Portable and Recyclable Luminescent Lanthanide Coordination Polymer Film Sensors for Adenosine Triphosphate in Urine.

Adenosine triphosphate (ATP) is a small molecule that is released to the urine from bladder urothelial cells and the bladder mucosal band of the human body. In certain cases, ATP can serve as a biomarker in bladder disease. For the practical applicability of luminescent sensors for ATP in urine, it is significant to find a new strategy for making the detection progress simple and available for in-field urine analysis. Here, a novel luminescent lanthanide coordination polymer (Tb-BPA) was designed and synthesized for quick and sensitive detection of ATP through luminescence quenching with a quenching constant of 4.90 × 103 M-1 and a detection limit of 0.55 × 10-6 M. Besides, Tb-BPA has excellent anti-interference ability and can detect ATP in simulated urine with a small relative standard deviation (<4%). Moreover, the luminescent polyacrylonitrile nanofiber films modified by Tb-BPA were prepared by electrospinning and were used for ATP visual detection. Notably, this film is easy to recover and reuse, and maintains good detection performance after at least 7 cycles.

Highly sensitive sensing of DPA by lanthanide metal-organic frameworks and detection of fiber membranes.

The detection of 2,6-pyridinecarboxylic acid (DPA), as a biomarker of Bacillus anthracis, has attracted wide attention. In previous reports of DPA detection, fluorescent probes may not have high specificity. Therefore, the rational design and development of fluorescent sensors with excellent performance is of great significance for the detection of DPA. In this study, two novel lanthanide metal-organic frameworks (Ln-MOFs) were synthesized by hydrothermal method using 3-polyfluorobiphenyl-3 ', 4,5 ' -tricarboxylic acid (H2FPTA) as ligand. Studies have shown that Ln-MOFs can detect DPA in real time, with detection limits of 0.54 µM and 0.67 µM, respectively, and have a high recovery rate (95 % -108 %) in fetal bovine serum. As a self-calibration sensor, other substances in the blood can be clearly distinguished by a two-dimensional fluorescence code diagram. After the Ln-MOFs were spun into nanofiber membranes, they responded quickly to DPA. This increases practicability and provides a promising idea for the development of simple and efficient ratio sensors.

Two novel zinc-based MOFs as luminescence sensors to detect phenylglyoxylic acid.

Automobile exhaust gases, plastic pollutants, smoking, and other harmful substances can cause serious harm to human beings and the environment. Styrene, as a common airborne toxin, enters the human body through breathing or the skin and is discharged in the form of phenylglyoxylic acid (PGA). Therefore, specific, sensitive and trace detection of PGA is particularly important. Here, two zinc-based metal-organic frameworks {[Zn2L1(DMF)2H2O](DMF)2H2O}n, {[Zn4(L2)2(DMF)2(H2O)3](DMF)8}n (L1 = 2,5-bis((3-carboxylphenyl)amino)terephthalic acid, L2 = 2,5-bis((4-carboxyphenyl)amino)terephthalic acid) have been reported as 1 and 2, respectively. Both 1 and 2 present 3D structures, which can both be simplified as 4,4,4-c net topology. It is worth mentioning that 2 has two different kinds of Zn SBUs as connecting nodes in the structure. Besides, compared with the other materials for the detection of PGA, 1 and 2 exhibit relatively low detection limits (LODs), both in water and in urine (where the LODs for 1 in water and urine were 0.33 µM and 0.43 µM in the range of 0-0.39 mM, and those for 2 were 0.28 µM and 0.49 µM in the range of 0-0.59 mM, respectively). In addition, the sensors have excellent anti-interference ability, high stability, rapid response, and can easily distinguish between different concentrations of PGA with the naked eye. The developed paper probes were suitable for practical sensing applications for portable detection of PGA in urine.

Nanoarchitectonics of Indocyanine Green/Doxorubicin-Loaded Hydroxyl Boron Nitride Nanosheets for Chemophotothermal Therapy.

Biocompatible hydroxylated boron nitride nanosheets were effectively loaded with indocyanine green and doxorubicin using successive assembly. The indocyanine green/doxorubicin-loaded hydroxyl boron nitride nanosheets (ICG/DOX@OH-BNNS) integrated photothermal therapy and chemotherapy into a single nano vehicle. It had been confirmed that ICG/DOX@OH-BNNS could produce reactive oxygen species and exhibit excellent photothermal effects and light-triggered faster DOX release with NIR laser irradiation. On the other hand, the fluorescence of DOX in ICG/DOX@OH-BNNS was also used for visualizing subcellular location. Compared with individual chemotherapy and photothermal therapy, the combined treatment of ICG/DOX@OH-BNNS could synergistically induce the apoptosis and death of A549 cells and suppress S180 tumor growth in vivo.

Three novel metal-organic frameworks with different coordination modes for trace detection of anthrax biomarkers.

Dipicolinic acid (DPA) is an anthrax biomarker. Its serious consequences make its detection a great need. In this paper, three novel metal-organic frameworks (MOFs) with different coordination modes were synthesized by a simple solvothermal method, which can be used as highly efficient fluorescence sensors for the highly selective and sensitive trace detection of DPA. MOFs 1-3 showed rapid responses to DPA (<30 s), and the limits of detection (LODs) were calculated to be 1.01 × 10-6 M-1 (MOF 1), 1.17 × 10-6 M-1 (MOF 2) and 2.07 × 10-6 M-1 (MOF 3). DPA detection based on MOFs 1-3 in fetal bovine serum is highly reliable based on the high recovery rates (90% to 115%). Hence, the three MOF-based sensors can be used in the real-time detection of DPA.

Two new lanthanide complexes with 5-(Pyrazol-1-yl)nicotinic acid: Structures and their anti-cancer properties.

Two new lanthanide complexes [PrL2(EA)2]NO3 (complex 1) and [SmL2(EA)2]NO3 (complex 2) (H2L = 5-(Pyrazol-1-yl)nicotinic acid, EA = CH3CH2OH) were synthesized. The structures were characterized by single crystal X-ray and elemental analysis. The interaction between the complex and fish sperm DNA(FS-DNA) was monitored using ultraviolet and fluorescence spectroscopy, and the binding constants were determined. Both complexes showed the ability to effectively bind DNA, and the molecular docking technology was used to simulate the binding of the complex and DNA. In addition, through the annexin V-Fluorescein Isothiocyanate(FITC)/ Propidium Iodide (PI) test experiment, tetrazollium [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide(MTT) in vitro test, and cell morphology apoptosis studies, it was shown that the complex can effectively induce HeLa tumor cell apoptosis. Compared with cisplatin and complex, complex 1 shows significant cancer cell inhibition, and we hope that this new type of complex will open up new ways for the next generation of drugs in biomedical applications.

Highly Emissive Metal-Organic Frameworks for Sensitive and Selective Detection of Nitrofuran and Quinolone Antibiotics.

The overuse of antibiotics makes its detection very significant for human health. New facile methods and high-performance sensory materials will be urgently needed for detection of antibiotics. Unfortunately, there are few reports on fluorescence enhancement of antibiotics detection. Herein, based on the modulability of the coordination mode, we proposed two MOFs with different coordination modes based on different metal ions: Zn-MOF (1) and Cd-MOF (2). The fluorescence of 1 and 2 can be efficiently and selectively quenched by nitrofuran antibiotics (nitrofurazone, NFZ and furazolidone, FZD) and chloramphenicol (CAP), respectively. Particularly, the matched energy levels between 2 and enrofloxacin (ENR) enables 2 with turn-on sensing for ENR. Moreover, apart from the sensitivity and selectivity, 1 and 2 also have strong recyclable ability, fast response time and anti-interference ability, which make them great potential sensory materials to detect antibiotics.

On the redox property of Ag16Au13 clusters: One-way conversion from anionic [Au13Ag16L24]3- to charge neutral [Au13Ag16L24]0.

The redox property of metal nanoclusters plays a pivotal role and is of particular interest in catalysis and other applications, such as aerobic oxidation, hydrogenation, and singlet oxygen generation, over intact nanoclusters. In this study, we report a one-way conversion process of the anionic [Ag16Au13L24]3- nanocluster into a charge neutral nanocluster of [Ag16Au13L24]0 via oxidation in a solution phase using H2O2 as the oxidant. Three-electron loss of [Ag16Au13L24]3- occurred during the oxidation process, which was confirmed by electron paramagnetic resonance and electrospray ionization mass spectrometry methods. The one-way conversion from [Ag16Au13L24]3- to [Ag16Au13L24]0 nanoclusters is in situ monitored by UV-visible spectroscopy. A nanocluster charge effect is manifested in the UV-visible spectra of nanoclusters; an ∼10 nm redshift is observed compared with the optical absorption spectrum of [Ag16Au13L24]3-.

Three coordination polymers with regulated coordination interactions as fluorescent sensors for monitoring purine metabolite uric acid.

A facile optical sensor for uric acid (UA), an early pathological signature for the metabolic function of humans, was developed based on water-stable coordination polymers (CPs). Herein, three new isostructural fluorescent CPs, [Ln(TCPB)(DMF)3]n (Ln = La, CP 1; Ce, CP 2 and Pr, CP 3; H3TCPB = 1,3,5-tris(1-(2-carboxyphenyl)-1H-pyrazol-3-yl)benzene), with various metal ions were solvothermally synthesized. Significantly, by regulating the metal-organic coordination interactions, the fabricated CP 3 can quantitatively recognize UA with higher sensitivity compared with CP 1 and CP 2. The mechanism for the sensing properties further demonstrates the best performance of CP 3 and the excellent selectivity for UA monitoring. This work represents the strategy of designing fluorescent CP sensors to determine UA and provides a convenient approach for developing analysis platforms for the assessment of related disease progress and human health monitoring.

A Water-Stable Lanthanide Coordination Polymer as Multicenter Platform for Ratiometric Luminescent Sensing Antibiotics.

As a hot topic of global concern, the distinguishing and detecting of antibiotic pollution is crucial owing to its adverse effect on ecosystems and human health stemming from excessive use and poor management. Herein, a water-stable lanthanide coordination polymer sensor (Dy-TCPB) with multiple emitting centers is prepared. The versatile Dy-TCPB can conveniently differentiate various antibiotics, and displays a self-calibration luminescent response to nitrofurazone (NFZ) and furazolidone (FZD). Each antibiotic exhibits notable correlation to a unique combination of the two ligand-to-Dy ion emission intensity ratios, enabling two-dimensional fingerprint recognition. Furthermore, the novel self-calibration sensor demonstrates effective recognition of NFZ and FZD with excellent sensitivity and selectivity, and detection limits as low as 0.0476 and 0.0482 µm for NFZ and FZD, respectively. The synthetic approach for the fabrication of a singular coordination polymer exhibiting multiple emissions provides a promising strategy for the development of facile and effective ratiometric sensors.

A series of novel complexes firstly constructed by 1,4-phenylenedioxydiacetic acid plays a role in disruption of DNA gene expression and induction of apoptosis.

A set of five metal-organic frameworks, namely, [Cd2(L)2BIP(H2O)2·6H2O]n(1), [Ce(L)1.5(H2O)2·H2O]n(2),[Sm(L)1.5(H2O)2·3H2O]n(3),[Gd(L)1.5(H2O)2·3H2O]n(4),[Ho(L)1.5(H2O)2·3H2O]n(5), have been prepared under hydrothermal conditions (1,4-H2L=1,4-Pheny lenedioxydiacetic acid; 1,4-BIP=1,4-bis(2-pyridylmethyl)piperazi-ne; C2H5OH=EtOH). The long BIP ligand (N⋯N separation of ca. 8.355Å) induces interpenetration of 1 to increase both the framework stability and the density of effective catalytic metal centers. Characterization of all complexes has been carried out by means of IR spectroscopy, single crystal and powdered sample X-ray diffraction (PXRD) through conventional and synchrotron radiation, Thermogravimetric (TG), fluorescent measurement (liquid and solid), DNA molecular docking, cancer cell apoptosis morphology through fluorescent inverted microscope, IC50, which the cytotoxic activity of the complexes was tested against two different cancer and one normal cell lines. The results indicate that all the complexes are potential fluorescent light-emitting materials and the flour (2, 3, 4, 5) complexes present remarkable anti-cancer effect.

Two novel dinuclear ellipsoid Ni(II) and Co(II) complexes bridged by 4,5-bis(pyrazol-1-yl)phthalic acid: Synthesis, structural characterization and biological evaluation.

Two novel complexes, [Ni2(L)2(H2O)3]·4(H2O) (1) and [Co2(L)2(H2O)3]·5(H2O) (2) [H2L = 4,5-bis(pyrazol-1-yl) phthalic acid] were synthesized and characterized by spectroscopy (IR, 1H NMR), and elemental analysis. The structures for the complexes were determined by X-ray crystallography providing the dinuclear ellipsoid Ni(II) and Co(II) complexes bridged by 4,5-bis(pyrazol-1-yl)phthalic acid ligands with same coordination modes. The interaction capacity of the complexes with FS-DNA (fish sperm DNA) has been investigated by UV and fluorescence spectroscopy. Gel electrophoresis assay demonstrated the ability of the complexes to cleave the pBR322 plasmid DNA. The cytotoxic activity of the complexes was tested against two different cancer cell lines, HeLa (human cervix epithelia carcinoma cells) and KB (human oral epithelial carcinoma cells), exhibiting significant cancer cell inhibitory rate. Furthermore, flow cytometry experiments and morphological apoptosis studies showed that the complexes induced apoptosis of KB tumor cell lines. The good visualization images supported with the experimental results of structure-activity relationship.

pH Dependent synthesis of two isomeric dinuclear Cerium(II) complexes: Structures, DNA interactions, cytotoxic activity and apoptotic study.

Two isomeric dinuclear Cerium(II) complexes 1 and 2, formulated as Ce2(phen)2(NO3)2(L)4 [L=phenylacetic acid, phen=1,10-phenanthroline] was synthesized under solvothermal conditions at different pH values. The two complexes were characterized by elemental analysis, IR and single crystal X-ray diffraction. Complexes 1 and 2 were studied the binding with DNA and against cytotoxic activity. Fluorescence analysis indicated that the two complexes can bind to DNA. The changes with different gradient concentration of DNA added into the complexes in absorption spectra show a strongπ-stacking interaction between the complexes and DNA base pairs. The Cerium(II) complexes showed good cytotoxic activity against cancer cell lines, being 2 the most potent complex. Apoptotic studies of the two novel dinuclear complexes showed significant inhibitory rate on cancer cell growth line KB.

Synthesis, structures, molecular docking, cytotoxicity and bioimaging studies of two novel Zn(II) complexes.

Two novel compounds [Zn2(Endc)2(bipy)2(H2O)3]·4(H2O)·2(O)(1), [Zn2(Endc)2(phen)2(H2O)]·(O)(2) (bipy = 2,2-bipyridine, phen = 1,10-phenanthroline, and Endc = endo-norbornene-cis-5,6-dicarboxylicacid) have been synthesized and characterized. In this paper abbreviations are FS-DNA (fish sperm DNA), HeLa (human cervix epithelia carcinoma cells), KB (human oral epithelial carcinoma cells), LO2 (human liver cell L-O2), EtBr (ethidium bromide), DMF (Dimethyl Formamide), MTT ([3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium]). The binding of complexes with Fish Sperm DNA were measured by electronic absorption spectra and fluorescence spectroscopy. The ability of these complexes to cleave the pBR322 plasmid DNA or the KB and HeLa DNA extracted in our laboratory was demonstrated by gel electrophoresis assay. The cytotoxic effects of these complexes were examined on two tumor cell lines, HeLa, KBr and one normal cell line LO-2. UV absorption and fluorescence spectra indicate the ability of the complexes bond to DNA with different binding affinity. Gel electrophoresis assay demonstrates which one complex more effective DNA-cleavage activity. The cytotoxic activity of the complexes was tested against two different cancer and one normal cell lines. The two complexes exhibited cytotoxic specificity and significant cancer cell inhibitory rate and lower cytotoxicity toward the normal cell lines. The unique interaction mode with DNA and cancer cells inhibition effect clearly revealed the relationship between the structure and the activity of the novel antitumor agent Zn(II) complexes.

The Syntheses, Structures, Fluorescence Properties and Biological Activity of two Novel Zinc(II) Complexes Controlled by the Tripodal Imidazole Ligand.

Two new zinc complexes, namely Zn(L(1))ClCH2NO(1) and {Zn(L(2))CH2NO}n▪N(CH3)3▪ClO4(2) (L(1) = 3,5-di(1H-imidazol-1-yl)pyridine L(2) = 1,3,5-tris(1-imidazolyl) benzene), have been synthesized, and characterized by IR spectra, elemental analysis, and a single crystal X-ray diffraction. Fluorescence spectroscopy indicated that two complexes presented strong DNA binding affinity constants to fish sperm DNA (FS-DNA). Gel electrophoresis assay demonstrated the ability of the complex to cleave the HL-60 DNA. Apoptotic study showed the complex exhibited significant cancer cell(KB) inhibitory rate.

The structures, cytotoxicity, apoptosis and molecular docking controlled by the aliphatic chain of palladium(II) complexes.

A new series of Pd(II) complexes derived from benzenealkyl dicarboxylate ligands, [Pd(Ln)(phen)] (phen=2,9-dimethyl-1,10-phenanthroline, complex 1: L1=phenylmalonate; complex 2: L2=benzylmalonate; complex 3: L3=(2-phenylethyl)malonate; complex 4: L4=(3-phenylpropyl)malonate) have been synthesized under room temperature condition. These complexes contain a long dicarboxylate aliphatic chain. They were characterized by elemental analysis, infrared spectroscopy, single crystal X-ray diffraction. The binding of complexes with fish sperm DNA (FS-DNA) was investigated by UV absorption and fluorescence spectra. Gel electrophoresis assay demonstrated the ability of the complexes to cleave the pBR322 plasmid DNA. The cytotoxic activity of the complexes was tested against two different cancer cell lines, HeLa and HL-60. Cytotoxic activity studies showed the four complexes exhibited significant cancer cell inhibitory rate. Further flow cytometry experiments showed that the cytotoxic Pd(II) complexes induced apoptosis of HL-60 tumor cell lines. The molecular dynamic simulations and docking methods were used to predict the DNA binding affinity of Pd(II) complexes by the resulting relative binding energy of complexes with DNA -6.01, -6.25, -7.24 and -7.59 kcal/mol, while with DNA-topoisomerase I (Topo I) -7.98, -9.25, -10.2 and -11.5 kcal/mol, respectively. The good visualization images supported with the experimental results of structure-activity relationship between cytotoxicity and carbon chain length.

A Multi-Scale Approach to Investigating the Red-Crowned Crane-Habitat Relationship in the Yellow River Delta Nature Reserve, China: Implications for Conservation.

The red-crowned crane (Grus japonensis (Statius Müller, 1776)) is a rare and endangered species that lives in wetlands. In this study, we used variance partitioning and hierarchical partitioning methods to explore the red-crowned crane-habitat relationship at multiple scales in the Yellow River Delta Nature Reserve (YRDNR). In addition, we used habitat modeling to identify the cranes' habitat distribution pattern and protection gaps in the YRDNR. The variance partitioning results showed that habitat variables accounted for a substantially larger total and pure variation in crane occupancy than the variation accounted for by spatial variables at the first level. Landscape factors had the largest total (45.13%) and independent effects (17.42%) at the second level. The hierarchical partitioning results showed that the percentage of seepweed tidal flats were the main limiting factor at the landscape scale. Vegetation coverage contributed the greatest independent explanatory power at the plot scale, and patch area was the predominant factor at the patch scale. Our habitat modeling results showed that crane suitable habitat covered more than 26% of the reserve area and that there remained a large protection gap with an area of 20,455 ha, which accounted for 69.51% of the total suitable habitat of cranes. Our study indicates that landscape and plot factors make a relatively large contribution to crane occupancy and that the focus of conservation effects should be directed toward landscape- and plot-level factors by enhancing the protection of seepweed tidal flats, tamarisk-seepweed tidal flats, reed marshes and other natural wetlands. We propose that efforts should be made to strengthen wetland restoration, adjust functional zoning maps, and improve the management of human disturbance in the YRDNR.

Syntheses, characterization, interaction with DNA, cytotoxic and apoptosis of two novel complexes of Zn(II) and Mn(II) with 2-methyl-1H-4,5-imidazoledicarboxylic acid.

Two new complexes, Zn(L)2(H2O)2 (1) and Mn(L)2(H2O)2 (2) [L = 2-Methyl-1H-4,5-imidazoledicarboxylic acid] were synthesized and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction. Intramolecular weak interactions, such as hydrogen-bond and intermolecular interactions were presented in the complexes. The activities of the complexes binding with DNA, and cytotoxic activities were studied. The binding of complexes with fish sperm DNA (FS-DNA) was investigated by fluorescence spectra. Gel electrophoresis assay demonstrated the ability of the complexes to cleave the pBR322 plasmid DNA. The cytotoxic activities of the complexes were tested against the KB cell line. Cytotoxic activity studies showed the two complexes exhibited significant cancer cell inhibitory rate. The most active compound was complex 1 with IC50 and CC50value of 36.5, 429, with the selectivity index (SI = 11.75) among the tested compounds.

A Novel Cobalt(II) Coordination Complex Constructed from H2Pyri and 4,4'-Bipy: Synthesis, Characterization and Bioactivity.

The new complex of {[Co(4,4'-Bipy)(H2O)4]·(Pyri) · 3H2O}n (4,4'-Bipy = 4,4'-bipyridyl, H2Pyri = 3,5- Pyridinedicarboxylic acid) was synthesized and characterized by IR, element analysis and X-ray single-crystal diffraction. The binding of the complex with extracted HeLa cells DNA was investigated by UV and fluorescence spectrum. Gel electrophoresis assay demonstrated the ability of the complex cleaving the extracted HC-DNA. The complex exhibited a higher cytotoxicity against tumor cells in vitro. Furthermore, the apoptotic tests indicated the complex had an apoptotic effect on HeLa cells.

Effect of carbon chain length on biological activity of novel palladium (II) complexes.

A series of complexes [Pd(L1)(Phen)]·2H2O (1), [Pd(L2)(Phen)]·H2O (2), [Pd(L3)(Phen)]·H2O (3), [Pd(L4)(Phen)]·2H2O (4) and [Pd(L5)(Phen)]·2H2O (5) were prepared. The complexes were characterized by IR, (1)H NMR, elemental analysis, and single-crystal X-ray diffractometry. The binding of the complexes was investigated by fluorescence spectrum and UV spectrum, showing the ability of interaction with DNA of intercalative mode. Gel electrophoresis assay demonstrated the ability of the complexes to cleave the pBR322 DNA. Moreover, the five complexes bind to DNA with different binding affinities, in ascending order: complex 1 < 2<3 < 4 < 5. Evaluation of cytotoxic activity of the complexes against five different cancer cell lines proved that the complexes exhibited cytotoxic specificity and significant cancer cell inhibitory rate.