Construction of porphyrinic manganese-organic frameworks based on structural regulation for electrochemical determination of nitrobenzene in water and vegetable samples.

Nitrobenzene (NB) is one of the major organic pollutants that has seriously endangered human health and the environment even in trace amounts. Therefore, it is of great significance to detect trace NB efficiently and sensitively. Herein, a porphyrinic metal-organic framework (MOF) of Mn-PCN-222 (PCN, porous coordination network) was first synthesized by the coordination between Zr6 cluster and tetrakis (4-carboxyphenyl)-porphyrin-Mn (Ⅲ) (MnTCPPCl) ligand. To regulate its structure and the electrochemical properties, a phenyl group was inserted in each branched chain of TCPP to form the TCBPP organic ligand. Then, we used Zr6 clusters and manganese metalloporphyrin (MnTCBPPCl) to synthesize a new porphyrin-based MOF (Mn-CPM-99, CPM, crystalline porous material). Due to the extended chains of TCPP, the rod-shaped structure of Mn-PCN-222 was switched to concave quadrangular bipyramid of Mn-CPM-99. Mn-CPM-99 exhibited higher porosity, larger specific surface area, better electrochemical performances than those of Mn-PCN-222. By using modular assembly technique, Mn-CPM-99 film was sequentially assembled on the surface of indium-tin-oxide (ITO) to prepare an electrochemical sensor (Mn-CPM-99/ITO). The proposed sensor showed excellent electrochemical reduction of NB and displayed three linear response ranges in the wide concentration ranges. The obtained low limit of detection (LOD, 1.3 nM), high sensitivity and selectivity, and good reproducibility of the sensor for NB detection fully illustrate that Mn-CPM-99 is an excellent candidate for electrochemical sensor interface material. Moreover, the sensor was successfully applied to the detection of NB in lake water and vegetable samples showing satisfactory recovery of 98.9%-101.8%.

Aggregation-induced emission activity of sensor TBM-C1 hybrid of methoxy-triphenylamine (OMe-TPA) and dicyanovinyl for cyanide detection in aqueous THF: Mechanistic insights and potential applications.

A series fluorescent probes (TBM-Cx (x = 1, 4, 8)) were designed based on embedding various alkoxy chains on the electron donor of triphenylamine (TPA)-based dicyanovinyl (MT) compound with an electron-deficient benzothiadiazole (BTD) for sensitive, selective, and visualizing detection of cyanide in aqueous solution. Due to the nucleophilic addition of CN-, the intramolecular charge transfer (ICT) of these probes was inhibited by the destroyed conjugated structure, exhibiting excellent "turn-on" fluorescence response toward cyanide anion (CN-) in tetrahydrofuran (THF). However, the alkoxy chains with different lengths embedded in TPA not only enhance the sensitivity and solubility, but also regulate the emission behavior from ICT to aggregation-induced emission (AIE) characteristics. The binding mechanism and AIE sensing performances between the probes and CN- have been investigated and compared in THF/water mixture by spectral tools and theoretical calculations. The results showed that the ICT-based TBM-C1 probe with methoxy chain showed significantly turn-on fluorescence response to CN- as low as 0.077 µM in THF/water solution at high water fraction (90 %). Due to the AIE sensing process, TBM-C1 was successfully employed to determine CN- in food and water samples, image CN- in living cells and BALB/c mice, and prepare test kits for visualizing cyanide.

Bioimaging and detecting endogenous and exogenous cyanide in foods, living cells and mice based on a turn-on mitochondria-targeted fluorescent probe.

A novel fluorescent probe, with advanced features including "turn-on" fluorescence response, high sensitivity, good compatibility, and mitochondria-targeting function, has been synthesized based on structural design for detecting and visualizing cyanide in foods and biological systems. An electron-donating triphenylamine group (TPA) was employed as the fluorescent and an electron-accepting 4-methyl-N-methyl-pyridinium iodide (Py) moiety was used as a mitochondria-targeted localization unit, which formed intramolecular charge transfer (ICT) system. The "turn-on" fluorescence response of the probe (TPA-BTD-Py, TBP) toward cyanide is attributed two reasons, one is the insertion of an electron-deficient benzothiadiazole (BTD) group into the conjugated system between TPA and Py, and the other is the inhibition of ICT induced by the nucleophilic addition of CN-. Two active sites for reacting with CN- were involved in TBP molecule and high response sensitivity were observed in tetrahydrofuran solvent containing 3 % H2O. The response time could be reduced to 150 s, the linear range was 0.25-50 µM, and the limit of detection was 0.046 µM for CN- analysis. The TBP probe was successfully applied to the detection of cyanide in food samples prepared in aqueous solution, including the sprouting potato, bitter almond, cassava, and apple seeds. Furthermore, TBP exhibited low cytotoxicity, clear mitochondria-localizing capability in HeLa cells and excellent fluorescence imaging of exogenous and endogenous CN- in living PC12 cells. Moreover, exogenous CN- with intraperitoneal injection in nude mice could be well monitored visually by the "turn-on" fluorescence. Therefore, the strategy based on structural design provided good prospects for optimizing fluorescent probes.

Switching to a "turn-on" fluorescent probe for selective monitoring of cyanide in food samples and living systems.

A fluorescent probe (TPA-BTD-MT) was designed to monitor cyanide ions (CN-) with a "turn-on" response, changing from "turn-off" behavior due to the structural change. TPA-BTD-MT exhibited high selectivity for sensing CN- in several food samples and was successfully used for imaging CN- in living cells and animals with strong "turn-on" fluorescence.

Insights into the binding behavior of bovine serum albumin to black carbon nanoparticles and induced cytotoxicity.

Black carbon (BC) is a main component of particulate matter (PM2.5). Due to their small size (<100nm), inhaled ultrafine BC nanoparticles may penetrate the lung alveoli, where they interact with surfactant proteins and lipids, causing more serious damage to human health. Here, BC was analyzed to investigate the binding mechanism of its interaction with protein and induction of cytotoxicity changes. The binding process and protein conformation between BC and a serum protein (bovine serum albumin, BSA) were monitored by using a fluorescence quenching technique and UV-vis absorption, Fourier transform infrared (FTIR) and circular dichroism (CD) spectroscopies. The experimental results revealed that the fluorescence quenching of BSA induced by BC was a static quenching process and the hydrophobic force played the critical role in the interaction. The native conformation of BSA on the BC surface was slightly disturbed but obvious structural unfolding of the secondary structure did not occur. In the cytotoxicity study, BC nanoparticles with low concentrations exhibited strong toxicity towards BEAS-2B cells. However, the toxicity of BC nanoparticles could be mitigated by the presence of BSA. Therefore, proteins in biological fluids likely reduce the toxic effect of BC on human health. These findings delineated the binding mechanism and the toxicity between BC and the BSA-BC system, contributing to the understanding of the biological effects of BC exposure on human health in polluted atmospheres.

Adding a Feature: Can a Pop-Up Chat Box Enhance Virtual Reference Services?

Online users seek help from virtual reference services via email, phone, texting, and live chat. Technologies have enabled new features in library websites to help make this service more accessible and effective. This article is an evaluation of an experimental pop-up live chat box on the website of a health sciences library to see whether the feature would enhance virtual reference services.

Zinc porphyrin-fullerene derivative noncovalently functionalized graphene hybrid as interfacial material for electrocatalytic application.

In this paper, a p-methoxy zinc porphyrin-fullerene derivative (ZnPp-C60) noncovalently functionalized electrochemically reduced graphene oxide (ERGO) hybrid (ERGO@ZnPp-C60) was facilely obtained by π-π stacking interaction between zinc porphyrin ring and ERGO. The hybrid was characterized by scanning electron microscope (SEM), electrochemistry, UV-vis spectra, and density functional theory (DFT), which demonstrated that the presence of ERGO caused more redox reversibility and higher electrocatalytic activity of ZnPp-C60. By using their synergistic effects of the remarkable mechanical, electrical, catalytic, and structural properties, ERGO@ZnPp-C60 incorporated in tetraoctylammonium bromide (TOAB) film was modified on the glassy carbon electrode (GCE) to construct a novel non-enzymatic electrochemical sensor. The sensor exhibited enhancing response sensitivity for the electrocatalyic reduction of hydrogen peroxide with a high sensitivity of 451.3µAmM(-1) and a limit of detection (LOD) as low as 0.27µM. The sensitivity is 2-fold larger than that of TOAB/ZnPp-C60/GCE in the absence of ERGO. Although a high detecting sensitivity of 162.5µAmM(-1) for electrocatalytic oxidation of nitrite could be also obtained on the presented sensor, the sensitivity is lower than that of TOAB/ZnPp-C60/GCE (233.9µAmM(-1)) due to the change in the structure of ZnPp-C60 and the electronic interactions between GO and ZnPp-C60. Even though, the smart hybrid (ERGO@ZnPp-C60) possesses obvious advantage for the fabrication of non-enzymatic electrochemical sensor and paves a new avenue for constructing C60 derivative and graphene based materials.

Content Analysis of Virtual Reference Data: Reshaping Library Website Design.

An academic health sciences library wanted to redesign its website to provide better access to health information in the community. Virtual reference data were used to provide information about user searching behavior. This study analyzed three years (2012-2014) of virtual reference data, including e-mail questions, text messaging, and live chat transcripts, to evaluate the library website for redesigning, especially in areas such as the home page, patrons' terminology, and issues prompting patrons to ask for help. A coding system based on information links in the current library website was created to analyze the data.

Effect of the co-sensitization sequence on the performance of dye-sensitized solar cells with porphyrin and organic dyes.

To obtain a broad spectral response in the visible region, TiO2 film is co-sensitized with a porphyrin dye (FNE57 or FNE59) and an organic dye (FNE46). It is found that the stepwise co-sensitization in one single dye solution followed by in another single dye solution is better than the co-sensitization in a cocktail solution in terms of photovoltaic performance. The stepwise co-sensitization first with a porphyrin dye and then with an organic dye outperforms that in a reverse order. DSSC devices based on co-sensitizers FNE57 + FNE46 and FNE59 + FNE46 with a quasi-solid-state gel electrolyte generate power conversion efficiencies of 7.88% and 8.14%, respectively, which exhibits remarkable efficiency improvements of 61% and 35%, as compared with devices sensitized with the porphyrin dyes FNE57 and FNE59, respectively. Co-sensitization brings about a much improved short-circuit photocurrent due to the complementary absorption of the two sensitizers. The observed enhancement of incident monochromatic photon-to-electron conversion efficiency from individual dye sensitization to co-sensitization is attributed to the improved charge collection efficiency rather than to the light harvesting efficiency. Interestingly, the open-circuit photovoltage for the co-sensitization system comes between the higher voltage for the porphyrin dye (FNE57 or FNE59) and the lower voltage for the organic dye (FNE46), which is well correlated with their electron lifetimes. This finding indicates that not only the spectral complementation but also the electron lifetime should be considered to select dyes for co-sensitization.

[The Latest Research Progress of Coupling between BiOX and Semiconductor Photocatalyst].

The heterojunction was formed between two kinds of coupling semiconductors , which improved the charge separation efficiency of system, widened the spectral response range of catalysts and improved photocatalytic propertirs of catalysts. The process of preparation of semiconductors coupling was easily affected by preparation methods and reaction temperature and so on, which would cause the changes in crystal structure and surface properties of coupling semiconductors, thus photocatalytic quantum efficiency of coupling semiconductors was increased. In this article, the following three aspects were mainly discussed. (1) About the coupled system of halogen bismuth oxide and oxide, because generaling BiOX with the semiconductor material compound, the efficient heterojunction structure could be formed, photocatalytic performances of the photocatalytic degradation of pollutants were improved. (2) About the coupled system of AgX and BiOX, compared with the pure AgI or BiOI, composite photocatalytic materials of AgI/BiOI had higher photocatalytic reactivity in visible light. (3) About the coupled system of halogen bismuth oxide and other compounds, after Bi2S3 coupled with BiOX, photoproduction electronic migrated in the two kinds of catalysts, the separation efficiency of electrons and holes was improved, and photocatalytic performances of coupling compound were improved. In addition, in recent years, the latest research progress of the preparation method, the influencing factors of the photocatalytic performance and improving the utilization efficiency of visible light of semiconductors coupling at home and abroad was reviewed in this paper. Finally, the main problems and the future striving direction in semiconductors coupling were presented.

[A Study on Preparation and Photocatalytic Activity of Mn-BiOCl].

Using Bi2O3 and MnC2 x 4H2O as raw materials, with HCl as solvent, photocatalysts of Mn-BiOCl with different molar ratio of Mn and Bi were prepared by a hydrolysis method. The obtained samples were characterized by XRD, HRTEM, TEM, UV-Vis DRS and SPS. The UV light photocatalytic activity of Mn-BiOCl was evaluated by using methyl orange as model compounds of photocatalytic reaction. The active species in the degradation process of methyl orange were studied. The results show that the Mn content of Mn-BiOCl photocatalysts has an important effect on the catalytic activity. When the molar ratio of Mn and Bi is 0.25%, the as-prepared Mn-BiOCl photocatalyst has the highest catalytic activity toward the degradation of methyl orange. Photocatalytic degradation rate of methyl orange can reach 95.1%.

[Porphyrins with different electron groups: spectral and DFT study].

UV-Vis absorption spectra and electrochemical properties of 5-(o-hydroxyphenyl)-10, 15, 20-tri-(p-phenyl)porphyrin (TPPOH) and 5-(o-hydroxyphenyl)-10, 15, 20-tri-(p-methoxyphenyl) porphyrin [(p-OCH3)TPPOH] with different electron groups were investigated by experiments and density functional theory (DFT). Due to the introduction of para-methoxyl group (-OCH3), obvious red shift of 3 nm in the maximum absorbance of the UV-Vis spectra, negative shift in redox potential of (p-OCH3)TPPOH, and the decrease (0.06 eV) in the energy gap (DE) of the frontier highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) (of (p-OCH3)TPPOH occurred as compared to those of TPPOH. The results are due to that electron donating groups of -OCH3 increase the electron density of porphyrin ring in (p-OCH3)TPPOH. Electron distributions of the frontier orbital calculated by DFT showed that the increase in the energy levels of HOMO and LUMO, while the decrease of 0.05 eV in the energy gap. The agreement between experimental result and theoretical value and the further illustration of the mechanism for the spectral change and electrochemical properties provide important bases for the design and application of the porphyrin derivatives with different electron groups.

Controlling the charge transfer in D-A-D chromophores based on pyrazine derivatives.

A series of symmetrical donor-acceptor-donor (D-A-D) chromophores bearing various electron-withdrawing groups, such as quinoxaline (Qx), benzo[g]quinoxaline (BQ), phenazine (Pz), benzo[b]phenazine (BP), thieno[3,4-b]pyrazine (TP), and thieno[3,4-b]quinoxaline (TQ), has been designed and synthesized. Intramolecular charge transfer (ICT) interactions can be found for all the chromophores due to the electron-withdrawing properties of the two imine nitrogens in the pyrazine ring and the electron-donating properties of the other two amine nitrogens in the two triphenylamines. Upon the fusion of either benzene or thiophene ring on the pyrazine acceptor unit, the ICT interactions are strengthened, which results in the bathochromically shifted ICT band. Moreover, the thiophene ring is superior to the benzene ring in enlarging the ICT interaction and expanding the absorption spectrum. Typically, when a thiophene ring is fused on the Qx unit in DQxD, a near-infrared dye is realized in simple chromophore DTQD, which displays the maximum absorption wavelength at 716 nm with the threshold over 900 nm. This is probably due to the enhanced charge density on the acceptor moiety and better orbital overlap, as revealed by theoretical calculation. These results suggest that extending the conjugation of a pyrazine acceptor in an orthogonal direction to the D-A-D backbone can dramatically improve the ICT interactions.

Construction of a zinc porphyrin-fullerene-derivative based nonenzymatic electrochemical sensor for sensitive sensing of hydrogen peroxide and nitrite.

Enzymatic sensors possess high selectivity but suffer from some limitations such as instability, complicated modified procedure, and critical environmental factors, which stimulate the development of more sensitive and stable nonenzymatic electrochemical sensors. Herein, a novel nonenzymatic electrochemical sensor is proposed based on a new zinc porphyrin-fullerene (C60) derivative (ZnP-C60), which was designed and synthesized according to the conformational calculations and the electronic structures of two typical ZnP-C60 derivatives of para-ZnP-C60 (ZnP(p)-C60) and ortho-ZnP-C60 (ZnP(o)-C60). The two derivatives were first investigated by density functional theory (DFT) and ZnP(p)-C60 with a bent conformation was verified to possess a smaller energy gap and better electron-transport ability. Then ZnP(p)-C60 was entrapped in tetraoctylammonium bromide (TOAB) film and modified on glassy carbon electrode (TOAB/ZnP(p)-C60/GCE). The TOAB/ZnP(p)-C60/GCE showed four well-defined quasi-reversible redox couples with extremely fast direct electron transfer and excellent nonenzymatic sensing ability. The electrocatalytic reduction of H2O2 showed a wide linear range from 0.035 to 3.40 mM, with a high sensitivity of 215.6 µA mM(-1) and a limit of detection (LOD) as low as 0.81 µM. The electrocatalytic oxidation of nitrite showed a linear range from 2.0 µM to 0.164 mM, with a sensitivity of 249.9 µA mM(-1) and a LOD down to 1.44 µM. Moreover, the TOAB/ZnP(p)-C60/GCE showed excellent stability and reproducibility, and good testing recoveries for analysis of the nitrite levels of river water and rainwater. The ZnP(p)-C60 can be used as a novel material for the fabrication of nonenzymatic electrochemical sensors.

Investigation of electrocatalytic pathway for hemoglobin toward nitric oxide by electrochemical approach based on protein controllable unfolding and in-situ reaction.

An electrochemical approach based on protein controllable unfolding was developed and applied in combination with in-situ reaction in order to investigate the electrocatalytic pathway for hemoglobin (Hb) toward nitric oxide (NO). Hb was entrapped in a dimethyldidodecylammonium bromide (DDAB) film modified glassy carbon electrode (DDAB/Hb/GCE). Two typical denaturants of acid and urea were synergistically utilized to control the incorporated Hb to a most unfolded state without losing heme groups. Under optimal conditions, the unfolded DDAB/Hb/GCE exhibited accelerated direct electron transfer. The sensitivities for the detection of ascorbic acid (AA), NaNO(2) and NO were improved as 3, 10 and 12 times higher than those on the native DDAB/Hb/GCE, and the limits of detection (LODs) for AA, NaNO(2) and NO were down to 0.33, 0.83 and 0.063 µM, respectively. The unfolded DDAB/Hb/GCE was further applied for the investigation of Hb-NO interaction in NaNO(2) solution. With successive additions of AA, NO was generated in situ on DDAB/Hb/GCE. A new reduction peak of the intermediate HbFe(II)-HN(2)O(2) was successfully revealed near -0.65 V. The whole electrocatalytic mechanism was proposed and verified by density functional theory. The method can be a promising platform for facile study of the interaction between NO and heme proteins.

A triphenylamine-grafted imidazo[4,5-f][1,10]phenanthroline ruthenium(II) complex: acid-base and photoelectric properties.

A new heteroleptic ruthenium(II) complex of [Ru(Hipdpa)(Hdcbpy)(NCS)(2)](-).0.5H(+).0.5[N(C(4)H(9))(4)](+) Ru(Hipdpa) {where Hdcbpy = monodeprotonated 4,4'-dicarboxy-2,2'-bipyridine and Hipdpa = 4-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-N,N-diphenylaniline} was synthesized and characterized by elementary analysis, standard spectroscopy techniques, and cyclic voltammetry. The ground- and excited-state acid-base properties of Ru(Hipdpa) were studied by means of UV-vis absorption spectrophotometric and spectrofluorimetric titrations in 4:1(v/v) Britton-Robinson/dimethylformamide buffer solution. The four-step separate protonation/deprotonation processes were found in the ground states, and one of which taking place near the physiological pH range. The two observable excited-state protonation/deprotonation processes were found for the Ru(Hipdpa), constituting pH-induced "off-on-off" emission switches. The performance of the complexes as photosensitizers in nanocrystalline TiO(2)-based liquid solar cells containing an electrolyte solution (0.05 M I(2), 0.5 M LiI, and 0.5 M 4-tert-butylpyridine in 50% acetonitrile and 50% propylene carbonate) was investigated and found to achieve a much improved device performance (a short-circuit photocurrent density of 18.7 mA cm(-2), an open-circuit voltage of 630 mV, and an overall conversion efficiency of 6.85%) compared to a triphenylamine-free parent complex [Ru(Hpip)(Hdcbpy)(NCS)(2)](-).[N(C(4)H(9))(4)](+)-based device {Hpip = 2-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline} and a comparable performance to that of cis-bis(isothiocyanato)bis(2,2'-bipyridine-4,4'-dicarboxylic acid)ruthenium(II) (N3) under identical experimental conditions. A density functional theory calculation of the molecular structures and electronic properties of the complexes was also carried out in an effort to understand their effectiveness in TiO(2)-based solar cells.