Inverted loading strategy regulates the Mn-OV-Ce sites for efficient fenton-like catalysis.

Regulating interfacial active sites to improve peroxymonosulfate (PMS) activation efficiency is a hot topic in the heterogeneous catalysis field. In this study, we develop an inverted loading strategy to engineer asymmetric Mn-OV-Ce sites for PMS activation. Mn3O4@CeO2 prepared by loading CeO2 nanoparticles onto Mn3O4 nanorods exhibits the highest catalytic activity and stability, which is due to the formation of more oxygen vacancies (OV) at the Mn-OV-Ce sites, and the surface CeO2 layer effectively inhibits corrosion by preventing the loss of manganese ion active species into the solution. In situ characterizations and density functional theory (DFT) studies have revealed effective bimetallic redox cycles at asymmetric Mn-OV-Ce active sites, which promote surface charge transfer, enhance the adsorption reaction activity of active species toward pollutants, and favor PMS activation to generate (•OH, SO4•-, O2•- and 1O2) active species. This study provides a brand-new perspective for engineering the interfacial behavior of PMS activation.

Spatial confinement of styryl pyridine salt derivative in MCM-22 molecular sieve network for boosted fluorescence emission and stable ratiometric sensing of bacillus anthracis biomarkers.

In this work, a stable ratiometric nanofluorescent probe for the detection of 2,6-dipicolinic acid (DPA), a Bacillus anthracis biomarker, was developed based on confinement-induced emission enhancement of cationic styrylpyridine salt derivative L in MCM-22 molecular sieve pores. The cationic L and the lanthanide Tb3+ were loaded into the pores of the molecular sieve by electrostatic interaction with the negatively charged AlO4 tetrahedron unit, and L exhibited enhanced red fluorescence emission as a stable fluorescence reference mark in the nanoprobe platform due to the restricted molecular torsion of L in the pores of MCM-22. At the same time, the characteristic green fluorescence emission of Tb3+ can be excited by energy transfer due to the "antenna effect" of DPA. The prepared Tb-L@MCM-22 nanoprobe showed specific selectivity and stable fluorescence ratiometric detection of DPA in tap water, lake water, bovine serum and actual bacterial spores. Benefiting from the confinement-induced fluorescence enhancement effect of L in the MCM-22 molecular sieve pores, the obtained Tb-L@MCM-22 can provide a stable reference signal for the fluorescence ratiometric detection of DPA with a limit of detection (LOD) of 78.6 nM and 1.310 × 104 spores per mL. More importantly, combining of the Tb-L@MCM-22 based DPA detection test strips with a smartphone app demonstrated a stable, convenient and rapid method for detecting of anthrax biomarkers.

A Novel D-π-A Type Fluorescent Probe for Cu2+ Based on Styryl-Pyridinium Salts Conjugating Di-(2-picolyl)amine (DPA) Units.

A novel D-π-A type fluorescent probe L(NO3) for Cu (II) sensing was designed and fully characterized. The probe consists of a styryl-pyridine cation fluorescent group and a di-(2-picolyl)amine (DPA) receptor unit, which are linked by a phenyl group to form an electron donor-π-acceptor (D-π-A) conjugate system, especially the introduction of a nitrate counter anion for significantly enhanced water solubility of the probe. Fluorescence titration studies of the probe L(NO3) showed a higher selectivity for Cu2+ than other metal ions, and the emission spectrum was strongly quenched upon binding. The competitive binding assay and the low detection limit (0.932 µM) showed that the probe L(NO3) had strong anti-interference ability and excellent Cu2+ detection performance. The binding ratio of probe L(NO3) and Cu2+ was determined from Job's plot to be 1:1, which is consistent with the results obtained from X-ray crystal structures. Meanwhile, the probe showed instantaneous chemical reversibility when titrated with EDTA solution, indicating potential recycling properties of the probe. In addition, the design of inexpensive fluorescent test strips can perform the on-site and real-time detection Cu2+ with a color recognition application.

Ion exchange fabrication of lanthanide functionalized layered double hydroxides microcapsules for rapid and visual detection of anthrax biomarker.

Lanthanide ion probes have recently been considered as promising sensing materials due to their high sensitivity and good optical properties. Herein, the 3D hierarchical lanthanide functionalized layered double hydroxides microcapsules were synthesized via a facile ion exchange strategy and further developed as novel fluorescent probes for detecting trace amounts of the anthrax biomarker dipicolinicacid (DPA). Benefiting from the 3D porous superstructure and abundant unsaturated coordination sites of lanthanide ion, the ternary Ni-Fe-Ln-LDHs (Ln = Tb/Eu) not only possess a large reactive contact area to improve the sensitivity of DPA detection, but also demonstrate very fast reaction rate. The design of inexpensive fluorescent test strips can perform the on-site and real-time detection via a smartphone with a color recognition application. More prominently, the sensitivity of the system was evaluated by actual spore samples with the detection limit as low as 3.54 × 104 spores/mL. The 3D lanthanide functionalized LDHs nanoprobe constructed by ion exchange exhibits a new vision for the development of a sensing platform in other research areas.

Synthesis, crystal structures, and two-photon absorption of a series of cyanoacetic acid triphenylamine derivatives.

A specific series of chromophores (CN1, CN2, CN3, and CN4) have been synthesized, in which contained a triphenylamine moiety as the electron donor (D), a cyanoacetic acid moiety as the electron acceptor (A), vinylene or phenylethyne as the π-bridge, and ethyoxyl groups as auxiliary electron donor (D') to construct the D-π-A or D'-D-π-A molecular configuration. Photophysical properties of them were systematically investigated. These results show that the chromophores display a solvatochromism (blue shift) and large Stokes shifts for their absorption bands with increasing polarity of the solvent. Furthermore, the chromophore CN4 shows the strongest intensity of two-photon excited fluorescence and largest two-photon absorption cross section (2783 GM) in the near infrared region. Finally, the connections between the structures and properties are systematically investigated relying on the information from linear and nonlinear optical properties, crytsal structures and quantum chemical calculation.

Solvent-dependent "turn-on" fluorescence chemosensor for Mg(2+) based on combination of C=N isomerization and inhibition of ESIPT mechanisms.

A fluorescent chemosensor (L) for Mg(2+) has been synthesized and characterized, which exhibits turn-on fluorescence response for Mg(2+) only in alcohol solvent (methanol or ethanol) with high sensitivity and selectivity. But in both nonpolar and polar solvents (cyclohexane, DCM, DMSO or MeCN), L showed negligible fluorescent response for Mg(2+). In order to discover the unique phenomenon, optical measurements, liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) and a high performance liquid chromatography with a fluorescence detector (HPLC-FLD) of L and L with Mg(2+) ions in solvents were studied. In alcohol solvent, [L+alcohol molecule] was formed and the mechanism aspect of L concerning the remarkable fluorescence response for Mg(2+) has been discussed.

Synthesis and nonlinear optical properties in the near-IR range of stilbazolium dyes.

A series of stilbazolium salts based on donor-π-acceptor (D-π-A) structure have been synthesized and fully characterized. Photophysical properties including linear absorption, one-photon excited fluorescence (OPEF), two-photon absorption (2PA) properties were systematically investigated. The results suggest that increasing electron-releasing character of the terminal group leads to a more pronounced donor-to-acceptor intramolecular charge transfer (ICT). In addition, the dyes possess the largest 2PA cross sections in the near infrared region (NIR) and display maximum two-photon absorption cross sections within the narrow wavelength range from 950 to 970nm and BL3 exhibits a large nonlinear refractive index coefficient and possesses very large values of the real part of the cubic hyperpolarizability χ((3)) at 960nm. Furthermore, the initial density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations provide reasonable explanations for their absorption spectra, meanwhile we used the Lippert-Mataga equation to evaluate the dipole moment changes of the dyes with photoexcitation, the results are corresponding with linear and nonlinear optical properties of the dyes.

Four new two-photon polymerization initiators with varying donor and conjugated bridge: synthesis and two-photon activity.

A specific series of dumbbell-shaped bis-carbazoles or bis-phenothiazines dyes (1, 2, 3 and 4) constructed with styrene or biphenylethyne as the π-bridge have been synthesized and characterized. Detailed spectral properties including linear absorption, one and two-photon fluorescence properties were investigated. The results show that extending conjugated chain and introducing donors have substantial effect on their photophysical properties. Among them, two-photon absorption cross sections (σ) of the four dyes in DMF determined by the Z-scan technique are successively increased from 1 to 4 with enhancing electron-donating ability and extending conjugated chain, but electron-donating ability has larger contribution to the σ values than extending conjugated chain based on the comparison of small molecules (D-π-D). Two-photon initiation polymerization (TPIP) microfabrication experiments have been carried out using compound 4 as an initiator under irradiation of 200 fs, 76 MHz femtosecond laser at 760 nm. The results confirm that the four dyes can be effectively used as organic two-photon photopolymerization initiators.

4-Eth-oxy-N-(4-eth-oxy-phen-yl)-N-(4-nitro-phen-yl)aniline.

In the title mol-ecule, C22H22N2O4, the eth-oxy-phenyl rings are oriented at dihedral angles of 69.31 (13) and 75.90 (13)° to the nitro-phenyl ring and are twisted to each other, making a dihedral angle of 78.55 (13)°. In the crystal, weak C-H⋯O hydrogen bonds and C-H⋯π inter-action link the mol-ecules into a three-dimensional supra-molecular architecture.

Biochemical characterization of an ATP-dependent DNA ligase from the hyperthermophilic crenarchaeon Sulfolobus shibatae.

A gene encoding a putative ATP-dependent DNA ligase was identified in the genome of the hyperthermophilic archaeon Sulfolobus shibatae and expressed in Escherichia coli. The 601 amino acid recombinant polypeptide was a monomeric protein capable of strand joining on a singly nicked DNA substrate in the presence of ATP ( K(m)=34 micro mu) and a divalent cation (Mn(2+), Mg(2+), or Ca(2+)). dATP was partially active in supporting ligation catalyzed by the protein, but GTP, CTP, UTP, dGTP, dCTP, dTTP, and NAD(+) were inactive. The cloned Ssh ligase showed an unusual metal cofactor requirement; it was significantly more active in the presence of Mn(2+) than in the presence of Mg(2+) or Ca(2+). Unexpectedly, the native Ssh ligase preferred Mg(2+) and Ca(2+) rather than Mn(2+). Both native and recombinant enzymes displayed optimal nick-joining activity at 60-80 degrees C. Ssh ligase discriminated against substrates containing mismatches on the 3'-side of nick junction and was more tolerant of mismatches at the 5'-end than of those at the penultimate 5'-end. The enzyme showed little activity on a 1-nucleotide gapped substrate. This is the first biochemical study of a DNA ligase from the crenarchaeotal branch of the archaea domain.

Studies on the two-photon pumped upconverted fluorescence and superradiance of a new organic dye material in solutions.

The linear and nonlinear optical properties of a new organic dye, trans-4-[p-(N-ethyl-N-ethylamino)-styryl]-N-methyl-pyridinium tris(thiocyanato) cadmates (II), are reported in this paper. When pumped with a picosecond laser at the wavelength range of 850-1200 nm, intense upconversion fluorescence can be obtained. The upconversion efficiencies at different pump energies were measured when pumped with a 1064-nm laser beam from a mode-locked Nd:YAG laser. The highest upconversion efficiencies were measured to be 5.8% and 7.6% in dimethyl formamide (DMF) and methanol. The lifetime of the dye in DMF was measured to be 75 ps. The strongest nonlinear absorption was at the wavelength of 940 nm, and the highest upconversion efficiency was at the wavelength of 1030 nm. The difference of the two wavelengths was caused by excited state absorption in the dye at wavelengths shorter than 1000 nm. The dye solution in DMF and methanol show a clear optical power limiting effect.

Cloning and expression of metallothionein mutant alpha-KKS-alpha in Anabaena sp. PCC 7120.

The mouse metallothionein (mMT) mutant alpha-KKS-alpha has a higher capacity for binding heavy metals than wild type mMT. The mMT mutant alpha-KKS-alpha gene was placed under the control of the strong promoter PpbsA to generate the intermediate vector pRL-alpha-KKS-alpha. pRLalpha-KKS-alpha was then linked with the plasmid pDC-08 to construct shuttle expression vector pDC-alphaKKS-alpha. This expression vector was transformed into Anabaena sp. PCC 7120 using triparental conjugative transfer. After antibiotic selection (ampicillin and kanamycin), transgenic Anabaena was identified by PCR and Western blotting. The expression level of the mMT mutation alpha-KKS-alpha reached 7.4 mg/g dry cells weight, as detected by ELISA, and heavy metal resistance of the transgenic Anabaena was significantly improved.

Expression, purification and activity measurement of soluble BACE protein in E.coli.

To express BACE (beta-site APP cleaving enzyme), an aspartic protease related to Alzheimer's disease in E.coli to obtain the active protein after refolding and purification, the sequence for soluble form of BACE was inserted into prokaryotic expression vector pET11a. After expression in E.coli BL21(DE3), the protein was obtained as inclusion bodies, after refolding and purification. The proteolytic activity of the protein was measured by HPLC and MS. After refolding and purification, the protein exhibited beta-secretase activity by cleaving the synthetic peptide, which was designed according to the beta-secretase site at Swedish mutant of APP, and according Hanes method the kinetics constants for the synthetic peptide of BACE protein were measured. The study will facilitate BACE protein structure determination and inhibitor development efforts, which may lead to the evolution of promising and effective treatments for Alzheimer's disease.