Oxygen‐Sensing Methods in Biomedicine from the Macroscale to the Microscale

Oxygen monitoring has been a topic of exhaustive study given its central role in the biochemistry of life. The ability to quantify the physiological distribution and real‐time dynamics of oxygen from sub‐cellular to macroscopic levels is required to fully understand the mechanisms associated with both normal physiology and disease states. This Review will present the most significant recent advances in the development of oxygen‐sensing materials and techniques, including polarographic, nuclear medicine, magnetic resonance, and optical approaches, that can be applied specifically for the real‐time monitoring of oxygen dynamics in cellular and tissue environments. As some of the most exciting recent advances in synthetic methods and biomedical applications have been in the field of optical oxygen sensors, a major focus will be on the development of these toolkits.     

Cobalt Phosphide Nanowires: Efficient Nanostructures for Fluorescence Sensing of Biomolecules and Photocatalytic Evolution of Dihydrogen from Water under Visible Light

The detection of specific DNA sequences plays an important role in the identification of disease‐causing pathogens and genetic diseases, and photochemical water splitting offers a promising avenue to sustainable, environmentally friendly hydrogen production. Cobalt–phosphorus nanowires (CoP NWs) show a high fluorescence quenching ability and different affinity toward single‐ versus double‐stranded DNA. Based on this result, the utilization of CoP NWs as fluorescent DNA nanosensors with a detection limit of 100 pM and a selectivity down to single‐base mismatch was demonstrated. The use of a thrombin‐specific DNA aptamer also enabled the selective detection of thrombin. The photoinduced electron transfer from the excited dye that labels the oligonucleotide probe to the CoP semiconductor led to efficient fluorescence quenching, and largely enhanced the photocatalytic evolution of hydrogen from water under visible light.     

Triarylboron‐Linked Conjugated Microporous Polymers: Sensing and Removal of Fluoride Ions

A luminescent conjugated microporous polymer (BCMP‐3) has been synthesized in high yield by a carbon–carbon coupling reaction using triarylboron as a building unit. BCMP‐3 was fully characterized by using powder X‐ray diffraction analysis, Fourier transform infrared spectroscopy, ¹³C solid‐state NMR spectroscopy, field emission scanning electron microscopy, thermogravimetric analysis, and nitrogen and carbon dioxide adsorption. The new three‐dimensional conjugated framework possess a high Brunauer–Emmett–Teller (BET) specific surface area up to 950 m² g^?1 with a pore volume of 0.768 cm³ g^?1, good stability, and abundant boron sites in the skeleton. Under excited‐light irradiation, BCMP‐3 exhibits strong fluorescent emission at 488 nm with a high absolute quantum yield of 18 % in the solid state. Polymer BCMP‐3 acts as a colorimetric and fluorescent chemosensor with high sensitivity and selectivity for F^? over other common anions. In addition, the polymer also works as an adsorbent for F^? removal and shows good adsorption capacities of up to 24 mg g^?1 at equilibrium F^? concentrations of 16 mg L^?1 and a temperature of 298 K. The adsorption kinetics and isotherm were analyzed by fitting experimental data with pseudo‐second‐order kinetics and Langmuir equations. Furthermore, we highlight that BCMP‐3 is an adsorbent for fluoride removal that can be efficiently reused many times without loss of adsorption efficiency.     

A regenerable zinc(II) coordination polymer as a dual-luminescent sensor for detection of Cr2O72– and 2,4,6-trinitrophenol in aqueous phase

Abstract

Developing a fast and sensitive method for the detection of 2,4,6-trinitrophenol (TNP) or Cr₂O₇^2– in aqueous solution has received great attention. In this work, a regenerable fluorescent coordination polymer [Zn(L)(H₂L)]_n (1) has been successfully constructed using a novel Schiff base ligand N'-[(E)-(3,5-dibromo-2-hydroxyphenyl)methylene]isonicotinohydrazide(H₂L) and exploited as a dual detection probe for the selective sensing of Cr₂O₇^2– and TNP in water media. Competitive fluorometric experiments involving mixtures of anions or nitro compounds demonstrated 1 as an efficient and selective sensor for both Cr₂O₇^2– and TNP. The limits of detection for Cr₂O₇^2– and 2,4,6-trinitrophenol in aqueous solutions were found to be 11.4 and 1.19?μM, respectively. Moreover, 1 can detect TNP and Cr₂O₇^2– in real water samples. All these features clearly demonstrate its great potential of practical TNP and Cr₂O₇^2– detection in water media for public safety and security.     

Selective metal ion recognition using a fluorescent 1,8-diquinolylnaphthalene-derived sensor in aqueous solution

The use of anti-1,8-bis(2,2′-diisopropyl-4,4′-diquinolyl)naphthalene, 1, for metal ion-selective fluorescence recognition has been investigated. Employing CuCl₂, ZnCl₂, FeCl₂, and FeCl₃ in fluorescence titration experiments of 1 revealed formation of a bluegreen light emitting bimetallic complex. A dramatic red-shift of the fluorescence maximum of 1 and metal ion-selective quenching was observed in the presence of Cu(II), Fe(II), and Fe(III)chlorides in acetonitrile. By contrast, addition of ZnCl₂ was found to result in fluorescence enhancement, whereas Cu(I) did not induce any significant fluorescence change of 1. The sensor was found to undergo highly ion-selective fluorescence quenching in aqueous solution. Screening of main group and transition metal ions showed excellent selectivity for FeCl₃ even in the presence of competing metal ions.     

Ratiometric dual fluorescent receptors for anions under intramolecular charge transfer mechanism

A series of the intramolecular charge transfer (ICT) dual fluorescent receptors with anion binding site in the electron acceptor were designed and synthesized. These receptors exhibited dual fluorescence in acetonitrile and the charge transfer (CT) emission energy was found to correlate linearly with the Hammett constant of the substituent existing in the electron acceptor, which is the basis for anion sensing. Dual fluorescence of these receptors was found to be sensitive to the presence of anions such as fluoride and acetate and the receptors can be employed as ratiometric fluorescent sensors for anions.     

Structure of a di-zinc complex of a bis-calix[4]arene conjugate and its sensing of cysteine among the amino acids

Abstract

A triethylene glycol di-imine locked triazole linked bis-calix[4]arene conjugate (L) and its Zn²⁺ complex [Zn₂L], were synthesised, characterised and the three-dimentional (3-D) structure of the complex was established by single crystal XRD. In this complex, the Zn²⁺ centre exhibits distorted tetrahedral geometry with N₂O₂ binding core. The complex showed selectivity towards cysteine (Cys) with greater sensitivity followed by histidine (His) among the naturally occurring amino acids studied based on fluorescence and absorption spectroscopy. The fluorescence quenching of the complex is much greater with Cys as compared to that of His. The detection limit of Cys is 650 ppb. Release of Zn²⁺ from its complex [Zn₂L] followed by its capture by –SH containing molecules was shown based on absorption and emission spectroscopy. This was also shown in one case by ¹H NMR spectroscopy.     

Benzothiazole‐Pyimidine‐Based BF2 Complex for Selective Detection of Cysteine

Due to the similar structure and reactivity of cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), the simultaneous discrimination of Cys over Hcy and GSH by a single fluorescent sensor is still a great challenge. In this work, a benzothiazole‐pyimidine‐based boron difluoride complex ( BPB ) was developed as a new fluorescent sensor for Cys. The sensor exhibits a highly selective “turn‐on” response to cysteine over Hcy, GSH and other amino acids in aqueous solution at physiological pH. The observed pseudo‐first‐order rate constant for the reaction of BPB with Cys was calculated to be about 0.062 min⁻¹. The detection limit of this sensor for Cys was determined to be 332 nm, and bioimaging of exogenous Cys by this sensor was successfully applied in living cells, thus indicating that this sensor holds great potential for biological applications.     

Sensing cytochrome P450 1A1 activity by a resorufin-based isoform-specific fluorescent probe

Cytochrome P450 1A1 (CYP1A1), a heme-containing monooxygenase, is of particular importance for human health because of its vital roles in the metabolic activation of pro-carcinogenic compounds to the carcinogens. Deciphering the relevance of CYP1A1 to human diseases and screening of CYP1A1 modulators require reliable tool(s) for probing this key enzyme in complex biological matrices. Herein, a practical and ultrasensitive fluorescence-based assay for real-time sensing CYP1A1 activities in biological systems has been developed, via designing an isoform-specific fluorogenic sensor for CYP1A1 (CHPO). The newly developed fluorogenic substrate for CYP1A1 has been carefully investigated in terms of specificity, sensitivity, precision, quantitative linear range and the anti-interference ability. The excellent selectivity, strong anti-interference ability and fast response kinetics, making the practicability of CHPO-based CYP1A1 activity assay is better than that of most reported CYP1A1 activity assays. Furthermore, CHPO has been successfully used for imaging CYP1A1 activities in living cells and human tissues, as well as for high-throughput screening of CYP1A1 inhibitors using tissue preparations as enzyme sources. Collectively, this study provided a practical fluorogenic sensor for real-time sensing CYP1A1 in complex biological systems, which would strongly facilitate the investigations on the relevance of CYP1A1 to human diseases and promote high-throughput screening of CYP1A1 modulators for biomedical applications.     

中空多壳层结构材料的制备及气体传感应用研究进展

先进气体传感器技术在现代社会安全生产生活中扮演着极为重要的角色,而高效敏感材料的设计与开发是其中的关键.中空多壳层结构材料因其独特的层层嵌套的多壳层与多腔体结构而表现出特别的物理化学性质,在气体传感领域显现出巨大的应用潜力.传统的硬模板法、软模板法以及基于奥斯特瓦尔德熟化和柯肯德尔效应的无模板法在中空多壳层纳米结构材料的普适制备及壳层结构的精确调控等方面存在诸多限制.次序模板法的出现突破了上述限制,促进了该领域的迅速发展.本文简要回顾了中空多壳层结构材料制备方法的发展历程,介绍了其在甲醛、乙醇、丙酮、甲苯及二氧化氮等有害气体检测中的具体应用,分析了其在气体传感领域的独特优势,最后对该领域面临的挑战和发展前景进行了总结与展望.