversion owing to the extensive range of applications associated with thiocyanate compounds in the field of organic chemistry. In past centuries, the thiocyanation reaction incorporated metal thiocyanates or thiocyanate salts as sources of thiocyanate, which are environmentally detrimental and undesirable. In recent literature, there have been numerous instances where combined or indirect alternative sources of thiocyanate have been employed as agents for thiocyanation, showcasing their noteworthy applications. The present literature review focuses on elucidating the ramifications associated with the utilization of indirect or combined alternative sources of thiocyanate in various thiocyanation reactions.

Atomically dispersed Fe-Zn dual-site nanozymes with synergistic catalytic effects for the simultaneous detection of Cr(VI) and 8-hydroxyquinoline.

Single-atom catalysts with atomically dispersed sites have been widely used as nanozymes for colorimetric sensing because their tunable M-Nx active centers are similar to those of natural enzymes. However, their low metal atom loading leads to insufficient catalytic activity and affects the sensitivity of colorimetric sensing, which limits their further applications. Herein, multi-walled carbon nanotubes (MWCNs) are selected as carriers to reduce the aggregation of ZIF-8 and improve the electron transfer efficiency of nanomaterials. Meanwhile, MWCN/FeZn-NC single-atom nanozymes with excellent peroxidase-like activity were prepared by pyrolysis on ZIF-8 doped with a second metal Fe. Based on the excellent peroxidase activity of MWCN/FeZn-NCs, a dual-functional colorimetric sensing platform for Cr(VI) and 8-hydroxyquinoline was established. The detection limits of the dual-function platform are 40 nM for Cr(VI) and 55 nM for 8-hydroxyquinoline. This work provides a highly sensitive and selective strategy for the detection of Cr(VI) and 8-hydroxyquinoline in hair care products, which has great application prospects in the field of pollutant detection and control.

Fabrication of Two Luminescent Imidazolyl Cadmium-Organic Frameworks and Their Sensing Mechanism for 2,6-Dichloro-4-nitroaniline.

2,6-Dichloro-4-nitroaniline, alias dicloran (DCN), is a broad-spectrum pesticide that can cause irreversible damage to the human body. Therefore, it is of great significance to develop a technology for the rapid and convenient detection of DCN. Luminescent metal organic frameworks have attracted extensive attention in the field of sensing and detection due to their excellent optical properties. In this study, two kinds of 2D Cd-MOFs (CdMOF-1 and CdMOF-2) were developed for the detection of residual DCN in the environment. Both CdMOFs exhibit excellent solvent and acid-base stability and can respond to DCN quickly and sensitively in a short time (30 s). CdMOFs not only have good selectivity and anti-interference toward DCN but also have good reusability. Under the conditions of DCN concentrations of 1-15 and 0.3-30 µM, the change in fluorescence intensity of CdMOF-1 and CdMOF-2 showed a good linear relationship with DCN concentration (R2 = 0.999/0.991), and the detection limits were 0.36 and 0.12 µM, respectively. Through ultraviolet-visible absorption spectroscopy (UV-Vis), X-ray photoelectron spectroscopy, fluorescence lifetime, and density functional theory calculations, it is revealed that the fluorescence quenching mechanisms of DCN for two kinds of Cd-MOFs are competitive absorption and photoinduced electron transfer, and there may be a weak π-π interaction. Finally, it is demonstrated that by using two types of fluorescent CdMOFs to make the fluorescent test paper and detect actual soil, these can be applied to the actual scene and achieve onsite real-time detection.

Dual-Color 2D Lead-Organic Framework with Two-Fold Interlocking Structures for the Detection of Nitrofuran Antibiotics and 2,6-Dichloro-4-nitroaniline.

The misuse of organic pollutants such as nitrofuran antibiotics (NFAs) and 2,6-dichloro-4-nitroaniline (DCN) has become a hot topic of global concern, and developing rapid, efficient, and accurate techniques for detecting NFAs and pesticides in water is a major challenge. Here, we designed a novel lead-based anion 2D metal-organic framework (MOF){[(CH3)2NH2]2[Pb(TCBPE)(H2O)2]}n (F3) with interlocking structures, in which TCBPE stands for 1,1,2,2-tetra(4-carboxylbiphenyl)ethylene. Powder X-ray diffraction and thermogravimetric analysis revealed that F3 has excellent chemical and solvent stability. It is worth noting that F3 has a grinding discoloration effect. The solvent-protected grinding approach achieved F3B with a high quantum yield (QY = 73.77%) and blue fluorescence, while the direct grinding method produced F3Y with a high quantum yield (QY = 37.27%) and yellow-green fluorescence. Importantly, F3B can detect NFAs in water rapidly and sensitively while remaining unaffected by other antibiotics. F3Y can identify DCN in water quickly and selectively while remaining unchanged by other pesticides. F3B demonstrated high selectivity and rapid response to NFAs at a limit of detection (LOD) as low as 0.26 µM, while F3Y indicated high selectivity and responded quickly to DCN in water at an LOD as low as 0.14 µM. The method was successfully applied to detect NFAs in actual water samples of the fish tanks and ponds as well as the pesticide DCN in soil samples. The recovery rates were 97.0-105.15% and 102.2-106.48%, and the relative standard deviations were 0.63-1.45% and 0.29-1.69%, respectively. In addition, F3B and F3Y can be made into fluorescent test papers for the visual detection of NFAs and DCN, respectively. Combined with experiments and density functional theory calculations, the mechanism of fluorescence quenching of MOFs by target analytes was also revealed.

Recent advances in photochemical and electrochemically induced thiocyanation: a greener approach for SCN-containing compound formation.

Techniques utilizing photo- and electrochemically induced reactions have been developed to accelerate organic processes. These techniques use light or electrical energy (electron transfer) as a direct energy source without using an initiator or reagent. Thiocyanates are found in biologically active and pharmacological compounds and can be converted into various functional groups. It is one of the most prominent organic scaffolds. Significant development in photo- and electro-chemically induced thiocyanation procedures has been made in recent years for the conception of carbon-sulfur bonds and synthesis of pharmaceutically important molecules. This review discusses different photo- and electro-chemically driven thiocyanation C(sp3)-SCN, C(sp2)-SCN, and C(sp)-SCN bond conception processes that may be useful to green organothiocyanate synthesis. We focus on the synthetic and mechanistic characteristics of organic photo- and electrochemically accelerated C-SCN bond formation thiocyanation reactions to highlight major advances in this novel green and sustainable research field.

Enhanced light-emitting diode induced fluorescence detection system with capillary electrophoresis.

An enhanced fluorescence detection system of capillary electrophoresis (CE) was equipped with a concave silver mirror, by which the detection sensitivity of light-emitting diode induced fluorescence (LEDIF) can be increased greatly. The silver concave mirror and the cathode window in photomultiplier tube (PMT) were accurately set face to face at the same axis. When the two labeled tumor markers exactly moved to the center of detection window, the emission from analytes are excitated by LED source. Currently, the analytes may be regarded as a luminescent source point. When the source point exactly moves to the focus of the concave mirror, the emission of the labeled sample was collected effectively, enhanced by convergence and reflected by the concave mirror. Then it was sensitively detected by the PMT. The optical mechanism of enhancing detection sensitivity was explored. A simple comparative test on sensitivity was carried out, which aimed to compare sensitivity of the new detection system with concave mirror to that without concave mirror but the other conditions were kept the same. Two tumor markers labeled with FITC were selected for the test, using the simple LEDIF detect system. The results (LOD, 150 nM for L-Leu and L-Val) showed that the detection sensitivity matched with concave mirror reached more 16 times than the detection method without concave mirror.

Enantioselective Organocatalyzed Direct α-Thiocyanation of Cyclic ß-Ketoesters by N-Thiocyanatophthalimide.

A new electrophilic thiocyanation reagent, N-thiocyanatophthalimide, was synthesized and applied to the first example of catalytic asymmetric electrophilic α-thiocyanation of various cyclic ß-ketoesters by the bifunctional cinchona alkaloid catalysis. Thus, a variety of chiral α-thiocyanato ß-ketoesters with a quaternary carbon center have been achieved in excellent yields (up to 99%) and high enantioselectivities (up to 94% ee) in a convenient manner.

N-Thiocyanatosaccharin: A "Sweet" Electrophilic Thiocyanation Reagent and the Synthetic Applications.

N-Thiocyanatosaccharin (R1) was readily prepared from the sweet additive Saccharin in two steps with a 71% overall yield. By applying this new reagent to diverse nucleophiles such as benzothiophenes, indoles, oxindoles, aromatic amines, phenols, ß-keto carbonyl compounds, and aromatic ketones, a novel electrophilic thiocyanation reaction was achieved with high yields (up to 99%). The potential recycling of Saccharin, the wide scope of substrates, and the mild reaction conditions made this protocol much more practical.

Enantioselective electrophilic cyanation of ß-keto amides catalysed by a cinchona organocatalyst.

An operationally simple protocol for the enantioselective electrophilic α-cyanation of ß-keto amides catalyzed by cinchona-derived catalysts has been demonstrated. The resulting products could be obtained with good to high enantioselectivities (up to 88% ee) and with excellent yields (up to 94%) by employing the mild active 4-acetylphenyl cyanate as the cationic cyano source in the catalytic asymmetric α-cyanation reaction.

Catalytic Asymmetric Electrophilic Cyanation of 3-Substituted Oxindoles.

The first example of catalytic asymmetric electrophilic cyanation of 3-substituted oxindoles has been achieved using readily accessible 4-acetylphenyl cyanate as the cyano source. Thus, a series of all-carbon quaternary center 3-aryl-3-cyano oxindoles were prepared using a zinc complex of a chiral pincer ligand as the catalyst in high yields (up to 95%) and excellent enantioselectivities (up to >99% ee) in the presence of 4 Å MS and 2,6-lutidine in THF at 0 °C.

The direct electrophilic cyanation of ß-keto esters and amides with cyano benziodoxole.

The direct electrophilic α-cyanation of ß-keto esters and amides has been developed using a hypervalent iodine benziodoxole-derived cyano reagent. The procedure is accomplished within 10 min and without the use of any catalyst in DMF, at room temperature. Thus, the highly functionalized quaternary carbon-centered nitriles were produced in high to excellent yields.