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Coordination geometry-induced optical imaging of <scp>l</scp> -cysteine in cancer cells using imidazopyridine-based copper( <scp>ii</scp> ) complexes
摘要： Overexpression of cysteine cathepsins proteases has been documented in a wide variety of cancers, and enhances the L-cysteine concentration in tumor cells. We report the synthesis and characterization of copper(II) complexes [Cu(L1)2(H2O)](SO3CF3)2, 1, L1 = 3-phenyl-1-(pyridin-2-yl)imidazo[1,5-a]pyridine, [Cu(L2)2(SO3CF3)]SO3CF3, 2, L2 = 3-(4-methoxyphenyl)-1-pyridin-2-yl-imidazo[1,5-a]pyridine, [Cu(L3)2(H2O)](SO3CF3)2, 3, L3 = 3-(3,4-dimethoxy-phenyl)-1-pyridin-2-yl-imidazo[1,5-a]pyridine and [Cu(L4)2(H2O)](SO3CF3)2, 4, L4 = dimethyl-[4-(1-pyridin-2-yl-imidazo[1,5-a]pyridin-3-yl)phenyl]amine as 'turn-on' optical imaging probes for L-cysteine in cancer cells. The molecular structure of complexes adopted distorted trigonal pyramidal geometry (τ, 0.68–0.87). Cu–Npy bonds (1.964–1.989 ?) were shorter than Cu–Nimi bonds (2.024–2.074 ?) for all complexes. Geometrical distortion was strongly revealed in EPR spectra, showing gk (2.26–2.28) and Ak values (139–163 × 10?4 cm?1) at 70 K. The d–d transitions appeared around 680–741 and 882–932 nm in HEPES, which supported the existence of five-coordinate geometry in solution. The Cu(II)/Cu(I) redox potential of 1 (0.221 V vs. NHE) was almost identical to that of 2 and 3 but lower than that of 4 (0.525 V vs. NHE) in HEPES buffer. The complexes were almost non-emissive in nature, but became emissive by the interaction of L-cysteine in 100% HEPES at pH 7.34 via reduction of Cu(II) to Cu(I). Among the probes, probe 2 showed selective and efficient turn-on fluorescence behavior towards L-cysteine over natural amino acids with a limit of detection of 9.9 × 10?8 M and binding constant of 2.3 × 105 M?1. The selectivity of 2 may have originated from a nearly perfect trigonal plane adopted around a copper(II) center (～120.70°), which required minimum structural change during the reduction of Cu(II) to Cu(I) while imaging Cys. The other complexes, with their distorted trigonal planes, required more reorganizational energy, which resulted in poor selectivity. Probe 2 was employed for optical imaging of L-cysteine in HeLa cells and macrophages. It exhibited brighter fluorescent images by visualizing Cys at pH 7.34 and 37 °C. It showed relatively less toxicity for these cell lines as ascertained by the MTT assay.
关键词： optical imaging,cancer cells,turn-on fluorescence,imidazopyridine,L-cysteine,Copper(II) complexes
更新于2025-11-21 11:08:12
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Spectrophotometric Characterization of Thin Copper and Gold Films Prepared by Electron Beam Evaporation: Thickness Dependence of the Drude Damping Parameter
摘要： Copper and gold films with thicknesses between approximately 10 and 60 nm have been prepared by electron beam evaporation and characterized by spectrophotometry from the near infrared up to the near ultraviolet spectral regions. From near normal incidence transmission and reflection spectra, dispersion of optical constants have been determined by means of spectra fits utilizing a merger of the Drude model and the beta-distributed oscillator model. All spectra could be fitted in the full spectral region with a total of seven dispersion parameters. The obtained Drude damping parameters shows a clear trend to increase with decreasing film thickness. This behavior is discussed in the context of additional non-optical characterization results and turned out to be consistent with a simple mean-free path theory.
关键词： optical constants,gold,copper,ultrathin metal films,thickness dependence
更新于2025-11-21 11:01:37
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Study of (AgxCu1a??x)2ZnSn(S,Se)4 monograins synthesized by molten salt method for solar cell applications
摘要： The open circuit voltage (VOC) deficit of Cu2ZnSn(S,Se)4 (CZTSSe) kesterite solar cells is higher than that of the closely related Cu(InGa)Se2 solar cells. One of the most promising strategies to overcome the large VOC deficit of kesterite solar cells is by reducing the recombination losses through appropriate cation substitution. In fact, replacing totally or partially Zn or Cu by an element with larger covalent radius one can significantly reduce the concentration of I–II antisite defects in the bulk. In this study, an investigation of the impact of partial substitution of Cu by Ag in CZTSSe solid solution monograins is presented. A detailed photoluminescence study is conducted on Ag-incorporated CZTSSe monograins and a radiative recombination model is proposed. The composition and structural quality of the monograins in dependence of the added Ag amount are characterized using Energy Dispersive X-ray Spectroscopy and X-Ray Diffraction method, respectively. The Ag-incorporated CZTSSe monograin solar cells are characterized by temperature dependent current-voltage and electron beam induced current methods. It was found, that low Ag contents (x ≤ 0.02) in CZTSSe lead to higher solar cell device efficiencies.
关键词： Copper zinc tin sulfur selenide,Monograins,Electron beam induced current,Photoluminescence,Kesterite,Cations substituation
更新于2025-11-21 10:59:37
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Demonstration of Photovoltaic Action and Enhanced Stability from a Quasi-Two-Dimensional Hybrid Organic–Inorganic Copper–Halide Material Incorporating Divalent Organic Groups
摘要： Commercialization of solar cells based on photoactive lead–halide perovskites is in-part limited by their toxicity and instability. In this study, new and related copper–halide hybrid organic–inorganic materials containing dicationic 1,6-hexanediammonium (+H3N-C6H12-NH3+) demonstrated superior stability to heat and moisture in comparison to the analogous material containing monocationic 1-propylammonium (C3H7-NH3+) in twice the stoichiometry. Electronic absorption spectra taken of the materials were consistent with an indirect optical bandgap of ~1.8 eV, making them well-suited for application as the photoactive layer in the top cell of a tandem solar cell with silicon. The best-performing single-junction solar cells containing the dicationic material as the photoactive layer exhibited an open-circuit photovoltage in excess of 400 mV and a short-circuit photocurrent density of ~30 μA/cm2. These values are similar to those reported for state-of-the-art copper–halide hybrid organic–inorganic materials containing organic monocations and motivate further research on this class of materials.
关键词： photovoltaic,two-dimensional material,dications,solar cell,copper halide,hybrid material,stability,perovskite
更新于2025-11-19 16:56:42
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Molybdenum Disulfide Catalytic Coatings via Atomic Layer Deposition for Solar Hydrogen Production from Copper Gallium Diselenide Photocathodes
摘要： We demonstrate that applying atomic layer deposition-derived molybdenum disulfide (MoS2) catalytic coatings on copper gallium diselenide (CGSe) thin film absorbers can lead to efficient wide band gap photocathodes for photoelectrochemical hydrogen production. We have prepared a device that is free of precious metals, employing a CGSe absorber and a cadmium sulfide (CdS) buffer layer, a titanium dioxide (TiO2) interfacial layer, and a MoS2 catalytic layer. The resulting MoS2/TiO2/CdS/CGSe photocathode exhibits a photocurrent onset of +0.53 V vs RHE and a saturation photocurrent density of ?10 mA cm?2, with stable operation for >5 h in acidic electrolyte. Spectroscopic investigations of this device architecture indicate that overlayer degradation occurs inhomogeneously, ultimately exposing the underlying CGSe absorber.
关键词： hydrogen evolution,molybdenum disulfide,photoelectrochemical water splitting,atomic layer deposition,copper gallium diselenide
更新于2025-11-19 16:56:35
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Au@Cu Core-Shell Nanocubes with Controllable Sizes in the Range of 20-30 nm for Applications in Catalysis and Plasmonics
摘要： Predominantly covered by a single type of {100} facets, Cu nanocubes are attractive catalytic material toward reactions such as electrochemical reduction of CO2. Here we report a seed-mediated approach to the facile synthesis of Au@Cu core-shell nanocubes with hexadecylamine and Cl- serving as capping agents toward the {100} facets of Cu and glucose as a reducing agent. The large (12%) lattice mismatch between Cu and Au led to the localized epitaxial growth of Cu shells on the Au seeds and the formation of nanocubes with randomly distributed Au cores. Compared to the same synthesis in the absence of Au seeds, the reduction of Cu(II) ions was greatly accelerated in the presence of Au seeds because of the autocatalytic surface reduction. It was also found that the structure and morphology of the products were highly dependent on the concentration of Cu(II) precursor in the reaction solution. Nanoplates rather than nanocubes were obtained when the concentration of Cu(II) precursor was reduced down to a certain level. By varying the reaction time and/or the amount of Au seeds, the size of the Au@Cu nanocubes could be tuned in a range of 20–30 nm. The as-synthesized core-shell nanocubes exhibited a strong localized surface plasmon resonance peak at 581 nm and the resonance was dominated by absorption rather than scattering. It is expected that the Au@Cu nanocubes with uniform and controllable sizes will find use in a variety of applications such as plasmonics and catalysis.
关键词： lattice mismatch,Copper nanocubes,core-shell nanocrystals,plasmonics,seed-mediated growth
更新于2025-11-19 16:56:35
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Homogeneous immunoassay for alpha-fetoprotein based on the quenching of the fluorescence of quantum dots by antibody labelled with complexed copper ion tags
摘要： A homogeneous fluorescent immunoassay is described for the determination of alpha fetoprotein (AFP) relying on the interaction between copper ion complex and quantum dots (QDs). The copper ion complex-labelled antibody can be employed as a quencher of fluorescence of QDs and capture probe of AFP in homogeneous solution. The labelled antibody is mixed with QDs to form the immune ensemble probe. Upon the addition of AFP, the labelled antibody is stripped away from QDs by antigen-antibody combination leading to the increase in the fluorescence signal. Thus, the determination of AFP can be realized by fluorometry (best measured at excitation/emission wavelengths of 360/520 nm). The fluorescence intensity shows a good linear relationship with the AFP concentration ranging from 40 to 640 ng mL?1, and the LOD is 26 ng mL?1. The proposed method provides a new approach to incorporate metal complexes into QD-based biomolecule sensing.
关键词： Stern-Volmer plot,Metal complex,DTPAA,Copper ion complex-labelled antibody,Fluorescence quenching
更新于2025-11-19 16:46:39
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Highly Photoluminescent and Stable N-Doped Carbon Dots as Nanoprobes for Hg2+ Detection
摘要： We developed a microreactor with porous copper fibers for synthesizing nitrogen-doped carbon dots (N-CDs) with a high stability and photoluminescence (PL) quantum yield (QY). By optimizing synthesis conditions, including the reaction temperature, flow rate, ethylenediamine dosage, and porosity of copper fibers, the N-CDs with a high PL QY of 73% were achieved. The PL QY of N-CDs was two times higher with copper fibers than without. The interrelations between the copper fibers with different porosities and the N-CDs were investigated using X-ray photoelectron spectroscopy (XPS) and Fourier Transform infrared spectroscopy (FTIR). The results demonstrate that the elemental contents and surface functional groups of N-CDs are significantly influenced by the porosity of copper fibers. The N-CDs can be used to effectively and selectively detect Hg2+ ions with a good linear response in the 0~50 μM Hg2+ ions concentration range, and the lowest limit of detection (LOD) is 2.54 nM, suggesting that the N-CDs have great potential for applications in the fields of environmental and hazard detection. Further studies reveal that the different d orbital energy levels of Hg2+ compared to those of other metal ions can affect the efficiency of electron transfer and thereby result in their different response in fluorescence quenching towards N-CDs.
关键词： carbon dots,microreactor,Hg2+ detection,porous copper fibers
更新于2025-11-19 16:46:39
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RbF post deposition treatment for narrow bandgap Cu(In,Ga)Se2 solar cells
摘要： Multi-junction solar cells are known to have a considerably increased efficiency potential over their typical single junction counterparts. In order to produce low cost and lightweight multi-junction devices, the availability of suitable narrow (<1.1 eV) bandgap bottom cells is paramount. A possible absorber for such a bottom cell is the Cu(In,Ga)Se2 (CIGS) compound semiconductor, one of the most efficient thin film materials to date. In this contribution we report on the RbF post deposition treatment of narrow bandgap CIGS absorbers grown with a single bandgap grading approach. We discuss the necessary deposition conditions and the observed improvements on solar cells performance. A certified record efficiency of 18.0 % for an absorber with 1.00 eV optoelectronic bandgap is presented and its suitability for perovskite/CIGS tandem devices is shown.
关键词： Post deposition treatment,Narrow bandgap,Tandem solar cells,Thin film solar cells,photovoltaics,Rubidium fluoride,Copper indium gallium selenide
更新于2025-11-14 17:28:48
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Copper-Based Volumetric Filler Dedicated for Ag Paste for Depositing the Front Electrodes by Printing on Solar Si Cells
摘要： In this work we present research results on a new paste NPCuXX (where: NP—new paste, CuXX—component, XX—a modifier consisting of Ni and other important elements) based on a copper composite (CuXX) for fabrication of front electrodes in silicon solar cells. The CuXX composite is obtained by chemical processing of copper powder particles and can be used in two ways: as an additive to commercially available paste or as a base material for a new paste, NPCuXX. The CuXX offers the possibility to exchange up to 30 and 50 wt.% Ag into Cu, which significantly decreases the solar cells material costs, and therefore, the overall solar cell price. Emphasis was placed on a proper mass suitable fabrication process of the CuXX component. The NPCuXX paste has been applied both to conventional cell structures such as aluminum-back surface field (Al-BSF) and passivated emitter and rear contact (PERC), and finally solar cells with front electrodes deposited by screen-printing method were fabricated and characterized by current-voltage techniques. This paper reports the first implementation of the copper volumetric material into a screen print paste used in a high-temperature metallization process to fabricate the front contacts of Si solar cells with a highest fill factor of 77.92 and 77.69% for the abovementioned structures, respectively.
关键词： crystalline silicon solar cells,front electrode,copper-based volumetric filler
更新于2025-11-14 17:04:02