DNAzyme@CuSNPs dual mimic enzyme probe-amplified chemiluminescent imaging array immunosensor for multiple chicken cytokines detection

The detection of cytokines plays an important role in clinical diagnosis and immune mechanism research of chicken diseases.In this work,a novel and ultrasensitive chemiluminescent(CL)imaging array immunosensor was proposed to detect multiple chicken cytokines based on DNAzyme@CuS nanoparticles(DNAzyme@CuSNPs)dual mimic enzyme signal amplification strategy.DNAzyme@CuSNPs owns excellent peroxidase property,which was modified with second antibody(Ab_(2))to prepare DNAzyme@CusNPs detection probe,and demonstrated high catalysis CL imaging signal due to synergistic catalysis.Chicken interleukin-4(ChIL-4)and chicken interferon-y(ChIFN-y)were used as model analysis samples,the DNAzyme@CusSNPs-based CL imaging immunosensor achieved simultaneous and high-throughput detection of ChIL-4 and ChIFN-y with wide linear range of 10^(-3)-10^(2) ng/mL,and the detection limits are 0.41 pg/mL and 0.36 pg/mL,respectively.The multiplex chicken cytokines CL imaging array immunosensor shows a high sensitivity,wide linear range,excellent specificity and acceptable stability.This research opens dual mimic enzyme signal-amplified strategy to develop sensitive CL imaging immunoassay for chicken diseases detection application.

Target-induced mimic enzyme deactivation based on mixed-node metal-organic frameworks for colorimetric assay of hydrogen sulfide

Accurate detection of hydrogen sulfide(H_(2)S)is of great significance for environmental monitoring and protection.We propose a colorimetric method for the detection of H_(2)S by the use of mixed-node Cu-Fe metal organic frameworks(Cu-Fe MOFs)as highly efficient mimic enzymes for target-induced deactivation.The Cu-Fe MOFs were synthesized by a simple solvothermal method and could catalyze the H_(2)O_(2)mediated oxidation of 3,30,5,50-tetramethylbenzidine(TMB)to oxTMB with a blue color.The presence of dissolved H_(2)S would deactivate the mimic enzymes,and then the blue color disappeared.The mechanism of the sensor was discussed by steady-state kinetic analysis.The designed assay was highly sensitive for H_(2)S detection with a linear range of 0à80 mmol/L and a detection limit of 1.6 mmol/L.Moreover,some potential substances in the water samples had no interference.This method with the advantages of low cost,high sensitivity,selectivity,and visual readout with the naked eye was successfully applied to the determination of H_(2)S in industrial wastewater samples.

Study on Synthesis and Deplete Harmful Radical of Cobalt Porphyrins as the Mimic of Enzyme

The four cobalt porphyrins [Co (3, 4, 5 MeO TPP) (1) ; Co (TTP) (2) ; Co (4 CI TPP) (3);Co (4 HSO 3 TPP) (4)] were synthesized and considered as two mimic of superoxide dismutaes (SOD) and catalase (CAT). The catalytic efficiency of them on deplete the harmful radical have been proved using riboflavin methionine photoreduction method in the concentration range of 10 6 ～10 5 mol/L. The catalytic efficiency of them at decomposing H 2O 2 has been performed by spectrophotometer. The percentage of decomposing H 2O 2 while the increasing the concentration of the imitating compounds. The lipid peroxidationproduced in liver homogenatcd of mice was determined by spectrophotometer detecting the content of MDA.

Effect of 2-Selenium Bridged β-Cyclodextrin,Glutathione Peroxidase Mimic on Stroke of Stroke-prone Spontaneously Hypertensive Rats

To investigate the treatment effect of 2-selenium bridged β -cyclodextrin(2-SeCD),a GPX mimic,on the stroke of stroke-prone spontaneously hypertensive rats(SHRSP),fifty-two SHRSP of 8-week old were randomly divided into four groups A,B,C and control group D. The rats of groups A,B,C and D were given 1.0%-1.5% NaCl mass fraction as drinking fluid. After onset of stroke,groups A,B and C were given \{orally\} 16.05,160.5 and 1605 mg·kg -1 ·day -1 of 2-SeCD,respectively,and group D was given water for \{2 weeks.\} The clinical score of stroke,systolic blood pressure(SBP),survival time of rats were recorded and the histopathologic examinations of their brain and carotid artery were made after decapitation. The clinical scores of stroke after treatment with 160.5 mg·kg -1 ·day -1 (Group B) and 1605 mg·kg -1 ·day -1 (Group C) of 2-SeCD are 2.55±0.98 and 1.98±0.79,respectively,those are obviously lower than that of group D(3.41±0.83,p<0.01). The survival days in group B(10.0±8.6) and group C(14.4±7.9) are longer than that for group D(4.7±2.9,p<0.01). The electron microscope study showed that the endothelium of carotid artery was near to normal in group B and group C,while it was seriously injured in control group D and mildly injured in group A. 2-SeCD may effectively be used to treat the stroke for SHRSP.

Unveiling enzyme-mimetic active intermediate of a bioinspired oxo-MoS_(x) electrocatalyst for aqueous nitrate reduction

Excessive nitrate in groundwater has emerged as a serious environmental concern. The elevated nitrate concentration in drinking water causes a serious threat to public health on account of the possible transformation of nitrate to nitrite, which is one of the main predisposing factors of methemoglobinemia [1].

PREPARATION AND CATALYTIC ACTIVITY OF BIOACTIVE FIBERS

Two kinds of water-soluble metallophthalocyanines, binuclear cobalt phthalocyanine （Co2Pc2） and binuclear ferric phthalocyanine （Fe2Pc2）, were synthesized through phenylanhydride-urea route and characterized by elemental analysis and FT-IR spectra. Binuclear metallophthalocyanine derivatives （Mt2Pc2） were immobilized on silk fibers and modified viscose fibers to construct bioactive fibers of mimic enzyme. Mt2Pc2 was used as the active center of bioactive fibers, viscose and silk fibers as the microenvironments. The catalytic oxidation ability of bioactive fibers on the malodors of methanthiol and hydrogen sulfide was investigated at room temperature. The experimental results indicated that the catalytic activity of such bioactive fibers was closely correlative to the types ofbioactive fibers and substrates.

Copper Phthalocyanine Catalysis to Oxidation of Adrenaline by Oxygen and Its Application in Adrena-line Detection

The oxidation of adrenaline by dioxygen using copper phthalocyanine （CuPc） as the catalyzer was studied. CuPc has the optimal catalytic pH of 8.0 and the optimal catalytic temperature of 55 ℃. It also has good storage and operation stability. The fiber optic adrenaline biosensor based on CuPc catalysis and fluorescence quenching was fabricated and studied. This sensor has the detection range of 7.0 × 10^-5 1.5 × 10^-4mol/L, the response time of 4 rain, good reproducibility and stability.

Nanozymes:Versatile Platforms for Cancer Diagnosis and Therapy

Natural enzymes usually suffer from high production cost,ease of denaturation and inactivation,and low yield,making them difficult to be broadly applicable.As an emerging type of artificial enzyme,nanozymes that combine the characteristics of nanomaterials and enzymes are promising alternatives.On the one hand,nanozymes have high enzyme-like catalytic activities to regulate biochemical reactions.On the other hand,nanozymes also inherit the properties of nanomaterials,which can ameliorate the shortcomings of natural enzymes and serve as versatile platforms for diverse applications.In this review,various nanozymes that mimic the catalytic activity of different enzymes are introduced.The achievements of nanozymes in different cancer diagnosis and treatment technologies are summarized by highlighting the advantages of nanozymes in these applications.Finally,future research directions in this rapidly developing field are outlooked.

Selenium-functionalized metal-organic frameworks as enzyme mimics

The development of artificial enzyme mimics has been rapidly growing in recent years, and it is attracting increasing attention owing to their remarkable advantages over natural enzymes. Herein, we developed a general and facile method to fabricate efficient glutathione peroxidase （GPx） mimics by grafting selenium-containing molecules （phenylselenylbromide, PhSeBr） to a Zr（W）-based UiO-66-NH2 framework. In the presence of glutathione （GSH） serving as substrate, the fabricated UiO-66-Se catalysts can catalyze the reduction of hydroperoxides. The as-prepared UiO-66-Se systems show good catalytic activity over three cycles. These high-efficiency GPx mimic metal-organic frameworks （MOFs） are endowed with excellent thermal and structural stability, providing a promising avenue for the development of artificial enzyme mimics.

Comparison Between the Effects of 2-Selenium Bridged β-Cyclodextrin and Ebselen on Treating SHRsp Stroke

A glutathione peroxidase（GPX） mimic, 2-selenium bridged β-cyclodextrin（2-SeCD）, was synthesized. In order to examine its role and mechanism in treating stroke we chose stroke-prone spontaneously hypertensive rats（SHRsp） as animal model. 56 SHRsps of 8-week olds were randomly divided into several groups： test groups （low, moderate, high dose of 2-SeCD） and control groups（positive and negative）. After onset of the stroke, the rats in test groups were orally administrated with different amounts of 2-SeCD, the positive control group with ebselen, and the negative control group with drinking water. The treatment lasted two weeks, followed by observation of the rats for 10 days, meanwhile blood pressure, biochemical parameters of plasma, and the contents of nitric oxide（NO） and malondialdehyde（MDA） in plasma and brain were determined. The results show that there were significant differences in contents of NO and MDA in plasma and brain between the test groups（high, moderate dose of 2-SeCD） and negative control group. The NO contents of the test groups were obviously higher than that of the negative control group （P〈0.01）. The MDA contents of the test groups（high, moderate dose of 2-SeCD） were obviously lower than that of the negative control group（P〈0.01）. The mechanism of 2-SeCD in treating stroke was discussed, which maybe related to the increase of NO and the decrease of MDA in plasma and brain tissue, but the exact mechanism should be further studied. Moreover, the tendencies of changes in systolic blood pressure, contents of NO and MDA, and other physiological parameters for the test groups were shown to be much better than the corresponding parameters for the positive group（the group with ebselen）（P〈0.05）, indicating that the treatment effect of 2-SeCD is better than that of ebselen.

Porous Pt/Ag nanoparticles with excellent multifunctional enzyme mimic activities and antibacterial effects

Enhancing the activity of Pt-based nanocatalysts is of great significance yet a challenge for the oxygen reduction reaction （ORR）. In this work, a series of porous Pt/Ag nanoparticles （NPs） were fabricated from regular PtxAg100-x （x = 25, 50, 75） octahedra by a facile and economical dealloying process. Remarkable enhancement in multiple enzyme-mimic activities related to ORR was observed for the dealloyed Pt50Ag50 （D-Pt50Ag50） NPs. This effect can be attributed to the resulting Pt-rich surface structure, increased surface area, and a synergistic effect of Pt and Ag atoms in the D-Pt-a-gs0 NPs. Furthermore, the D-Pt50Ag50 NPs exerted excellent antibacterial effects on two model bacteria （gram-negative Escherichia coli and gram-positive Staphylococcus aureus）. The present work represents a significant advance in the exploration of the relation between controllable synthesis of high-quality nanoalloys and their novel catalytic properties for various promising applications, including catalysts, biosensors, and biomedicine.

Bifunctional nanozyme activities of layered double hydroxide derived Co-A1-Ce mixed metal oxides for antibacterial application

Marine biofouling is an expensive problem that needs evolved chemical or physical antifouling strategies.However,most of the current antifouling materials that would damage the environment through metal leaching and bacteria resistance are being halted.Nanozyme is one kind of environmental antifouling materials through generating reactive oxygen species(ROS).We prepared various contents of CeO2 that could uniform disperse compounding with Co3 O4 and CoAl2 O4 to form a stable Co-Al-Ce mixed metal oxide(MMO) by a layered double hydroxide derived method.We find that coupling with CeO2 can improve the peroxidase(POx) activity.When the molar ratio of Ce is 2.5% and the calcination temperature is 200℃,the POx activity of Co-Al-Ce MMO is the best caused by the good dispersion of catalytically active components and the high specific area(150.10±4.95 m2/g).This novel Co-Al-Ce MMO also exhibits an antibacterial mode of action Gram-negative bacteria in near-neutral pH solution through generating ROS(mainly ·O2-)in the presence of H2 O2.Ce containing MMO can be utilized as potential green marine antifouling material.

Imprinted Human Serum Albumin with Antioxidant Activity

In order to create a new mimic of glutathione peroxidase（GPx）, bioimprinting was used to generate gluta-thione（GSH） binding site and chemical modification was used to incorporate catalytic group selenocystine（Sec）. Human serum albumin（HSA） and S-substituted dinitrophenyl glutathione（GSH-S-DNP） were chosen as the imprinted matrix and imprinting template, respectively, to generate a GSH-imprinted protein（GSH-HSA） by bioimprinting. Sec was incorporated into the GSH-HSA by chemical modification to give a new GPx mimic（Se-GSH-HSA）. Se-GSH-HSA displayed considerably higher GPx activity than non-printed HSA（Se-HSA）. The enzymic properties and kinetics of Se-GSH-HSA were studied. Moreover, Se-GSH-HSA was confirmed to have stronger antioxidant ability to protect mitochondria against oxidative damage with ferrous sulfate/ascorbate-induced mitochondria damage model, indicating that Se-GSH-HSA has potential application in medicine.

Catalytical oxidation of styrene by molecularly imprinted polymer with phenylacetic acid as template and hemin as co-monomer

This letter used the molecular imprinting technology to build up the microenvironment around co-monomer bemin to mimic the cytochrome P450 catalyzing the epoxidation of styrene. The results showed that the conversion rates of products were obviously enhanced by molecularly imprinted polymers, compared to free heroin solution, using three kinds of oxidants. The used axial ligand in polymers synthesis also improved the total conversion rates.

N,P,or S-doped carbon nanotubes as dual mimics of NADH oxidase and cytochrome c reductase

Most nanozyme research is limited to oxidase and peroxidase.Here,we reported the N,P,or S doped carbon nanotubes(CNTs)for enzyme mimics of nicotinamide adenine dinucleotide(NADH)oxidase and cytochrome c(Cyt c)reductase.Through the doping of N element,the NADH oxidase-like activity of CNTs is highly improved,the maximum initial velocity for N doped CNT(N-CNT)is increased by 4.28 times compared to that before the modification.Through the analysis of NADH oxidation products,we found that biologically active NAD+was produced,the oxygen was selectively reduced to water or hydrogen peroxide,which is consistent with natural NADH oxidase.Furthermore,we found for the first time that carbon nanotubes can promote the transfer of electrons from NADH to Cyt c,thereby can mimic the properties of Cyt c reductase.

Designed imidazole-based supramolecular catalysts for accelerating oxidation/hydrolysis cascade reactions

Reconstructing enzymatic active sites presents a significant challenge due to the intricacies involved in achieving enzyme-like scaffold folding and spatial arrangement of essential functional groups.There is also a growing interest in building biocatalytic networks,wherein multiple enzymatic active sites are localized within a single artificial system,allowing for cascaded transformations.In this work,we report the self-assembly of imidazole or its derivatives with fluorenylmethyloxycarbonyl-modified histidine and Cu2+to fabricate a supramolecular catalyst,which possesses catechol oxidase-like dicopper center with multiple imidazole as the coordination sphere.Transmission electron microscopy,low-temperature X-band continuous-wave electron paramagnetic resonance,K-edge X-ray absorption spectra/the extended X-ray absorption fine structure analysis,and density functional theory modeling were used for the structural characterization of the catalyst.The phenol derivatives and the dissolved oxygen were used as the substrates,with the addition of 4-aminoantipyrine to generate a red adduct with a maximum absorbance at 510 nm,for obtaining time-dependent absorbance change curves and estimating the activities.The results reveal that the addition of imidazole synergistically accelerates the oxidative activity about 10-fold and the hydrolysis activity about 14-fold than fluorenylmethyloxycarbonyl modified-histidine/Cu2+.The supramolecular nanoassembly also exhibits the ability to catalyze oxidation/hydrolysis cascade reactions,converting 2′,7′-dichlorofluorescin diacetate into 2′,7′-dichlorofluorescein.This process can be regulated through the methylation of the imidazole component at various positions.This work may contribute to the design of advanced biomimetic catalysts,and shed light on early structural models of the active sites of the primitive copper-dependent enzymes.

Cadmium sulfide as bifunctional mimics of NADH oxidase and cytochrome c reductase takes effect at physiological pH

Recently,a study of mimic enzyme has received more attentions.However,the investigation on the oxidoreductase activity of electron mediators in the biological respiratory chain is still rare.Herein,we found that cadmium sulfide(CdS)nanorods can catalyze the formation of superoxide anions.Due to the role of the photo-generated holes and the nicotinamide adenine dinucleotide(NADH)oxidation promoted by superoxide anion(O_(2)^(•−)),the CdS exhibits NADH oxidase-like activity and can be coupled with dehydrogenase to realize the recycling of NADH.It is worth mentioning that the bio-electron acceptor,cytochrome c(Cyt c),as a chromogenic substrate,can accept electrons transferred from O_(2)^(•−),which demonstrates the Cyt c reductase-like activity of CdS under physiological pH conditions.For different substrates,O_(2)^(•−)induced from CdS show oxidizing capacity for NADH and reducing capacity for Cyt c,which provides a new perspective for the in-depth study of new nanozyme.

Electrochemical aptasensor for the detection of vascular endothelial growth factor(VEGF) based on DNA-templated Ag/Pt bimetallic nanoclusters

In this paper, the DNA-templated Ag/Pt bimetallic nanoclusters were successfully synthesized using an optimized synthetic scheme. The obtained DNA-Ag/Pt NCs have an ultrasmall particle size and excellent distribution. The DNA-Ag/Pt NCs show intrinsic peroxidase-mimicking activity and can effectively catalyze the H2O2-mediated oxidation of a substrate, 3,30,5,50-tetramethylbenzidine（TMB）, to produce a blue colored product. Based on this specific property, we employed the aptamer of VEGF to design a label-free electrochemical biosensor for VEGF detection. Under the optimized experimental conditions, a linear range from 6.0 pmol/L to 20 pmol/L was obtained with a detection limit of 4.6 pmol/L. The proposed biosensor demonstrated its high specificity for VEGF and could directly detect the VEGF concentration in human serum samples of breast cancer patients with satisfactory results. This novel electrochemical aptasensor was simple and convenient to use and was cost-effective and label-free in design, and would hold potential applications in medical diagnosis and treatment.

MoS2-Pt3Au1 Nanocomposites with Enhanced Peroxidase-Like Activities for Selective Colorimetric Detection of Phenol

MoS2-based nanocomposites are emerging as novel versatile materials.Here,uniform Pt3Au1 nanoparticles （NPs） decorated few-layer MoS2 nanosheets were fabricated as novel enzyme mimics.Compared to pure MoS2 nanosheets,the as-prepared MoS2-Pt3Au1 nanocomposites displayed enhanced peroxidase-like activity.The nanocomposites also possessed well dispersibility and high stability in water.With these findings,a simple,fast and low-cost colorimetric detection of phenol with high sensitivity and selectivity is developed,which is based on oxidative coupling reaction of phenol and 4-aminoantipyine in the presence of H2O2 as an oxidant to form pink color products.This work provides a type of MoS2-NP composites as enzyme mimics for many potential applications in catalysis.

Biomineralization-inspired copper-cystine nanoleaves capable of laccase-like catalysis for the colorimetric detection of epinephrine

Recently,many efforts have been dedicated to creating enzyme-mimicking catalysts to replace natural enzymes in practical fields.Inspired by the pathological biomineralization behaviour of L-cystine,in this study,we constructed a laccase-like catalyst through the co-assembly of L-cystine with Cu ions.Structural analysis revealed that the formed catalytic Cu-cystine nanoleaves(Cu-Cys NLs)possess a Cu(I)-Cu(II)electron transfer system similar to that in natural laccase.Reaction kinetic studies demonstrated that the catalyst follows the typical Michaelis-Menten model.Compared with natural laccase,the Cu-Cys NLs exhibit superior stability during long-term incubation under extreme pH,high-temperature or high-salt conditions.Remarkably,the Cu-Cys NLs could be easily recovered and still maintained 76%of their activity after 8 cycles.Finally,this laccase mimic was employed to develop a colorimetric method for epinephrine detection,which achieved a wider linear range(9–455μmol·L^(−1))and lower limit of detection(2.7μmol·L^(−1)).The Cu-Cys NLs also displayed excellent specificity and sensitivity towards epinephrine in a test based on urine samples.