Direct growth of orthorhombic Ta3N5-type Ta-O-N compound thin films, specifically Ta3-xN5-yOy, on Si and sapphire substrates with various atomic fractions is realized by unbalanced magnetron sputtering. Low-degree fiber-textural Ta3-xN5-yOy films were grown through reactive sputtering of Ta in a gas mixture of N-2, Ar, and O-2 with keeping a partial pressure ratio of 3:2:0.1 in a total working pressure range of 5-30 mTorr. With increasing total pressure from 5 to 30 mTorr, the atomic fraction of O in the as-grown Ta3-xN5-yOy films was found to increase from 0.02 to 0.15 while that of N and Ta decrease from 0.66 to 0.54 and 0.33 to 0.31, respectively, leading to a decrease in b lattice constant up to around 1.3%. Metallic TaNx phases were formed without oxygen. For a working pressure of 40 mTorr, an amorphous, O-rich Ta-N-O compound film with a high O fraction of similar to 0.48, was formed, mixed with non-stoichiometric TaON and Ta2O5. By analyzing the plasma discharge, the increasing O incorporation is associated with oxide formation on top of the Ta target due to a higher reactivity of Ta with O than with N. The increase of O incorporation in the films also leads to a optical bandgap widening from similar to 2.22 to similar to 2.96 eV, which is in agreement with the compositional and structural changes from a crystalline Ta3-xN5-yOy to an amorphous O-rich Ta-O-N compound.
We describe a method for magnetic solid phase extraction of trace-levels of Hg(II) ions by using Fe3O4 nanoparticles (NPs) covered with a shell of silica and modified with the chelator N-(2-acetylaminoethyl)-N-(3-triethoxysilylpropyl)thiourea. The new magnetic NPs enable rapid magnetic separation, thus leading to higher efficiency and accuracy. The extracted Hg(II) ions on the NPs were directly quantified using a mercury analyzer. Possible interferents are widely eliminated in this highly selective extraction process, and the NPs are not exerting an interfering effect either. The method has an enrichment factor of 100, and extraction recoveries are between 95 and 107 % when using 10 mg of the extracting NPs. The method works over a wide range of pH values and can be applied to even complex natural samples. The effects of pH value, extraction time, sample volume and adsorbent amount on the extraction efficiency were optimized. Under the optimal conditions, the detection limit is as low as 17 ng L-1. The method was applied to the preconcentration and detection of Hg(II) in three natural water samples using the standard addition method.
The innovative construction of bifunctional non-noble electrocatalyst for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is imperative for electrochemical water splitting. Herein, we provide a collaborative self-templating method to prepare a hybrid catalyst of nanoporous CoP nanowire (NWs) arrays decorated with carbon-coated CoP nanoparticles (NPs). Its found that the unique structure and morphology of the resultant catalyst can provide abundant available active sites and faciliatate the rapid H-2/O-2 transmission. Additionally, the N-doped carbon improves the conductivity of the catalyst and prevents the aggregation and deactivation of CoP nanoparticles. Forthermore, the strong coupling and synergistic effects by interface engineering are also conducive to the electrochemical performance. Benefiting from these advantages, the CoP NWs/CoP NPs@NC/CC only needs a low overpotential of 103 mV to achieve 10 mA cm(-2) with a small Tafel slope of 87 mV dec(-1) for HER. When employed in an electrolytic cell as an electrocatalyst for overall water splitting, a low voltage of 1.60 V is required to drive 10 mA cm(-2). This study may provide a novel way to fabricate transitionmetal-based catalysts for water splitting.
A new colorimetric and fluorogenic probe (RN3) based on rhodamine-B has been successfully designed and synthesized. It displays a selective response to Hg2+ in the aqueous buffer solution over the other competing metals. Upon addition of Hg2+, the solution of RN3 exhibits a naked eye observable color change from colorless to red and an intensive fluorescence with about 105-fold enhancement. The changes in the color and fluorescence are ascribed to the ring-opening of spirolactam in rhodamine fluorophore, which is induced by a binding of the constructed receptor to Hg2+ with the association and dissociation constants of 0.22 x 10(5) M-1 and 25.2 mM, respectively. The Jobs plot experiment determines a 1: 1 binding stoichiometry between RN3 and Hg2+. The resultant "turn-on" fluorescence in buffer solution, allows the application of a method to determine Hg2+ levels in the range of 4.0-15.0 mu M, with the limit of detection (LOD) calculated at 60.7 nM (3 sigma/slope). In addition, the fluorescence turn-off and color fading-out happen to the mixture of RN3-Hg2+ by further addition of I- or S2-. The reversible switching cycles of fluorescence intensity upon alternate additions of Hg2+ and S2- demonstrate that RN3 can perform as an INHIBIT logic gate. Furthermore, the potential of RN3 as a fluorescent probe has been demonstrated for cellular imaging. (C) 2016 Elsevier B.V. All rights reserved.
A new visible light excitable fluorescent probe (1) is synthesized by appending a hydroxymethyl-pyridine to rhodamine B hydrazide. The probe displays very specific Hg2+-induced colour change and fluorescent enhancement in the aqueous systems. The "turn-on" response of fluorescence is based on a binding-induced ring-opening process from the spirolactam (nonfluorescent) to acyclic xanthene (fluorescent) in rhodamine B. The coordinating atoms O-center dot-N-N-O-center dot from the hydroxymethyl-pyridine and rhodamine B hydrazide play dominant role in the formation of a complex with 1:1 stoichiometry of Hg2+ to 1. It exhibits a linear response in the range of 0.1-5 mu M with the limit of detection (LOD) of 15.7 nM (3 sigma/slope), while the calculated value of the association constant of Hg2+/1 is 0.70 x 10(5) M-1. Furthermore, confocal microscopy imaging experiment demonstrates the probe 1 can be applied as a fluorescent probe for visualization of Hg2+ in living HeLa cells.
We design and synthesize a new ratiometric fluorescent chemodosimeter (S1) for the selective and sensitive detection of Hg2+. Upon addition of Hg2+, the emission of the S1 exhibits a large bathochromic shift from 393 to 515 nm (up to 122 nm) which is ascribed to an intramolecular charge transfer process in the resultant. The Hg2+-induced dethioacetalization for sensing mechanism has been demonstrated by using high-performance liquid chromatography analysis of the sensing process. The interference experiments further demonstrate that S1 exhibits very high selectivity towards Hg2+ over other coexisting cations/anions. Subsequently, a good linearity of the concentrations of Hg2+ (0-15 mu M) vs the ratiometric signals (I-515/I-393) allows a fluorogenic method for the quantitative detection of Hg2+, with the limitation of detection determined to be 5.22 x 10(-7) M. (C) 2016 Elsevier B.V. All rights reserved.
By ingeniously using a (imino)coumarin-precursor, three reactive fluorogenic probes of MP, FP, and FMP have been fabricated in a single facile synthetic route. MP and FP are able to respectively act as selective "turn-on" fluorescent probes for detecting Hg2+ and F- in buffer solution via specific analyte-induced reactions. Linear ranges for the detection of Hg2+ and F- are 0-10 mu M and 0-100 mu M with the limits of detection (LODs) of 4.0 x 10(-8) M and 1.14 x 10(-6) M (3 delta/slope), respectively. FMP is able to work as a molecular "AND" logic gate-based fluorogenic probe for monitoring the coexistence of Hg2+ and F- via a multistep reaction cascade. The analytes-induced sensing mechanisms have been determined by using high-performance liquid chromatography analysis (HPLC). In addition, three probes show negligible toxicity under the experimental conditions, and are successfully used for monitoring Hg2+ and F- in living cells with good cell permeability. The success of the work demonstrates that ingenious utility of specific analyte-induced reactions and conventional concepts on the appropriate molecular scaffold can definitely deliver tailor-made probes for various intended sensing purposes. (C) 2018 Published by Elsevier B.V.
Water-dispersible and luminescent gadolinium oxide (GO) nanoparticles (NPs) were designed and synthesized for potential dual-modal biological imaging. They were obtained by capping gadolinium oxide nanoparticles with a fluorescent glycol-based conjugated carboxylate (HL). The obtained nanoparticles (GO-L) show long-term colloidal stability and intense blue fluorescence. In addition, L can sensitize the luminescence of europium(III) through the so-called antenna effect. Thus, to extend the spectral ranges of emission, europium was introduced into L-modified gadolinium oxide nanoparticles. The obtained Eu-III-doped particles (Eu:GO-L) can provide visible red emission, which is more intensive than that without L capping. The average diameter of the monodisperse modified oxide cores is about 4nm. The average hydrodynamic diameter of the L-modified nanoparticles was estimated to be about 13nm. The nanoparticles show effective longitudinal water proton relaxivity. The relaxivity values obtained for GO-L and Eu:GO-L were r(1)=6.4 and 6.3s(-1)mM(-1) with r(2)/r(1) ratios close to unity at 1.4T. Longitudinal proton relaxivities of these nanoparticles are higher than those of positive contrast agents based on gadolinium complexes such as Gd-DOTA, which are commonly used for clinical magnetic resonance imaging. Moreover, these particles are suitable for cellular imaging and show good biocompatibility.
Introduction
Ethylenediamine-grafted multiwalled carbon nanotubes (MWCNTs-EDA-I and MWCNTs-EDA-II) are optimized and employed to investigate the preconcentration of lead ions (Pb(II)) in trace level.
Results
The results show that Pb(II) can be adsorbed quantitatively on the optimized MWCNTs in the range of pH 4–7 and MWCNTs-EDA-I has a higher maximum Pb(II) adsorption capacity (157.19 mg/g) than MWCNTs-EDA-II (89.16 mg/g). The adsorbed Pb(II) can be eluted completely using 5 mL of 1 mol/L HNO3.
Discussion
A new approach using a microcolumn packed with the obtained MWCNTs-EDA-I has been developed for the preconcentration of trace amount of Pb(II). Parameters influencing the preconcentration of Pb(II), such as pH of the sample, sample volume, elution solution, and interfering ions, have been examined and optimized in detail. Under optimum experimental conditions, the limit of detection is 0.30 ng/mL with the enrichment factor of 60. The relative standard deviation (R.S.D) was 2.6% at the 20 ng/mL Pb(II) level.
Conclusion
The method has been applied for the preconcentration of trace amount of Pb(II) in environmental water samples with satisfying results.
A facile one-step Cu(I)-catalyzed "click" reaction, between a dansyl-azide and a propargyl-substituted rhodamine B hydrazide, is employed to fabricate a novel FRET ratiometric "off-on" fluorescent probe. The sensitive emission of the donor, a dansyl group, overlaps perfectly with the absorption of the acceptor, xanthene in the open-ring rhodamine. The proposed probe shows high selectivity towards Cu2+. The ratio of emission intensities at 568 and 540 nm (I-568/I-540) exhibits a drastic 28-fold enhancement upon addition of Cu2+. The probe shows an excellent linear relationship between emission ratios and the concentrations of Cu2+ from 10 to 50 mu M, with a detection limit (S/N = 3) of 0.12 mu M. The preliminary cellular studies demonstrated that the probe is cell membrane permeable and could be applied for ratiometric fluorescence imaging of intracellular Cu2+ with almost no cytotoxicity. The ingenuity of the probe design is to construct a FRET donor-acceptor interconnector and a selective receptor simultaneously by "click" reaction. The strategy was verified to have great potential for developing novel FRET probes for Cu2+.
Developing efficient and robust non-precious-metal-based catalysts to accelerate electrocatalytic reaction kinetics is crucial for electrochemical water-urea splitting. Herein, Fe-doped NiS-NiS2 heterostructured microspheres, an electrocatalyst, are synthesized via etching Prussian blue analogues following a controlled annealing treatment. The resulting microspheres are constructed by mesoporous nanoplates, granting the virtues of large surface areas, high structural void porosity, and accessible inner surface. These advantages not only provide more redox reaction centers but also strengthen structural robustness and effectively facilitate the mass diffusion and charge transport. Density functional theory simulations validate that the Fe-doping improves the conductivity of nickel sulfides, whereas the NiS-NiS2 heterojunctions induce interface charge rearrangement for optimizing the adsorption free energy of intermediates, resulting in a low overpotential and high electrocatalytic activity. Specifically, an ultralow overpotential of 270 mV at 50 mA cm(-2) for the oxygen evolution reaction (OER) is achieved. After adding 0.33 M urea into 1 M KOH, Fe-doped NiS-NiS2 obtains a strikingly reduced urea oxidation reaction potential of 1.36 V to reach 50 mA cm(-2), around 140 mV less than OER. This work provides insights into the synergistic modulation of electrocatalytic activity of non-noble catalysts for applications in energy conversion systems.
Nanoparticles exhibiting bright near-infrared (NIR) fluorescence, T-1-and T-2-weighted MR were synthesized for specific tumor imaging. Clinically used Fe3O4 nanoparticles exhibit an intrinsic dark signal (T-2-weighted MRI), which sometimes misleads clinical diagnosis. Here, for the first time we integrated ultrasmall Fe3O4 nanoparticles (2-3 nm) with an NIR emitting semiconducting polymer for both T-1-and T-2-weighted MRI as well as fluorescence imaging of tumors. Bio-functionalized multi-modality fluorescent magnetic nanoparticles (FMNPs) functionalized with folic acid exhibit bright fluorescence and high relaxation (r(1) = 7.008 mM(-1) s(-1), r(2) = 26.788 mM(-1) s(-1), r(2)/r(1) = 3.8). These FMNPs have a small average dynamic size of about 20 nm with low aggregation and long circulation time. In vitro studies revealed that FMNPs can serve as an effective fluorescent probe to achieve targeting images of human A549 lung cancer cells without obvious cytotoxicity. In vivo experimental results show that the FMNPs are able to preferentially accumulate in tumor tissues for specific fluorescence imaging, T-1-and T-2-weighted MRI.
Uniform, highly water-dispersible and ultra-small Fe3O4 nanoparticles were synthesized via a modified one-step coprecipitation approach. The prepared Fe3O4 nanoparticles not only show good magnetic properties, long-term stability in a biological environment, but also exhibit good biocompatibility in cell viability and hemolysis assay. Due to the ultra-small sized and highly water-dispersibility, they exhibit excellent relaxivity properties, the 1.7 nm sized Fe3O4 nanoparticles reveal a low r(2)/r(1) ratio of 2.03 (r(1) = 8.20 mM(-1) s(-1), r(2) = 16.67 mM(-1) s(-1)); and the 2.2 nm sized Fe3O4 nanoparticles also appear to have a low r2/r1 ratio of 4.65 (r(1) = 6.15 mM(-1) s(-1), r(2) = 28.62 mM(-1) s(-1)). This demonstrates that the proposed ultra-small Fe3O4 nanoparticles have great potential as a new type of T-1 magnetic resonance imaging contrast agents. Especially, the 2.2 nm sized Fe3O4 nanoparticles, have a competitive r(1) value and r(2) value compared to commercial contrasting agents such as Gd-DTPA (r(1) = 4.8 mM(-1) s(-1)), and SHU-555C (r(2) = 69 mM(-1) s(-1)). In vitro and in vivo imaging experiments, show that the 2.2 nm sized Fe3O4 nanoparticles exhibit great contrast enhancement, long-term circulation, and low toxicity, which enable these ultrasmall sized Fe3O4 nanoparticles to be promising as T-1 and T-2 dual contrast agents in clinical settings.
Zebrafish embryos were used to investigate the developmental effects of sulfide. Mortality, teratogenic effects, and developmental parameters of early developmental embryos were recorded. The biodistribution of sulfide in developing zebrafish embryos and larvae were measured through fluorescence imaging. The influences of sulfide on the cardiac function and development velocity of zebrafish embryos were dependent on sulfide concentration. Heart rate and development velocity increased with exposure to lower sulfide concentrations, which may be attributed to the cardioprotective properties of H2S. Meanwhile, heart rate and development velocity decreased, whereas pericardial edema, yolk sac edema, and trunk abnormalities occurred with exposure to higher sulfide concentrations. Sulfide accumulated in the blastoderm of early developmental embryos and was then transported to the yolk sac and yolk extension with the embryonic development. Finally, sulfide was transferred from the yolk to the eyes of zebrafish larvae. The details of mechanism of sulfide toxicity require further research. (C) 2016 Elsevier B.V. All rights reserved.
A major efficiency limit for solution-processed perovskite optoelectronic devices, for example light-emitting diodes, is trap-mediated non-radiative losses. Defect passivation using organic molecules has been identified as an attractive approach to tackle this issue. However, implementation of this approach has been hindered by a lack of deep understanding of how the molecular structures influence the effectiveness of passivation. We show that the so far largely ignored hydrogen bonds play a critical role in affecting the passivation. By weakening the hydrogen bonding between the passivating functional moieties and the organic cation featuring in the perovskite, we significantly enhance the interaction with defect sites and minimize non-radiative recombination losses. Consequently, we achieve exceptionally high-performance near-infrared perovskite light-emitting diodes with a record external quantum efficiency of 21.6%. In addition, our passivated perovskite light-emitting diodes maintain a high external quantum efficiency of 20.1% and a wall-plug efficiency of 11.0% at a high current density of 200 mA cm−2, making them more attractive than the most efficient organic and quantum-dot light-emitting diodes at high excitations.
The title composite was synthesized under facile conditions by hydrolysis and co-precipitation. Through comparative studies, it was found that the morphology, structure and properties were affected by hexadecyl trimethylammonium bromide (CTAB) doping. Although the surface area decreases from 53.5 to 7.5 m(2) g(-1), it was found that CTAB@BiOCl exhibits higher adsorption capacity than the isolated BiOCl, and still maintains good photocatalytic activity, which is a little worse than the isolated BiOCl has. This was caused by the lower content of BiOCl in CTAB@BiOCl, which is less than 70%. The studies show that, in high concentrations of dye-contaminated water, the composite exhibits strong adsorption capacities of 901 mg g(-1) to Congo Red (CR) and 699 mg g(-1) to Reactive Red 3 (X3B). In the low-concentration case, it is able to process photocatalysis of those dyes. In the recycling experiment, the CTAB@BiOCl composite was regenerated in situ. And CTAB in the composite was almost completely degraded after five cycles, resulting in the regenerated BiOCl. Subsequently, the surface area of the composite increases from 7.5 to 22.62 m(2) g(-1), and along with this the adsorption capacities to CR and X3B decrease obviously due to the absence of the CTAB component. In addition, the photocatalysis activity of the generated composite has been promoted to be similar to the isolated BiOCl.
Novel donor-pi-acceptor (D-pi-A) and donor-pi-acceptor-pi-donor (D-pi-A-pi-D) type pyrimidine imidazole derivatives with flexible ether chains (L1 and L2) have been efficiently synthesized through improved Knoevenagel condensation and Ullmann reactions with high yields. Based on systematic photophysical investigations and theoretical calculations, the structure-property relationships can be described as follows: (1) the linear and nonlinear optical properties of the target chromophores change regularly with increasing the number of branches and the polarity of the solvents. (2) The single-substituted chromophore L2 exhibited a remarkable negative solvato-kinetic effect, while the double-substituted chromophore L1 showed a positive solvato-kinetic effect. Significant bathochromic shifting of the emission spectra and larger Stokes shifts were observed in polar solvents. (3) The two-photon absorption (TPA) cross-section results further demonstrated that their TPA cross section values (delta) increase notably with increasing branch number, and the presence of high pi-delocalization could induce large size-scalable TPA enhancements. (4) By comprehensively considering the optical performance, cytotoxicity and solubility, L1 was identified as the better candidate for living cell (HepG2) imaging.
It is still a challenge to obtain two-photon excited fluorescent bioimaging probes with intense emission, high photo-stability and low cytotoxicity. In the present work, four Zn(II)-coordinated complexes (1-4) constructed from two novel D-A and D-p-A ligands (L-1 and L-2) are investigated both experimentally and theoretically, aiming to explore efficient two-photon probes for bioimaging. Molecular geometry optimization used for theoretical calculations is achieved using the crystallographic data. Notably, the results indicate that complexes 1 and 2 display enhanced two-photon absorption (2PA) cross sections compared to their corresponding D-A ligand (L1). Furthermore, it was found that complex 1 has the advantages of moderate 2PA cross section in the near-infrared region, longer fluorescence lifetime, higher quantum yield, good biocompatibility and enhanced two-photon excited fluorescence. Therefore, complex 1 is evaluated as a bioimaging probe for in vitro imaging of HepG2 cells, in which it is observed under a two-photon scanning microscope that complex 1 exhibits effective co-staining with endoplasmic reticulum (ER) and nuclear membrane; as well as for in vivo imaging of zebrafish larva, in which it is observed that complex 1 exhibits specificity in the intestinal system.
A series of novel D-pi-A type two-photon absorption (2PA) imidazole-pyrimidine derivatives (EX-1 similar to EX-4) have been synthesized and characterized, with EX-1 was crystallography confirmed. Based on systematic photophysical investigations, the structure property relationships can be drawn as follows: (1) Both theoretical and experimental studies indicated that the different donor groups have large influences on the optical properties. (2) The 2PA cross-section values (sigma) were obtained both by Z-Scan and two photon excited fluorescence (2PEF) measurements. 2PA cross sections show an increasing trend with increasing electron-donating strength and the number of branches. (3) Comprehensively considered the optical performance, molecular volume, cytotoxicity and solubility, EX-1 and EX-2 were identified to be the best candidates for living cells (HepG2) imaging. Moreover, the 2PA excitable features of EX-1 and EX-2 are capable of imaging in fresh mouses liver tissues with a depth of ca. 70 mu m. (C) 2015 Elsevier Ltd. All rights reserved.
Two novel NIR-region two-photon fluorescent probes CCP and COP, show strong fluorescence quenching and good ratiometric responses toward Fe3+ and Cu2+, respectively; and their two-photon fluorescence are reversible by the subsequent addition of EDTA. CCP and COP are valuable candidates for two-photon imaging in the biological transparency window. (C) 2015 Elsevier B.V. All rights reserved.
Mitophagy has a critical role in maintaining cellular homeostasis through acidic lysosomes engulfing excess or impaired mitochondria, thereby pH fluctuation is one of the most significant indicators for tracking mitophagy. Then such precise pH tracking demands the fluorogenic probe that has tailored contemporaneous features, including mitochondrial-specificity, excellent biocompatibility, wide pH-sensitive range of 8.0-4.0, and especially quantitative ability. However, available molecular probes cannot simultaneously meet all the requirements since it is extremely difficult to integrate multiple functionalities into a single molecule. To fully address this issue, we herein integrate two fluorogenic pH sensitive units, a mitochondria-specific block, cell-penetrating facilitator, and biocompatible segments into an elegant silica nano scaffold, which greatly ensures the applicability for real-time tracking of pH fluctuations in mitophagy. Most significantly, at a single wavelength excitation, the integrated pH-sensitive units have spectra-distinguishable fluorescence towards alkaline and acidic pH in a broad range that covers mitochondrial and lysosomal pH, thus enabling a ratiometric analysis of pH variations during the whole mitophagy. This work also provides constructive insights into the fabrication of advanced fluorescent nanoprobes for diverse biomedical applications.
n/a
This review highlights the recent progress of bulk and nanoscale coordination polymer (CP) materials forenergy transfer. Artificial light-harvesting materials with efficient energy transfer are practically usefulfor a variety of applications including photovoltaic, white emitting devices, and sensors. In the pastdecades CP (aka Metal-organic framework, MOF) has experienced rapid development due to a multitude of applications, including catalyst, gas storage and separations, non-linear optics, luminescence, and soon. Recent research has shown that CP is a very promising light-harvesting platform because the energytransfers can occur between different ligands, from ligand to metal centers, or from MOF skeleton to guestspecies. This review comprehensively surveyed synthetic approaches to light-harvesting CPs, and postfunctionalization. Sensing applications and achievements in energy-transfer CP nanoparticles and thinfilms were also discussed.