Highly sensitive fluorescent sensing and photocatalytic degradation performance of two-dimensional Tb-organic network

A novel tetra-nuclear Tb-organic network,named as [Tb_(4)(2-pyia)_(6)(HAc)_(0.5)(2,2'-bipy)(H_(2)O)_(4.5)]·2,2'-bipy·H_(2)O(1),was synthesized hydrothermally based on 5-(pyridin-2-ylmethoxy) isophthalic acid(H_(2)pyia) and 2,2'-bipyridine(2,2'-bipy) ligands,and characterized by single crystal X-ray diffraction,thermogravimetric(TG) analyses,powder X-ray diffraction(PXRD) and infrared(IR) technology.1 possesses a two-dimensional network based on the tetra-nuclear inorganic building units,and the π-πstacking interactions between the pyia^(2-) ligands and the guest 2,2'-bipy molecules play an important role in the forming of 3D supramolecular structure.1 exhibits excellent fluorescent sensing performance for Fe^(3+)(1.26×10^(-8) mol/L),Cr_(2)O_(7)^(2-)(8.1×10^(-7) mol/L),2,4,6-trinitrophenol(TNP)(2.71×10^(-8) mol/L)and tetracycline(TCT)(2.76×10^(-7) mol/L) in aqueous solution with lower detection concentrations.The sensing mechanisms of 1 were investigated by density functional theory(DFT) calculations,ultraviolet-visible(UV-Vis) diffuse reflectance spectroscopy,PXRD and fluorescent lifetime analyses.The activated product of 1 was prepared by heating at 255℃ under constant pressure and used to photo-catalytically degrade TCT.Both 1 and the activated one have good photocatalytic degradation performance for TCT with degradation rates of 84.29% and 96.07%,respectively.The photocatalytic mechanisms were discovered by UV-Vis diffuse reflectance spectroscopy and radical trap experiments.The Tb-organic framework might be an excellent multifunctional fluorescent sensor and a good photocatalytic agent for TCT degradation in the future.

Effect of Reaction Conditions on the Assembly, Structures and Fluorescent Sensing Behaviors of Cd（II） Metal-organic Complexes

Three Cd（II） metal-organic complexes, namely [Cd（phen）2Cl2]（1）, [Cd（phen）Cl2]（2） and [Cd（phen）（cam）]. H2O（3）（phen=1,10-phenanthroline, H2cam=camphoric acid）, were hydrothermally synthesized using Cd2＋, phen and Hacam as raw materials under different conditions of pH values, reaction temperatures or reactant ratios. The prepared complexes were structurally characterized by means of single-crystal X-ray diffraction, and the results show that complex 1 is a 2D supramolecular complex, which consists of [Cd（phen）2Cl2] mononuclear subunits, while complex 2 shows a 1D chain structure, in which Cd（II） ions are connected by chloride（Cl ） bridges, with phen hanging on both sides of the chain. No cam anions have been observed in the structures of complexes 1 and 2. In complex 3, cam connects Cd（lI） ions to construct a 2D network, in which phen acts as terminal ligands. The adjacent 1D chains for complex 2 and the adjacent 2D layers for complex 3 are further linked by hydrogen bonding interac- tions or π-π intermolecular interactions to form 3D supramolecular networks, respectively. The effects of reaction conditions on the assembly and structures of the complexes have been discussed. The fluorescent and photocatalytic properties of complexes 1-3 and the fluorescent sensing behaviors of complexes 2 and 3 have also been investigated.

Construction of Fluorescence Sensing Platform on the Basis of Carbon Nitride Nanosheet for the Detection of Interferon-γ

Purpose: Interferon-γ (INF-γ) is a cytokine that participates in the immune reaction of the body. Its level of secretion can reflect the immune response condition after the body is infected by pathogens, which is a significant indication of clinically-related diseases. Therefore, it is of great significance in application to develop a fluorescence biosensor to inspect INF-γ with rapidness, high sensitivity and high practicability. Method: The fluorescence sensor is made on the basis of the two-dimensional nano-material namely Carbon Nitride Nanosheet (CNNS) and the Aptamer probe to identify INF-γ (Apt®INF-γ). CNNS can quickly quench the Cy5 fluorescent dye modified on the Apt®INF-γ probe due to the Photoinduced Electron Transfer (PET), but when the INF-γ exists, Apt®INF-γ specifically identifies and combines it. The complex of Apt®INF-γ and INF-γ is away from CNNS, which can effectively block the fluorescent signal of Apt?INF-γ being quenched by CNNS. Result: The sensitive detection of IFN-γ protein can be achieved through the application of CNNS/Apt®INF-γ fluorescence sensing platform. In this method, the intensity of the fluorescent signal is positively correlated with the concentration of IFN-γ, of which the liner response range is 0.5 - 100 ng/mL and the limit of detection is 0.303 ng/mL. In addition, this fluorescence sensing platform has the advantages of high specificity, simple operation and low costs. It can inspect the content of IFN-γ in clinical serum samples without interference. The actual recovery rate of serum samples is 97.11% - 106.96%. Conclusion: Therefore, the CNNS/Apt®INF-γ sensing platform is expected to be implemented in the actual clinical detection, also conducive to developing a universal fluorescence biosensor to inspect other target materials.

Construction of Fluorescence Sensing Platform on the Basis of Molybdenum Disulfide Nanosheet for the Detection of AFB1

Purpose: Aflatoxin B1 is the most common mycotoxin in cereal crops;it is of stronger toxicity and has a carcinogenic effect. In recent years, a series of fluorescence sensors constructed on the basis of MoS2NS fluorescence quenching property have become a research hotspot. Therefore, we can construct a fast and simple analysis method with high specificity to detect AFB1 by utilizing MoS2NS, which can be effectively applied to food safety monitoring and clinical diagnosis. Method: In the current research, a fluorescence biosensor is developed on the basis of a new type of two-dimensional nano-material namely MoS2NS applied for the detection of AFB1. The fluorescence of Apt@AFB1 can be quickly quenched by MoS2NS through the fluorescence resonance energy transfer (FRET). When the target molecule AFB1 exists, after the specificity binding between AFB1 and aptamer, the Apt@AFB1 loses its single stranded structure and is away from MoS2NS, and the fluorescence of Apt®AFB1 cannot be quenched effectively. Such sensing signals can be used to achieve the sensitive detection of AFB1. Result: With this new method, under the optimized conditions, the AFB1 is analyzed in the MoS2NS/Apt®AFB1 sensing platform. Within the dynamic range of 0.2 - 25 ng/mL, the sensing platform expresses a good linear response to the level of AFB1 with the R2 = 0.9964 and LOD as 90 pg/mL. This method is applied to detect the actual serum samples and soybean milk with the recovery rate of 93.10% - 107.23% and 95.15% - 102.60% separately, and it can be used in the quantitative detection under the interference of other mycotoxins in a relatively accurate way. Conclusion: It is proved that this new detection method can be used as a potential biosensor platform for the detection of AFB1. This detection method features several advantages such as specificity, rapidness and low costs, which can meet the requirement of trace detection in clinical detection and food safety.

A Composite Catalytic Oxidation-fluorescence Sensing System for 2,4-dichlorophenol Analysis based on Fe(Ⅲ)PcTs-BuOOH-CdTe QDs

The active oxygen species in the catalytic oxidation system of Fe(Ⅲ)PcTs-t-BuOOH were identified,and the mechanism of the catalytic oxidation of phenolic substrates was proposed.Quinone imine molecules,the main products of catalytic oxidation reaction,can be adsorbed on the surface of CdTe QDs,resulting in their fluorescence quenching.A dual function of catalytic oxidation and fluorescence sensing was developed for the determination of dichlorophenol(DCP)based on the Fe(Ⅲ)PcTs-BuOOH-CdTe QDs system.The linear detection range of DCP was 1×10^(-6)-1.3×10^(-4) mol/L,and the detection limit 2.4×10^(-7) mol/L.This method was characterized by high selectivity,good repeatability and desirable stability,presenting promising potentials for analyzing DCP concentration in real water samples.

Direct Fluorescence Sensing of Metal Ions in Aqueous Solution Using Intramolecular Charge Transfer Emission from Aggregates of Pentaerythrityl Tetra(p-dimethylaminobenzoate)

Pentaerythrityl tetra(p-dimethylaminobenzoate) (PTDMAB) was synthesized and shown to emit in water-rich aqueous dioxane solutions the intramolecular charge transfer fluorescence that was sensitive to the presence of metal ions.

Development of porphyrin-based fluorescent sensors and sensor arrays for saccharide recognition

Saccharide sensing is a very meaningful research topic as saccharides are involved in many biological activities.However,it is challenging to design molecular sensors for saccharides because this family of compounds is hydromimetic in aqueous solutions and shares a similar chemical structure.In this review,research progress in the development of porphyrin-based saccharide sensors is described with representative examples.We focus on using porphyrin as the signal reporter because porphyrins exhibit unique advantages in high chemical stability,long emission wavelength,and multiple structural modification strategies.Reported literature results have been classified into mainly two sections according to the general working principles of the porphyrin sensor molecules.In the first section,recognition unit,design strategy and sensing performance of traditional porphyrin-based selective saccharide sensors are discussed.While in the second section,development of porphyrin-based sensor arrays for pattern recognition of saccharides has been summarized.Looking through the design strategy and sensing performance of reported achievements,it is reasonable to anticipate a bright future for designing practical porphyrin-based saccharide sensors.

Construction of Naphthalenediimide Lanthanide(Ⅲ)-MOFs and Composites Incorporated Electron-Rich Pyrene Derivative as Multifunctional Fluorescence Sensing for Nitro Aromatic Compounds and Aldehydes

The development of host-guest MOF luminescent composites has attracted considerable attention. However,it is still a challenge to reasonably design large scale conjugated polycarboxylic acids metal-organic framework (MOF) and modulate donor-acceptor interaction. Herein,a series of isostructural 3D porous lanthanide MOF [Ln_(2)(BINDI)0.5(NO_(3))(DMA)(H_(2)O)]∙DMA∙2.5H_(2)O (Ln = La (1),Ce (2),Pr (3) and Nd (4);H_(4)BINDI (N,N’-bis(5-isophthalic acid)-1,4,5,8-naphthalenediimide) were synthesized. Considering the electron-deficient performances of Ln-BINDI MOFs,D-A type composites Ln-MOFs (1—4@H_(4)TBAPy) were prepared via the incorporation of electron-rich H_(4)TBAPy (1,3,6,8-tetrakis(p-benzoic acid) pyrene),which more improved the luminescence performance of complexes 1—4 and can be used as fluorescence sensors for the detection of nitro compounds and aldehydes. High sensitivity of 1@H_(4)TBAPy towards pNBA,pNA PNP,DNP,and TNP could be achieved through hydrogen bond interactions between MOF and analytes,as well as the π-π interaction between H_(4)TBAPy and the naphthalene ring of BINDI,thus the fluorescence quenching efficiency of 1@H_(4)TBAPy was better than that of the complex 1. In addition,it is found that 1@H_(4)TBAPy has high selectivity and sensitivity to aromatic aldehyde SA,5-Mesal and HMBA. Such strategy to enhance the emission of NDI based Ln-BINDI MOFs,will open up an avenue to obtain more fluorescent MOFs for sensing.

Molecularly imprinted polymer based on upconversion nanoparticles for highly selective and sensitive determination of Ochratoxin A

A novel molecularly imprinted polymer (MIP) based on upconversion nanoparticles (UCNPs) was successfully synthesized for determination of Ochratoxin A (OTA). The MIP was developed on the silica-coated UCNPs using N-(1-hydroxy-2-naphthoyl amido)-(L)-phenylalanine (HNA-Phe) as the alternative template. The final composite combined the advantages of the high selectivity of MIP with the high fluorescence intensity of UCNPs which was selective and sensitive to OTA. Under the optimal condition, the fluorescence intensity of UCNPs@SiO2@MIP decreases linearly when the concentration of OTA increases from 0.05 to 1.0 mg/L. The detection limit of OTA with the method was 0.031 mg/L. At three spiked concentration levels (50, 100 and 200 μg/kg), the recovery ranges of OTA in corn, rice and feed are 88.0%–91.6%, 80.2%–91.6% and 89.2%–90.4%, respectively.

DNA template-synthesized silver nanoparticles:A new platform for high-performance fluorescent biosensing of biothiols

To develop the high-performance fluorescent bio-sensors, the metal nanoparticles were employed as nanoquenchers and at- tracted reasonable attention in the design of fluorescent biosensors. In this work, silver nanoparticles （AgNPs） were obtained via reduction of Ag＋ on FAM-labeled DNA template. For the tight binding between AgNPs and DNA, the tem- plate-synthesized AgNPs turned out high quenching efficiency and could be applied as super nanoquenchers to establish the biosensing platform for fluorescent detection. As an example, the template-synthesized DNA-AgNPs conjugates were em- ployed in sensing thiols. By forming S-Ag bonds, thiols interact intensely with AgNPs and replace the FAM-labeled DNA off from the surface of AgNPs, resulting in a fluorescence enhancement. Besides the advantages of lower background and higher signal-to-background ratio （S/B）, the conjugates present better stability, making them applicable in complicated biological fluids. To further evidence the feasibility of sensing thiols in real samples, the thiols in human urine were detected. The total amount of free thiols found in human urine was ranging from 229 μM to 302μM with the proposed sensor. To conclude the reliability, low content of Cys was added and the recovery was 98%-103%.

Non-covalently Functionalized Fluorescent Carbon Nanotubes： A Supramolecular Approach of Selective Zinc Ions Sensing in Living Cells

A fluorescent cyclodextrin/carbon nanotube assembly was easily constructed through the non-covalent attach- ment of adamantanylpyrene on carbon nanotube and the following association of cyclodextrin derivative bearing fluorescent substituent, and its structure was fully characterized by UV/Vis/NIR spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy and atomic force microscopy. Fluorescence spectroscopic and fluorescence microscopic studies showed that the resultant non-covalently functionalized fluo- rescent nanotube could be used as a highly selective fluorescent probe for Zn2＋ in both water and living cells. Without carbon nanotube, the fluorescence probe was unable to enter the cell but only anchored on the cell mem- brane. This approach will overcome the disadvantage of many spectral sensors that are unable to enter living cells and greatly improve the application of naotube-related supramolecular architecture in nanoscience and technology.

Flow velocity and temperature sensing using thermosensitive fluorescent polymer seed particles in water

Particle image velocimetry(PIV)is an experimental technique that uses microscale particles as tracers to measure the velocity of a fluid flow.In this paper,we seek to extend this technique to simultaneously measure fluid temperature as well,by employing a novel class of thermosensitive polymer particles.Towards this aim,we designed a process to encapsulate highly fluorescent thermosensitive NBD-AE-co-poly(N-isopropylacrylamide)polymers into optically transparent poly(dimethylsiloxane)particles.These novel PIV particles enable direct measurement of water velocity while serving as temperature probes that increase their fluorescence intensity when the temperature rises above 32°C.To demonstrate the ability of the particles to simultaneously serve as flow tracers and temperature sensors in water,we examine the flow velocity and temperature in the wake of a heated cylinder in a cross flow.Our results indicate the possibility of extending PIV to afford the spatial and temporal resolution of fluid velocity and temperature gradients in water,with potential application to the study of convection problems from life sciences to engineering.

Functional groups assisted-photoinduced electron transfer-mediated highly fluorescent metal-organic framework quantum dot composite for selective detection of mercury(Ⅱ) in water

The presence of toxic mercury (Ⅱ) in water is an ever-growing problem on earth that has various harmful effect on human health and aquatic living organisms.Therefore,detection of mercury (Ⅱ) in water is very much crucial and several researches are going on in this topic.Metal-organic frameworks (MOFs) are considered as an effective device for sensing of toxic heavy metal ions in water.The tunable functionalities with large surface area of highly semiconducting MOFs enhance its activity towards fluorescence sensing.In this study,we are reporting one highly selective and sensitive luminescent sensor for the detection of mercury (Ⅱ) in water.A series of binary MOF composites were synthesized using in-situ solvothermal synthetic technique for fluorescence sensing of Hg^(2+)in water.The welldistributed graphitic carbon nitride quantum dots on porous zirconium-based MOF improve Hg^(2+)sensing activity in water owing to their great electronic and optical properties.The binary MOF composite (2) i.e.,the sensor exhibited excellent limit of detection (LOD) value of 2.4 nmol/L for Hg^(2+).The sensor also exhibited excellent performance for mercury (Ⅱ)detection in real water samples.The characterizations of the synthesized materials were done using various spectroscopic techniques and the fluorescence sensing mechanism was studied.

TPE based aggregation induced emission fluorescent sensors for viscosity of liquid and mechanical properties of hydrogel

Two amphiphilic TPE E/Z isomers with aggregation induced emission(AIE)property have been synthesized and characterized.The logarithmic fluorescent intensity of the two molecules was in positive relationship with logarithmic viscosity of liquid.To note,the Z-TPE isomer exhibited more sensitivity in the viscosity of liquid sensing in comparison with the corresponding E-TPE counterpart(around 1.80 folds).Furthermore,two molecules could be used as fluorescent sensors for mechanical properties(viscosity and storage modulus)of hydrogel as well.In addition,two sensors displayed low cytotoxicity in normal tissue cell line(L929)within the concentration range of 2–10μmol/L.These results potentially promised their applications as fluorescent sensors for mechanical properties in the fields of biological and biomedical.

Metal-organic framework film for fluorescence turn-on H2S gas sensing and anti-counterfeiting patterns

Hydrogen sulphide(H2 S)is a common air pollutant,which is produced in various industry processes.Therefore,it is of crucial importance to detect H2 S in real time.Many fluorescent sensors were reported aiming at detecting H2 S in solution;however,the fluorescence sensing of gaseous H2 S has not yet been reported.In this work,we utilized the post-functionalized fluorescent film,MIL-100(In)@Eu3+/Cu2+film,realizing fluorescence turn-on sensing of gaseous H2 S at room temperature for the first time with the limit of detection as low as 0.535 ppm,which is comparable to some reported fluorescent probes for S2-ions and semiconductor based gaseous H2 S sensors.The sensor was designed due to the strong affinity of H2 S with Cu2+.With the formation of CuS,the"antenna effect"between the ligand and Eu3+recovered,resulting in the fluorescence turn-on of Eu3+emission.Additionally,we proposed a new method to realize multi-colour anti-counterfeiting patterns with lanthanide ions ink,taking advantage of the extraordinary smooth surface and uncoordinated carboxylate groups within the MIL-100(In)film.

Solvent-and metal-directed lanthanide-organic frameworks based on pamoic acid:observation of slow magnetization relaxation,magnetocaloric effect and luminescent sensing

Two types of lanthanide coordination polymers, namely, [Ln（PA）（NO3）（DMA）3]n （Ln=Gd （1）, Dy （2）, Eu （3）, Tb （4）） （type I）, and {[Ln2（PA）3（DMF）4]＇2DMF} （Ln=Eu （5）, Tb （6）） （type II） （PA=Pamoic acid, DMA=dimethylacetamide, DMF=N,N-dimethylformamide）, have been synthesized by the reaction of Ln（NO3）a-6H20 with pamoic acid through layer diffusion method. These complexes were characterized by single crystal X-ray diffraction, infrared spectroscopy （IR）, thermogravimetric analysis （TGA）, fluorescence and magnetic measurements. Solvents and lanthanide atoms in the reaction play an important role in controlling different structures. Type I demonstrated 1-D linear chain structure connected by Ln atoms and PA ligands. Type II exhibited non-interpenetrating 3-D 6-connected 43612 nets based on binuclear [Ln2（CO2）6（DMF）4] cores. Magnetic properties of complexes 1-4 were investigated in details. Complex 1 shows significant magnetocaloric effect with -△Sm=20.37 J kg^-1 K^-1 at 3.0 K and 7 T. Complex 2 exhibits slow relaxation of the magnetization. Complexes 3-6 exhibit both ligand- and metal-centered fluorescent properties. Complex 6 demonstrates fluorescent sensing of DMF and Cu^2＋ ion.

Novel luminescent europium-centered hybrid material covalently grafted with organically modified titania via 2-substituted imidazophenanthroline for fluorescence sensing

By employing a rational approach,we prepared a novel kind of luminescent europium-centered hybrid material named Eu(tta)_(3)NCP-TiO_(2).The resulting material was characterized by FT-IR spectra,SEM,X-ray diffraction,thermogravimetric analysis,and photoluminescence spectra.The hybrid material features the combined advantages of the europium complex and the titania host,exhibiting not only good thermostability,but also long luminescence lifetime.Owing to the excellent luminescence of this material,the application in detecting organic small molecule solvents and metal ions was explored systematically.Significantly,Eu(tta)_(3)NCP-TiO_(2) exhibits superior detection for nitrobenzene molecule and Cu^(2+) ion in DMF(N,N-dimethylformamide) medium.Furthermore,the limit of detection(LOD) of Eu(tta)_(3)NCP-TiO_(2) for nitrobenzene and Cu^(2+) ion can be counted as 5.593× 10^(-5) and 9.566 ×10^(-5) mol/L,respectively.The results demonstrate that Eu(tta)_(3)NCP-TiO_(2) can serve as an efficient fluorescence probe for the detection of sensing of nitrobenzene and Cu^(2+) ion.

Two New Coordination Polymers Based on H4BIPA-TC: Syntheses and Fluorescence Sensing for Nitroaromatic Compounds and Fe^3+ Ion

Based on the solvothermal reaction of 5,5΄-(1,3,6,8-tetraoxobenzo[lmn][3,8]phenanthrolin-2-7-diyl)bis-1,3-benzenedicarboxylic acid(H4L)linker and Zn(Ⅱ)/ⅡCd(Ⅱ),two new 2D coordination polymers(CPs),namely{[ZnH2L(4,4΄-bibp)]·H2O}n(1)and{[CdL0.5(1,4-bimb)0.5(H2O)]·EtOH}n(2)(L=BIPA-TC),have been successfully constructed and characterized by EA,PXRD and IR with the aid of 4,4΄-bis(benzoimidazo-1-yl)biphenyl(4,4΄-bbib)/1,4-bis(imidazol-1-ylmethyl)benzene(1,4-bimb).The structural analysis showed that complex 1 exhibits a 3D supramolecular structure with the topology of sql,and complex 2 possesses a 2-nodal(4,6)-c framework with the topology of(32·42·52)(34·44·54·63)-4,6T26.Fluorescent experiments showed that 1 and 2 have high selectivity and sensitivity for the sensing of nitroaromatic compounds and Fe3+in aqueous solutions.

Valorization of agro-industrial fruit peel waste to fluorescent nanocarbon sensor:Ultrasensitive detection of potentially hazardous tropane alkaloid

Millions of tonnes of agro-industrial waste are generated each year globally,with the vast majority of it going untreated,underutilized,and disposed of by burning or landfilling,causing severe environmental distress and economic downturn.A practical solution to this global issue is to use green chemistry to convert this waste into value-added products.Accordingly,in the present study,agro-industrial orange peel waste was valorized into fluorescent nanodiamond-like carbon sensor via a green route involving hydrothermal treatment of microwave carbonized orange peel waste.The developed sensor,used for the fluorescence detection of potentially hazardous drug atropine sulfate,exhibits unique dual linearity over concentration ranges of 300 nM to 1 M and from 1 M to 10 M,as well as ultra-low sensitivity of 34.42 nM and 356.46 nM,respectively.Additionally,the sensor demonstrates excellent reproducibility,high stability,and satisfactory recovery when used to identify and quantify atropine sulfate in biological samples and commercially available pharmaceuticals,indicating promising multidisciplinary applications.

High sensitivity ratiometric fluorescence temperature sensing using the microencapsulation of CsPbBr3 and K2SiF6:Mn4+phosphor

A dual emission sensing film has been prepared for colorimetric temperature sensing using CsPbBr_(3)perovskite nanocrystals(CsPbBr_(3)NCs)and manganese doped potassium fluorosilicate(K_(2)SiF_(6):Mn^(4+),KSF)encapsulated in polystyrene by a microencapsulation strategy.The CsPbBr_(3)-KSF-PS film shows good temperature sensing response from 30℃to 70℃,with a relative temperature sensitivity(Sr)up to 10.31%℃^(−1) at 45℃.Meanwhile,the film maintains more than 95%intensity after 6 heating-cooling cycles and keeps its fluorescence characteristics after 3 months.The film can be used to monitor temperature change by naked eye under a UV lamp.In particular,the temperature discoloration point of the sensing film can be controlled by the ratio change of CsPbBr_(3):KSF to expand its applications.The study of the CsPbBr_(3)-KSF-PS sensing mechanism in this work is helpful to provide effective strategies for the design of reliable,high sensitivity and stable temperature sensing system using CsPbBr_(3)NCs.