Xin Zhou,†,‡ Songyi Lee,† Zhaochao Xu,* and Juyoung Yoon*,† †Department of Chemistry and Nanoscience, Ewha Womans University, Seoul 120-750, Republic of Korea ‡Research Center for Chemical Biology, Department of Chemistry, Yanbian University, Yanjii 133002, People’s Republic of China Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Shahekou, Dalian, Liaoning, People’s Republic of China

Recent Progress on the Development of Chemosensors for Gases.

Developing efficient sensor materials with superior performance for selective, fast and sensitive detection of gases and volatile organic compounds (VOCs) is essential for human health and environmental protection, through monitoring indoor and outdoor air pollutions, managing industrial processes, controlling food quality and assisting early diagnosis of diseases. Metal–organic frameworks (MOFs) are a unique type of crystalline and porous solid material constructed from metal nodes (metal ions or clusters) and functional organic ligands. They have been investigated extensively for possible use as high performance sensors for the detection of many different gases and VOCs in recent years, due to their large surface area, tunable pore size, functionalizable sites and intriguing properties, such as electrical conductivity, magnetism, ferroelectricity, luminescence and chromism. The high porosity of MOFs allows them to interact strongly with various analytes, including gases and VOCs, thus resulting in easily measurable responses to different physicochemical parameters. Although much of the recent work on MOF-based luminescent sensors have been summarized in several excellent reviews (up to 2018), a comprehensive overview of these materials for sensing gases and VOCs based on chemiresistive, magnetic, ferroelectric, and colorimertic mechanisms is missing. In this review, we highlight the most recent progress in developing MOF sensing and switching materials with an emphasis on sensing mechanisms based on electricity, magnetism, ferroelectricity and chromism. We provide a comprehensive analysis on the MOF–analyte interactions in these processes, which play a key role in the sensing performance of the MOF-based sensors and switches. We discuss in detail possible applications of MOF-based sensing and switching materials in detecting oxygen, water vapor, toxic industrial gases (such as hydrogen sulfide, ammonia, sulfur dioxide, nitrous oxide, carbon oxides and carbon disulfide) and VOCs (such as aromatic and aliphatic hydrocarbons, ketones, alcohols, aldehydes, chlorinated hydrocarbons and N,N′-dimethylformamide). Overall, this review serves as a timely source of information and provides insight for the future development of advanced MOF materials as next-generation gas and VOC sensors.

Functional metal–organic frameworks as effective sensors of gases and volatile compounds

Propargylamines are a versatile class of compounds which find broad application in many fields of chemistry. This review aims to describe the different strategies developed so far for the synthesis of propargylamines and their derivatives as well as to highlight their reactivity and use as building blocks in the synthesis of chemically relevant organic compounds. In the first part of the review, the different synthetic approaches to synthesize propargylamines, such as A3 couplings and C–H functionalization of alkynes, have been described and organized on the basis of the catalysts employed in the syntheses. Both racemic and enantioselective approaches have been reported. In the second part, an overview of the transformations of propargylamines into heterocyclic compounds such as pyrroles, pyridines, thiazoles, and oxazoles, as well as other relevant organic derivatives, is presented.

/pdf/synthesis-and-reactivity-of-propargylamines-in-organic-2p342bmyhh.pdf

Synthesis and Reactivity of Propargylamines in Organic Chemistry

Combining nanotechnology with the other science disciplines is necessary to produce various materials with nanoscale structural and functional information, which is nanoarchitectonics as a novel paradigm to create useful materials. One of the basic ideas in the nanoarchitectonics concept is use of molecular-level information to architect functional materials. This kind of strategy is indeed used in some pre-existing science fields and technical methods. For example, molecular imprinting technique provides functional materials possessing molecular information in insides of fabricated materials. Revisiting such known concept with the nanoarchitectonics concept would have great meaning in unification of individual research disciplines into one key concept. In this review, we survey fundamentals and recent trends of the molecular imprinting approaches upon consideration with the nanoarchitectonics. Here, aspects and examples of molecular imprinting are surveyed from fundamentals to advanced applications: (i) ...

Molecular Imprinting: Materials Nanoarchitectonics with Molecular Information

Fluorescent sensors are attractive and versatile tools for both chemical sensing and biological imaging. Herein, a novel pyrene derivative fluorophore, Py-Cy, possessing the monomer/excimer conversion feature, was synthesized; and the design rationale for this fluorophore is combination of extending conjugation length and incorporating donor-π-acceptor structure. The positively charged Py-Cy shows quite good water solubility and exhibits absorption in the visible-light range, and its monomer and excimer emit red light and near-infrared light respectively, which is extremely beneficial for biosensing or bioimaging. To explore the potential utilization of this new fluorophore, we choose hypochlorite as a model analyte, which can break the double bond in the molecular structure, thereby generating the water-insoluble pyrenecarboxaldehyde; this process correspondingly leads to fluorescence changes and thus affords the ratiometric fluorescent detection of hypochlorite in real samples and cell imaging. The approach offers new insights for designing other fluorophores which emit red or near-infrared light and for devising technically simple ratiometric fluorescent sensors.

Pyrene Derivative Emitting Red or near-Infrared Light with Monomer/Excimer Conversion and Its Application to Ratiometric Detection of Hypochlorite

The chromo-fluorogenic detection of carbon monoxide in air has been achieved using a simple, inexpensive system based on ruthenium(II) This probe shows exceptional sensitivity and selectivity in its sensing behavior in the solid state A color response visible to the naked eye is observed at 5 ppb of CO, and a remarkably clear color change occurs from orange to yellow at the onset of toxic CO concentrations (100 ppm) in air Even greater sensitivity (1 ppb) can be achieved through a substantial increase in turn-on emission fluorescence in the presence of carbon monoxide, both in air and in solution No response is observed with other gases including water vapor Immobilization of the probe on a cellulose strip allows the system to be applied in its current form in a simple optoelectronic device to give a numerical reading and/or alarm

https://pubs.acs.org/doi/pdf/10.1021/ja507014a

A Chromo-Fluorogenic Synthetic Canary for CO Detection Based on a Pyrenylvinyl Ruthenium(II) Complex

https://pubs.rsc.org/en/content/articlepdf/2016/CC/C6CC01335J

Chromo-fluorogenic probes for carbon monoxide detection

A two-photon fluorescent probe based on a ruthenium(II) vinyl complex is capable of selectively detecting carbon monoxide in cells and ex vivo using mice with a subcutaneous air pouch as a model for inflammation. This probe combines highly selective and sensitive ex vivo detection of endogenous CO in a realistic model with facile, inexpensive synthesis, and displays many advantages over the widely used palladium-based systems.

Ex Vivo Tracking of Endogenous CO with a Ruthenium(II) Complex

The synthesis of enantiomerically pure 1,3-mercaptoalkanol volatile sulfur compounds through a one-pot photo-biocatalytic cascade reaction is described. Two new KRED biocatalysts with opposite enantioselectivity were discovered and proved to be efficient on a wide range of substrates. The one-pot cascade reaction combining photocatalytic thio-Michael addition with biocatalytic ketoreduction in an aqueous medium provides a green and sustainable approach to enantiomerically pure 1,3-mercaptoalkanols in high yields with excellent enantioselectivity.

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Anita Toscani

Papers

Synthesis and Reactivity of Propargylamines in Organic Chemistry

A Chromo-Fluorogenic Synthetic Canary for CO Detection Based on a Pyrenylvinyl Ruthenium(II) Complex

Chromo-fluorogenic probes for carbon monoxide detection

Ex Vivo Tracking of Endogenous CO with a Ruthenium(II) Complex

Photo-biocatalytic One-Pot Cascades for the Enantioselective Synthesis of 1,3-Mercaptoalkanol Volatile Sulfur Compounds