Because of the high catalytic activities and substrate specificity, natural enzymes have been widely used in industrial, medical, and biological fields, etc. Although promising, they often suffer from intrinsic shortcomings such as high cost, low operational stability, and difficulties of recycling. To overcome these shortcomings, researchers have been devoted to the exploration of artificial enzyme mimics for a long time. Since the discovery of ferromagnetic nanoparticles with intrinsic horseradish peroxidase-like activity in 2007, a large amount of studies on nanozymes have been constantly emerging in the next decade. Nanozymes are one kind of nanomaterials with enzymatic catalytic properties. Compared with natural enzymes, nanozymes have the advantages such as low cost, high stability and durability, which have been widely used in industrial, medical, and biological fields. A thorough understanding of the possible catalytic mechanisms will contribute to the development of novel and high-efficient nanozymes, and the rational regulations of the activities of nanozymes are of great significance. In this review, we systematically introduce the classification, catalytic mechanism, activity regulation as well as recent research progress of nanozymes in the field of biosensing, environmental protection, and disease treatments, etc. in the past years. We also propose the current challenges of nanozymes as well as their future research focus. We anticipate this review may be of significance for the field to understand the properties of nanozymes and the development of novel nanomaterials with enzyme mimicking activities.

Nanozymes: Classification, Catalytic Mechanisms, Activity Regulation, and Applications

Heavy metal ions are of great concern, not only among the scientific community, especially chemists, biologists, and environmentalists, but increasingly among the general population, who are aware of the some of the disadvantages associated with them. In spite of the fact that some heavy metal ions play important roles in living systems, they are very toxic and hence capable of causing serious environmental and health problems.1-6 Some heavy metal ions, such as Fe(III), Zn(II), Cu(II), Co(II), Mn(II), and Mo(VI), are essential for the maintenance of human metabolism. However, high concentrations of these ions can lead to many adverse health effects.1,2,7-20 It is also a fact that others such as Hg(II), Cd(II), Pb(II), and As(III) are among the most toxic ions known that lack any vital or beneficial effects. Accumulation of these over time in the bodies of humans and animals can lead to serious debilitating illnesses.2,21-30 Therefore, the development of increasingly selective and sensitive methods for the determination of heavy metal ions is currently receiving considerable attention.7,23,31-36 Several methods, including atomic absorption spectroscopy, inductively coupled plasma atomic emission spectrometry, electrochemical sensoring, and the use of piezoelectric quartz crystals make it possible to detect low limits.37-40 However, these methods require expensive equipment and involve time-consuming and laborious procedures that can be carried out only by trained professionals. Alternatively, analytical techniques based on fluorescence detection are very popular because fluorescence measurements are usually very sensitive (parts per billion/trillion), easy to perform, and inexpensive.23,37,41-45 Furthermore, the photophysical properties of a fluorophore can be easily tuned using a range of routes: charge transfer, electron transfer, energy transfer, the influence of the heavy metal ions, and the destabilization of nonemissive n-π* excited states.5 Consequently, a large number of papers involving fluorescent chemosensors (see definition in section 2) have been published. In general to date, fluorescent chemosensors for anions and cations have proven popular, but those for many heavy metal ions such as Hg(II), Pb(II), Cu(II), Fe(III), and Ag(I) present challenges because these ions often act as fluorescence quenchers. Cu(II) is a typical ion that causes the chemosensor to decrease fluorescent emissions due to quenching of the fluorescence by mechanisms inherent to the paramagnetic species.46-48 Such decreased emissions are impractical for analytical purposes because of their low signal outputs upon complexation. In addition, temporal separation of spectrally similar complexes by time-resolved fluorimetry is subsequently prevented.49 Compared to the relatively well-developed fluorescent chemosensors, fluorescent chemodosimeters (see definition in section 2) have recently emerged as a research area of * Corresponding author. E-mail: jongskim@korea.ac.kr. † Hue University. ‡ Korea University. Duong Tuan Quang was born in 1970 in Thanhhoa, Vietnam, and graduated from Hue University in 1992, where he obtained his M.S. degree two years later and began his career as a lecturer in Chemistry soon afterwards. He received his Ph.D. degree in 2003 from Institute of Chemistry, Vietnamese Academy of Science and Technology. In 2006, he worked as a postdoctoral fellow in Professor Jong Seung Kim’s laboratory, Dankook University, Seoul, Korea. He was promoted as an associate professor in 2009 and went to Korea University as a research professor in 2010. His main task involved the development of chromogenic and fluorogenic molecular sensors to detect specific cations and anions. Chem. Rev. 2010, 110, 6280–6301 6280

Fluoro- and Chromogenic Chemodosimeters for Heavy Metal Ion Detection in Solution and Biospecimens

Anion recognition and sensing in organic and aqueous media using luminescent and colorimetric sensors

Polymers in sensor applications

Luminescent sensors and switches in the early 21st century

A new naphthalene derivative containing a urea group at the 1,8-position of naphthalene was synthesized and showed a unique absorption and fluorescence peak with a fluoride ion Calculations suggested that a new peak was attributed to the increased anion character of urea nitrogen due to the strong interaction of the fluoride and N-H protons

A New Fluoride Selective Fluorescent as Well as Chromogenic Chemosensor Containing a Naphthalene Urea Derivative

Preparation de calix [4] arene et de derives fonctionnalises. Formation de complexes avec Ni, Cu, Pd, Co et Fe divalents. Donnees RMN et IR

Calixarenes. 22. Synthesis, properties, and metal complexation of aminocalixarenes.

Visible colorimetric fluoride ion sensors.

A new naphthalene derivative containing a urea group at the 1,8-position of naphthalene was synthesized and showed a unique absorption and fluorescence peak with fluoride ion. Calculations suggested that a new peak was attributed to the increased anionic character of urea nitrogen due to the strongly charged hydrogen bonding between fluoride and amide protons of the urea. The fluoride selectivity among halides (F-, Cl-, Br-) comes from the fact that the fluoride approaches much closer to the amide protons than other halides and resides in the cavity with fast dynamics. The nature of electronic transitions that were analyzed from the calculations by the collective electronic oscillator method also supports the anionic nature of the complex between host and fluoride.

/pdf/efficient-fluoride-selective-fluorescent-host-experiment-and-4vd1p9subl.pdf

Kye Chun Nam

Papers

A New Fluoride Selective Fluorescent as Well as Chromogenic Chemosensor Containing a Naphthalene Urea Derivative

Calixarenes. 22. Synthesis, properties, and metal complexation of aminocalixarenes.

Visible colorimetric fluoride ion sensors.

Efficient fluoride-selective fluorescent host: experiment and theory.

Co-immobilization of three cellulases on Au-doped magnetic silica nanoparticles for the degradation of cellulose