Postmortem Diffusion of Aconitum Alkaloids and Their Metabolites in Rabbits.

OBJECTIVES: To explore the postmortem diffusion rule of Aconitum alkaloids and their metabolites in poisoned rabbits, and to provide a reference for identifying the antemortem poisoning or postmortem poisoning of Aconitum alkaloids. METHODS: Twenty-four rabbits were sacrificed by tracheal clamps. After 1 hour, the rabbits were administered with aconitine LD50 in decocting aconite root powder by intragastric administration. Then, they were placed supine and stored at 25 ℃. The biological samples from 3 randomly selected rabbits were collected including heart blood, peripheral blood, urine, heart, liver, spleen, lung and kidney tissues at 0 h, 4 h, 8 h, 12 h, 24 h, 48 h, 72 h and 96 h after intragastric administration, respectively. Aconitum alkaloids and their metabolites in the biological samples were analyzed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). RESULTS: At 4 h after intragastric administration, Aconitum alkaloids and their metabolites could be detected in heart blood, peripheral blood and major organs, and the contents of them changed dynamically with the preservation time. The contents of Aconitum alkaloids and their metabolites were higher in the spleen, liver and lung, especially in the spleen which was closer to the stomach. The average mass fraction of benzoylmesaconine metabolized in rabbit spleen was the highest at 48 h after intragastric administration. In contrast, the contents of Aconitum alkaloids and their metabolites in kidney were all lower. Aconitum alkaloids and their metabolites were not detected in urine. CONCLUSIONS: Aconitum alkaloids and their metabolites have postmortem diffusion in poisoned rabbits, diffusing from high-content organs (stomach) to other major organs and tissues as well as the heart blood. The main mechanism is the dispersion along the concentration gradient, while urine is not affected by postmortem diffusion, which can be used as the basis for the identification of antemortem and postmortem Aconitum alkaloids poisoning.

Design and Construction of the Uranyl Coordination Polymer with Multifunction Stimulus Response: Fluorescent Sensors for Halide Ions and Photochromism.

It can provide ideas for the use of uranium elements in the treatment of spent fuel from nuclear wastewater to explore the application potential of uranium element. Thus, it is necessary to research the structure and properties of a novel uranyl coordination polymer (CP) for uranium recovery and reuse. Herein, we designed and prepared a new uranyl CP U-CMNDI based on UO22+ and H2CMNDI (H2CMNDI = N, N'-bis(carboxymethyl)-1,4,5,8-naphthalenediimide). Structural analysis shows that two uranyl ions are connected by two parallel deprotonated CMNDI ligands to form a discrete uranyl dimer structure. U-CMNDI can act as a potential stimulus-responsive halide ion sensor by a fluorescence "turn on" response in water. The limit of detection for fluoride (F-), bromide (Br-), iodide (I-), and chloride (Cl-) is 5.00, 5.32, 5.49, and 5.73 µM, respectively. The fluorescence "turn on" behavior is based on the photoinduced electron transfer (PET) mechanism between halide ions and electron-deficient NDI cores. In addition, U-CMNDI demonstrates a color response to ultraviolet light, exhibiting reversible photochromic behavior with a notable color change. The color change mechanism can contribute to the PET process and the radical process.

Smart crystalline framework materials with a triazole carboxylic acid ligand: fluorescence sensing and catalytic reduction of PNP.

Triazole polycarboxylic acid ligands are widely employed in the construction of MOFs due to their strong coordination ability and flexible coordination modes. In this work, three novel complexes (Pb(MCTCA)(H2O) (1), Co(HMCTCA)2(H2O)2 (2) and Cu(HMCTCA)2(H2O)2 (3)) based on the H2MCTCA ligand (5-methyl-1-(4-carboxyl)-1H-1,2,3-triazole-4-carboxylic acid) were successfully synthesized under hydrothermal conditions, respectively. X-ray single crystal structure analysis shows that complex 1 is a 3D network structure, where the central metal Pb(II) is six coordinated to form deformed triangular prism geometry. The complexes 2 and 3 are both 2D layer supramolecular structures connected through intermolecular hydrogen, where the central metals (Co/Cu) are six coordinated to form octahedral configuration geometry. Based on functional properties, it is found that complex 1 exhibits excellent detection ability for small-molecule drugs (azithromycin, colchicine and balsalazide disodium) and actinide cations (Th4+ and UO22+) within a lower concentration range without interference from other components. In particular, the detection limits of three small-molecule drugs are all lower than 0.30 µM. In addition, complexes 2 and 3 exhibited excellent catalytic reduction performance toward p-nitrophenol (PNP), with a reduction efficiency exceeding 98%. These experimental results evidence that complexes 1-3 have potential application prospects in fluorescence sensing and catalytic reduction.

A UOF based on a cyclotriphosphazene skeleton: fluorescence sensing of different substituted aldehydes and NACs.

A novel uranyl organic framework (U-hdpcp) based on flexible cyclic triphosphazene polycarboxylate ligands was prepared, which possesses the ability to sense aromatic aldehyde solutions (benzaldehyde, salicylaldehyde and 2-bromobenzaldehyde) and nitro compounds (2,4,6-trinitrophenol, 2,4-dinitrophenol and o-nitrophenol). A fluorescent thin film based on U-hdpcp@PVA with the ability to sense aldehyde vapors was prepared via a spin coating method. The work expands the library of UOF materials based on large-sized carboxylic acid ligands and demonstrates promising applications in the field of fluorescent sensors.

Multiple Stimulus Response 2D Framework Constructed by a Flexible Cyclotriphosphazene-Derived Carboxylic Acid Linker: Synthesis, Characterization, and Fluorescence Sensing to Phenolic Pollutants and Small-Molecule Drugs.

Hexachlorocyclotriphosphazene is one of the most representative phosphazene compounds which have been proved to have broad application prospects in many fields. However, it is an emerging research perspective to combine cyclotriphosphazene-derived polycarboxylic acid compounds with lanthanides for the construction of Tb-DPCP metal-organic framework (MOF) materials. Herein, a Tb-DPCP MOF, (CH3)2NH2[Tb3(HDPCP)(DMF)(H2O)3]·6DMF (1), was successfully prepared via the reaction of H12HDPCP [hexa(4-carboxyphenoxy) cyclotriphosphazene] and Tb(NO3)3·6H2O under the solvothermal condition. Through fluorescence sensing experiments, it was found that both nitrophenols and chlorophenols could cause the fluorescence quenching of compound 1. At the same time, the compound also exhibited nice trace detection ability for small-molecule drugs (moxifloxacin hydrochloride, balsalazide disodium, and colchicine); the limits of detection were all lower than 0.2 µM. These experimental results fully demonstrated the potential application value of 1 as a multifunctional fluorescent sensor.

Stimulus-Responsive Lanthanide MOF Materials Encapsulated with Viologen Derivatives: Characterization, Photophysical Properties and Sensing on Nitrophenols.

Viologens (1,1'-disubstituted 4,4'-bipyridyls) possessing electron-deficient properties and redox activity are a class of suitable chromophores to assemble metal-organic hybrid photochromic materials. Thus, viologen-functionalized metal-organic frameworks (MOFs) have attracted much attention for their photochromic properties; however, the syntheses of lanthanide-viologen hybrid crystalline photochromic materials still face many challenges. For example, the structures and properties of the final products are difficult to predict and are limited by molecular configurations. In this work, host-guest composite-material Ln-NH2 BDC-pbpy MOFs were constructed by encapsulating viologen derivative pbpyCl2 . The pbpy2+ moieties are uniformly embed by their π-π conjugation in the pores of the 3D structure by electrostatic interactions. Due to the encapsulation of the chromophore pbpy2+ moieties, Ln-NH2 BDC-pbpy MOFs have reversible photochromic properties: they can change color after irradiation and can return to the original color after being protected from light or heating. Interestingly, the fluorescence intensity decreases with illumination time and recovers in the dark. As a result, Ln-NH2 BDC-pbpy MOFs show both photochromic and photomodulated fluorescence. Based on the outstanding fluorescence performance of the Ln-NH2 BDC-pbpy MOFs, they also show a wonderful effect for detecting nitrophenols, especially TNP.

Cage Bismuth Metal-Organic Framework Materials Based on a Flexible Triazine-Polycarboxylic Acid: Subgram Synthesis, Application for Sensing, and White Light Tuning.

Bismuth-based metal-organic frameworks (MOFs) have always attracted the attention of many researchers. Here, we first report a crystalline Bi-MOF (Bi-TDPAT) based on a flexible triazine-polycarboxylic linker 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine (H6TDPAT) and bismuth nitrate; its crystallite quality is adequately good and the diffraction data can be collected directly by single crystal X-ray diffraction rather than 3D electron diffraction. The structure of Bi-TDPAT belongs to a novel topology type btt. Notably, the synthesis scale of Bi-TDPAT can be expanded, and sub-gram synthesis can be realized. At the same time, we synthesized a microcrystalline material Bi-TATAB utilizing 2,4,6-tris(4-carboxylphenylamino)-1,3,5-triazine (H3TATAB). The structures of the two materials were characterized by several microanalysis tools. Considering that Bi-TDPAT is a blue light-emitting material with a broad emission peak, we prepared a white light emitting composite material Eu/Tb@Bi-TDPAT by encapsulating Eu(III)/Tb(III) in Bi-TDPAT. In addition, the fluorescence sensing functions of Bi-TDPAT and Bi-TATAB were explored. The results showed that they could detect and recognize various nitrophenols, and the optimal limit of detection is as low as 0.21 µM, which can be reused even after five cycles. Energy competitive absorption (CA) and photo-induced electron transfer are the main sensing mechanisms. By comparing and analyzing the properties of these two bismuth-based crystalline materials, we believe that this work also provides inspiration for the synthesis and development of bismuth-based MOF in the future.

Integrated Photoresponsive Alkaline Earth Metal Coordination Networks: Synthesis, Topology, Photochromism and Photoluminescence Investigation.

Photoresponsive materials are a key part of the age of smart technology that have potential in a broad range of applications. Coordination networks (CNs) are widely used due to their designability and stability. In this work, three novel alkaline earth metal coordination networks (AEM-CNs): [Mg(CMNDI)(H2 O)2 ], [Ca(CMNDI)(H2 O)2 ]⋅H2 O, and [Sr(CMNDI)(H2 O)(DMF)] with fsl, cds, and scn topology nets were synthetized via N,N'-bis(carboxymethyl)-1,4,5,8-naphthalenediimide (H2 CMNDI); the scn net is not found in the Reticular Chemistry Structure Resource or ToposPro. The reusable and sensitive photochromic properties of the three CNs enable them to be used as secret inks or ultraviolet detectors. In addition, the CNs also exhibited reusable photoluminescent turn-off toward the drug molecules, balsalazide disodium (Bal.) and colchicine (Col.), with good limits of detection of 0.16 and 0.70 µM. To the best of our knowledge, this is the first study of a fluorescence sensor for Bal. Thus, the AEM-CNs provide a design idea for integrated photoresponsive materials that could be further improved in the near future by further study.

Spin-Orbit Charge-Transfer Intersystem Crossing in Anthracene-Perylenebisimide Compact Electron Donor-Acceptor Dyads and Triads and Photochemical Dianion Formation.

Perylenebisimide (PBI)-anthracene (AN) donor-acceptor dyads/triad were prepared to investigate spin-orbit charge-transfer intersystem crossing (SOCT-ISC). Molecular conformation was controlled by connecting PBI units to the 2- or 9-position of the AN moiety. Steady-state, time-resolved transient absorption and emission spectroscopy revealed that chromophore orientation, electronic coupling, and dihedral angle between donor and acceptor exert a significant effect on the photophysical property. The dyad PBI-9-AN with orthogonal geometry shows weak ground-state coupling and efficient intersystem crossing (ISC, ΦΔ =86 %) as compared with PBI-2-AN (ΦΔ =57 %), which has a more coplanar geometry. By nanosecond transient absorption spectroscopy, a long-lived PBI localized triplet state was observed (τT =139 µs). Time-resolved EPR spectroscopy demonstrated that the electron spin polarization pattern of the triplet state is sensitive to the geometry and number of AN units attached to PBI. Reversible and stepwise generation of near-IR-absorbing PBI radical anion (PBI-⋅ ) and dianion (PBI2- ) was observed on photoexcitation in the presence of triethanolamine, and it was confirmed that selective photoexcitation at the near-IR absorption bands of PBI.- is unable to produce PBI2- .

Cu-MOF Material Constructed with a Triazine Polycarboxylate Skeleton: Multifunctional Identify and Microdetecting of the Aromatic Diamine Family (o,m,p-Phenylenediamine) Based on the Luminescent Response.

Organic aromatic amines are widely used in various fields such as pharmaceuticals, pesticides, dyes, and tobacco smoke. The pollution of organic amines has become a problem that cannot be ignored, due to the extensive harmful effects on the environment and public health, which has become one of the most concerned frontier fields in the world. Identifying and microdetecting o-phenylenediamine (OPD), m-phenylenediamine (MPD), and p-phenylenediamine (PPD) using MOFs have rarely been reported. On the basis of the blue emission properties of Cu-TBDA constructed with 5,5'-((6-chloro-1,3,5-triazine-2,4-diyl)bis(azanediyl))diisophthalic acid (H4TBDA) ligand, Cu-TBDA was studied primarily to identify and detect aromatic diamine family as a multifunctional chemical sensor. Interestingly, Cu-TBDA has a very high selectivity and sensitivity to OPD and MPD with a low limit of detection (5.00 µM for OPD and 1.77 µM for MPD). Especially for OPD, Cu-TBDA has a unique switching function for it. When the concentration of OPD is less than 9.1 × 10-4 M, the fluorescence response of Cu-TBDA suspension exhibit enhanced. However, when the concentration of OPD is more than 9.1 × 10-4 M, the emission intensity displays quenching phenomenon. Therefore, Cu-TBDA as a chemical sensor not only has recognition and detection functions for organic aromatic amines but also first exhibits turn-on and -off sensing behavior toward OPD.

Polyiodine-Modified 1,3,5-Benzenetricarboxylic Acid Framework Zn(II)/Cd(II) Complexes as Highly Selective Fluorescence Sensors for Thiamine Hydrochloride, NACs, and Fe3+/Zn2.

Four new complexes, [Zn(TIBTC)(DMA)]·[NH2(CH3)2] (1), [Cd(TIBTC)(H2O)]·[NH2(CH3)2]·DMA (2), [Cd2(TIBTC)(2,2'-bipy)2(HCOO)] (3), and [Cd2(DIBTC)(2,2'-bipy)2(HCOO)] (4) (H3TIBTC = 2,4,6-triiodo-1,3,5-benzenetricarboxylic acid, H3DIBTC = 2,4-diiodo-1,3,5-benzenetricarboxylic acid, 2,2'-bipy = 2,2'-bipyridine, and DMA = dimethylacetamide), were successfully synthesized and characterized by elemental analysis, powder X-ray diffraction, infrared spectroscopy, ultraviolet-visible spectroscopy, and thermogravimetric analysis. Complexes 1 and 2 are three-dimensional supramolecular network structures, while complex 4 has a two-dimensional network structure. We preliminarily studied the fluorescence properties of the complexes and found that complexes 1-3 can detect thiamine hydrochloride, NACs, and Fe3+/Zn2+ with high sensitivity and selectivity.

Clinical Effects of CpG-Based Treatment on the Efficacy of Hepatocellular Carcinoma by Skewing Polarization Toward M1 Macrophage from M2.

OBJECTIVE: This study aims to explore the clinical efficacy of CpG-based therapy for treating hepatocellular carcinoma (HCC) by skewing polarization toward M1 macrophage from M2. METHODS: Pulmonary metastasis rate, overall survival time, and remission rate of 10 patients with HCC treated with transcatheter arterial chemoembolization (TACE) combined with CpG therapy and 10 age-, gender-, and TNM0-matched patients treated with TACE (control group) were compared. RESULTS: No pulmonary metastasis rate was 70% in the combined treatment group and 40% in the control group, respectively; and the differences between the two groups were statistically significant (p < 0.05). Median overall survival time was 22 months in the combined treatment group, compared with 6.65 months in the control group (p < 0.05). Remission rate in the combined treatment group (70%) was higher than in the control group (30%), but the differences between these two groups were not statistically significant (p > 0.05). CONCLUSION: Compared with TACE, CpG combined with TACE can decrease the pulmonary metastasis rate. This combined therapy can also improve the overall survival time of patients.

Tumor necrosis factor alpha-238G/A polymorphism and risk of breast cancer: An update by meta-analysis.

BACKGROUND: The association between the tumor necrosis factor-alpha gene (TNF-a) -238G/A polymorphism and the breast cancer has been analyzed in several studies, but the results have been inconclusive. We then performed a meta-analysis to get a precise estimation of the association. METHODS: Eight case-control studies with a total of 37,257 cases and 39,564 controls were identified by searching the ISI Web of Knowledge database and the PubMed database up to August 2014. RESULTS: Overall, no association was found between TNF-alpha-238G/A polymorphism and breast cancer in any of genetic model (additive model OR = 1.06, 95%CI: 0.94-1.21, Pheterogeneity = .02; homozygous model OR = 1.04, 95%CI: 0.83-1.30, Pheterogeneity = .98; dominant model OR = 1.06, 95%CI: 0.92-1.21, Pheterogeneity = .01; recessive model OR = 1.04, 95%CI: 0.83-1.30, Pheterogeneity = .98). Furthermore, no significant association was identified when stratified by ethnicity (Caucasian, Asian). CONCLUSION: This meta-analysis indicated that the TNF-alpha-238G/A polymorphism is not associated with breast cancer risk in the overall population.

Potential Neurogenesis of Human Adipose-Derived Stem Cells on Electrospun Catalpol-Loaded Composite Nanofibrous Scaffolds.

Catalpol, a natural active ingredient extracted from the traditional Chinese medicine, was verified exhibiting beneficial effects on neural differentiation compared with commonly used chemical inducers by our previous studies. The aim of this study was to evaluate the effects of catalpol-loaded scaffold on guiding neuronal differentiation of human adipose tissue-derived stem cells (hASCs). Fabrication technique of catalpol loading into the electrospun poly(lactic-co-glycolic acid)/multi-walled carbon nanotubes/silk fibroin nanofibrous scaffolds was successfully established. The topographical and mechanical properties of the nanofibers scaffolds were characterized by scanning electron microscopy and tensile instrument, respectively. In vitro catalpol release was studied in phosphate-buffered solution at 37 °C. Immunnocytochemistry, RT-PCR, and western blot assays were performed to estimate hASCs neuronal differentiation, and it was shown that catalpol has significantly upregulated the expressions of ßIII-tubulin and Nissl. Our experiments demonstrated that catalpol, as a traditional Chinese medicine extract, could be encapsulated into composite nanofibers and induce differentiation of hASCs into neural-like cells, which might offer new avenues in nerve regeneration.

Synthesis, crystal structure, photoluminescence property and photoelectronic behavior of two uranyl-organic frameworks constructed from 1, 2, 4, 5-benzenetetracarboxylic acid as ligand.

By using 1, 2, 4, 5-benzenetetracarboxylic acid as organic ligands, two uranyl coordination complexes, (UO2)2(bta)(DMA)2 (1) and [(UO2)2(bta)(µ3-OH2)]·2[HN(CH3)2]·H2O (2) (H4bta=1, 2, 4, 5-benzenetetracarboxylic acid, DMA=N,N-Dimethylacetamide) were synthesized. The X-ray single crystal analysis revealed that complex 1 exhibits a 3-demensional framework, while complex 2 exhibits a 2-demensional framework. In order to furthermore characterize the two complexes and extend their functional properties, spectroscopies of IR, UV-vis, photoluminescence and surface photovoltage were also studied primarily. In addition, thermogravimetric analyses and photocatalytic studies for complexes 1 and 2 were discussed in detail.

Application of multiple parallel perfused microbioreactors: Synthesis, characterization and cytotoxicity testing of the novel rare earth complexes with indole acid as a ligand.

Three novel complexes, [La(phen)2(IAA)2]·NO3 (1), [Sm(phen)2(IAA)2]·NO3 (2) and [Sm(IBA)3(phen)]·phen·HNO3·H2O (3) (phen: 1,10-phenanthroline, IAA: indole-3-acetic acid, IBA: indole-3-butyric acid), were synthesized and characterized with spectroscopy (infrared and UV-visible), X-ray crystal diffraction and elemental analysis. Structural analysis revealed that each lanthanide atom in complexes 1-3 held a distorted tricapped trigonal prism geometry in a nine-coordinate mode. There were two types of coordination modes of the IAA ligand in complexes 1 and 2: a µ2-η(1):η(2) bridging mode linking two lanthanide atoms and a µ2-η(1):η(1) double monodentate bridging mode. There were three types of coordination modes of the IBA ligand: a µ2-η(1):η(1) double monodentate bridging mode, a µ1-η(2) bridging mode and a µ2-η(1):η(2) bridging mode linking two lanthanide atoms. Adjacent Sm atoms were linked via the µ2-bridging carboxylate groups of the IBA ligands to generate a binuclear building unit. The biological activity of the complexes was evaluated in human adipose tissue-derived stem cells (hADSCs) and Chang liver cells using a multiple parallel perfused microbioreactor. The results showed that cytotoxicity increased as the concentrations of complexes 1-3 increased.

Synthesis, structures and properties of the catalytic bromination reaction of a series of novel scorperate oxidovanadium complexes with the potential detection of hydrogen peroxide in water.

A series of scorpionate oxovanadium (IV) complexes: [VO(Tp(4I))(pz)(SCN)]·1/2CH2Cl2 (1), [VO(Tp)(pzTp)]·2H2O (2), [VO(Bp)(Tp(4I))] (3) and [VO(C5H7O2)(Tp(4I))]·CH3OH (4) (Bp: [H2B(pz)(2-)], Tp: [HB(pz)(3-)], Tp(4I): [HB(4I-pz)(3-)], pzTp: [B(pz)(4-)]) have been synthesized and characterized by elemental analysis, IR spectra, UV-Vis spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction and thermal gravimetric analysis (TG). Structural analysis shows that the coordination environment of vanadium atom is N5O, to form a distorted octahedron geometry. In addition, the catalytic activities of the bromination reactions for complexes 1 and 2 in phosphate buffer with phenol red as a trap were evaluated primary by UV/Vis spectroscopy, and a practical application of H2O2 detection was firstly observed in the catalytic reaction system.