Simultaneous Defect Passivation and Electric Level Regulation with Rubidium Fluoride for High-Efficiency CsPbI2Br Perovskite Solar Cells.

Due to the good balance of efficiency and stability, CsPbI2Br perovskite solar cells (PSCs) recently have attracted widespread attention. However, the improvement in photovoltaic performance for CsPbI2Br PSCs was mainly limited by massive defects and unmatched energy levels. Surface modification is the most convenient and effective strategy to decrease defect densities of perovskite films. Herein, we deposited rubidium fluoride (RbF) onto the surface of CsPbI2Br perovskite films by spin-coating. The numerous defects could be significantly passivated by RbF, resulting in suppressed nonradiative recombination. Furthermore, the CsPbI2Br perovskite film after RbF treatment exhibits a deeper Fermi level, and an additional built-in electric field forms to promote charge transport. Consequently, the champion device achieves a high efficiency of 10.82% with an improved VOC of 1.14 V, and it also exhibits excellent stability after long-term storage. This work offers a simple and effective approach to enhance the photovoltaic performance and stability of PSCs for broader applications in the future.

Liquid buried interface to slide lattice and heal defects in inorganic perovskite solar cells.

The residual tensile strain, which is induced by lattice and thermal expansion coefficient difference between upper perovskite film and underlying charge transporting layer, significantly deteriorates the power conversion efficiency (PCE) and stability of a halide perovskite solar cell (PSC). To overcome this technical bottleneck, herein, we propose a universal liquid buried interface (LBI) by introducing a low melting-point small molecule to replace traditional solid-solid interface. Arising from the movability upon solid-to-liquid phase conversion, LBI plays a role of "lubricant" to effectively free the soft perovskite lattice shrinkage or expansion rather than anchoring onto the substrate, leading to the reduced defects due to the healing of strained lattice. Finally, the inorganic CsPbIBr2 PSC and CsPbI2Br cell achieve the best PCEs of 11.13 % and 14.05 %, respectively, and the photo-stability is improved by 33.3-fold because of the suppressed halide segregation. This work provides new insights on the LBI for making high-efficiency and stable PSC platforms.

In situ formation of inorganic healing overlayer for interface-stabilized all-inorganic CsPbIBr2 perovskite solar cells.

A perovskite layer functionalized to be an outermost screen can strongly affect the capacity of the underlying device to avoid becoming decomposed under external stimuli, and subsequently affect the photovoltaic performance as well. Herein, we report an interface-stabilization strategy for an all-inorganic CsPbIBr2 film involving forming in situ an inorganic ZrO2 layer to solidify the soft perovskite lattice. As a result of defect passivation and self-encapsulation, the best device achieved an enhanced efficiency of up to 10.12%, which was much higher than the 7.47% efficiency for the reference device tested, with prolonged stability under conditions of persistent light irradiation and exposure to air.

Source, Distribution, and Risk Estimation of Hazardous Elements in Farmland Soils in a Typical Alluvial-Lacustrine Transition Basin, Hunan Province.

Increased concentrations of heavy metals in soil due to anthropogenic activities pose a considerable threat to human health and require constant attention. This study investigates the spatial distribution of heavy metals (Cd, Pb, Zn, Sb) and metalloids (As) in a typical alluvial-lacustrine transition basin and calculates the bioavailable forms of elements posing a direct threat. Qualitative and quantitative methods were used to identify the sources of contaminants, after which an ecological risk assessment was conducted. Total (T) As, Pb, and Zn decreased with the depth, whereas Cd and Sb increased in surface (0-20 cm) soil. Bioavailable (Bio) Cd and Pb in the topsoil were regulated by pH and organic matter, whereas Bio-Zn was regulated by soil pH. Within deeper soil layers, the combined effects of pH, organic matter, and clay contents regulated the bio-elements. The results of multiple methods and local investigation showed that TSb (65.3%) was mainly derived from mining activities, TCd (53.2%) and TZn (53.7%) were derived from direct pollution by industrial production and agricultural fertilizers, respectively, and TA (55.6%) was mainly derived from the soil parent material. TPb was related to vehicle exhaust emissions and atmospheric deposition from industrial activities. Although the potential ecological risk in the study area remains relatively low, there is a need for continuous monitoring of the potential ecological risks of Cd and Sb. This study can act as a reference for the prevention and mitigation of heavy metal contamination of alluvial-lacustrine transition basins.

A Genetic Toxicology Study of the Rapid Detection of Nitrosamine Compounds by the rpsL Gene Mutation Assay.

In a rpsL gene mutation experiment, the mutagenicity of the nitrosamine compounds N-diethylnitrosamine (NDEA) and N-dipropylnitrosamine (NDPA) was investigated at the cellular level, as well as with PCR (polymerase chain reaction) and RCA (rolling-circle amplification) amplification systems. The experiments were set up with 10 ppm, 100 ppm, and 1000 ppm concentration gradients of NDEA and NDPA, and ethidium bromide (EB) was used as a positive control group. The results demonstrated that the mutagenic frequency of NDEA and NDPA was significantly higher than the spontaneous mutation frequency of the rpsL gene under the same conditions, but lower than the mutagenic rate of EB in the positive control, and there was a dose-effect relationship, indicating that NDEA and NDPA could induce rpsL gene mutation. The rpsL mutation system has a low spontaneous mutation background and high sensitivity, thus the system is expected to become an effective tool for the rapid detection of carcinogens in the field of food.

Universal Dynamic Liquid Interface for Healing Perovskite Solar Cells.

Healing charge-selective contact interfaces in perovskite solar cells (PSCs) highly determines the power conversion efficiency (PCE) and stability. However, the state-of-the-art strategies are often static by one-off formation of a functional interlayer, which delivers fixed interfacial properties during the subsequent operation. As a result, defects formed in-service will gradually deteriorate the photovoltaic performances. Herein, a dynamic healing interface (DHI) is presented by incorporating a low-melting-point small molecule onto perovskite film surface for highly efficient and stable PSCs. Arising from the reduced non-radiative recombination, the DHI boosts the PCE to 12.05% for an all-inorganic CsPbIBr2 solar cell and 14.14% for a CsPbI2 Br cell, as well as 23.37% for an FA0.92 MA0.08 PbI3 (FA = formamidinium, MA = methylammonium) cell. The solid-to-liquid phase conversion of DHI at elevated temperature causes a longitudinal infiltration into the bulk perovskite film to maximize the charge extraction, passivate defects at grain boundaries, and suppress ion migration. Furthermore, the stability is remarkably enhanced under air, heat, and persistent light-irradiation conditions, paving a universal strategy for advanced perovskite-based optoelectronics.

Thermal-Triggered Dynamic Disulfide Bond Self-Heals Inorganic Perovskite Solar Cells.

One great challenge for perovskite solar cells (PSCs) lies in their poor operational stability under harsh stimuli by humidity, heat, light, etc. Herein, a thermal-triggered self-healing polyurethane (PU) is tailored to simultaneously improve the efficiency and stability of inorganic CsPbIBr2 PSCs. The dynamic covalent disulfide bonds between adjacent molecule chains in PU at high temperatures self-heal the in-service formed defects within the CsPbIBr2 perovskite film. Finally, the best device free of encapsulation achieves a champion efficiency up to 10.61 % and an excellent long-term stability in an air atmosphere over 80 days and persistent heat attack (85 °C) over 35 days. Moreover, the photovoltaic performances are recovered by a simple heat treatment.

Influence of the introduction of a triphenylphosphine group on the anticancer activity of a copper complex.

Aiming at obtaining new copper complexes with good cytotoxicity against cancer cells, triphenylphosphine (TPP) was introduced to obtain insight into the influence of the co-ligands. In this paper, two copper complexes, Cu(2-pbmq)(CH3OH)Br2 (1) and [Cu(2-pbmq)(TPP)Br]2 (2) were designed, synthesized, and characterized by X-ray crystallography, 2-((2-(pyrazin-2-yl)-1H-benzo[d]imidazol-1-yl)methyl))quinolone (2-pbmq), to investigate the influence of the TPP group on the anticancer activity of the metal complex. Although the presence of the TPP group diminished the intensity of the interaction properties of the complex with DNA, the in vitro anticancer activity and cellular uptake of the TPP-containing complex were markedly superior to those of its TPP-lacking counterpart. Detailed studies on the more potently cytotoxic complex 2 revealed that it accumulated in nucleus, arrested the cell cycle at the G0-G1 phase, causing mitochondrial dysfunction, involving the potential simultaneous mitochondrial membrane collapse, cellular ATP level depletion, and Ca2+ leakage, eventually inducing cell apoptosis. In summary, the introduction of a TPP group enhances the biological activity and cytotoxicity of the complex.

Nickel complex co-catalyst confined by chitosan onto graphitic carbon nitride for efficient H2 evolution.

Developing earth-abundant H2-production heterogeneous photocatalysts with robust activity and stability has attracted great interests. Herein, a low-cost photocatalyst was prepared by binding nickel complex covalently from primary amines of chitosan (NiL) onto photosensitive carbon nitride nanosheets (CN) through electrostatic interaction. Introduction of NiL results in more efficient utilization of solar energy, photogenerated electrons' direct transfer and lower overpotential for water reduction. The optimized NiL3-CN photocatalyst shows the highest H2 evolution rate of 346 µmol g-1 h-1 under visible light irradiation and exhibits high stability during test. This work presents great potentials for sustainable conversion of solar energy, and sheds positive light on the development of heterogeneous photocatalysts via anchoring H2-evolving molecule catalysts confined by inexpensive macromolecules onto a semiconductor photosensitizer through a facile and valid method.

Chemical biology suggests pleiotropic effects for a novel hexanuclear copper(ii) complex inducing apoptosis in hepatocellular carcinoma cells.

A novel hexanuclear copper(ii)-based complex, [Cu6(tpbb)2(NO3)12] (1), was synthesized, which shows potent cytotoxicity to hepatoma carcinoma cells by inducing apoptosis and apoptosis-related processes. Furthermore, mechanistic investigations based on proteomes revealed that the induced apoptosis was mediated by acting on several targets and multiple pathways in a pleiotropic way.

Novel binuclear and trinuclear metal (II) complexes: DNA interactions and in vitro anticancer activity through apoptosis.

A water soluble trinuclear copper(II) complex and a binuclear cobalt(II) complex, namely Cu3(ppbm)2(SO4)3 (1) and Co2(ppbm)2(NO3)4 (2) (ppbm = 2-(pyridin-2-yl)-1-(pyridin-3-ylmethyl)- 1H-benzo[d]imidazole), have been successfully synthesized and characterized by elemental analysis, IR Spectroscopy, electrospray ionization mass spectra (ESI-MS). The interaction of the new complexes with DNA has been explored using spectroscopy methods, indicating that the complexes 1 and 2 bind to DNA via noncovalent interactions. DNA cleavage experiment suggested that the complex 1 exhibits efficient DNA cleavage activities in the presence of ascorbate (Asc), hydrogen peroxide may serve as the major cleavage active species. The cytotoxicity assay showed that complex 1 exhibited significant inhibitory activity toward the proliferation of several tumor cell lines, with a lower IC50 value than cisplatin and complex 2, indicating that it had the potential to act as effective anticancer agent. The morphological staining assays showed that 1 apparently induced the TFK-1 cells apoptosis. Besides, cellular uptake experiment on TFK-1 cells revealed that complex 1 accumulates primarily inside the nucleus. The apoptosis was attributable to the metal-assisted generation of reactive oxygen species (ROS).

Preparation of reduced graphene oxide nanosheet/FexOy/nitrogen-doped carbon layer aerogel as photo-Fenton catalyst with enhanced degradation activity and reusability.

In this manuscript, a novel reduced graphene oxide nanosheet/FexOy/nitrogen-doped carbon layer (rGS/FexOy/NCL) aerogel with FexOy NPs sandwiched between rGS and NCL was prepared via a two-step method. Their catalytic performance was evaluated in a photo-Fenton degradation of rhodamine B. It was found that rGS/FexOy/NCL aerogel represented higher degradation activity than the sum of rGS/NCL support and FexOy NPs, suggesting synergistic effect was established between support and reactive species. The degradation activity was investigated on the basis of aerogel usage, FexOy loading, H2O2 dosage, pH value and RhB concentration. To test stability and reusability, leaching experiments, cyclic experiments and structural analysis were carried out. Based on inhibitor experiment and intermediate detection, a possible catalytic mechanism and degradation pathway of RhB were proposed.

DNA interactions and in vitro anticancer evaluations of pyridine-benzimidazole-based Cu complexes.

Copper is an essential element and has redox potential, thus copper complexes have been developed rapidly with the hope of curing cancer. To further develop anticancer agents and investigate their anticancer mechanisms, two Cu complexes, [Cu(bpbb)0.5·Cl·SCN]·(CH3OH) (1) and [Cu2(bpbb)·Br3·(OH)] n (2), were synthesized and characterized using 4,4'-bis((2-(pyridin-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)biphenyl (bpbb), with associated Cu(ii) salts. Complex 1 is a binuclear structure, whereas 2 is a one-dimensional complex. Compared with 2, complex 1 exhibited potent in vitro cytotoxicity toward four cell lines (HCT116, BGC823, HT29, and SMMC7721), and was most effective against HCT116 cells. Therefore, further in-depth investigation was carried out using complex 1. Absorption spectral titration experiments, ethidium bromide displacement assays, and circular dichroism spectroscopic studies suggested that complex 1 binds strongly to DNA by intercalation. Complex 1 exhibited a clear concentration-dependent pBR322 DNA cleavage activity. Inductively coupled plasma mass spectrometry testing implied that complex 1 could enter cells and that DNA was one important target. Cellular level assays suggested that complex 1 activates the generation of intracellular reactive oxygen species, causing DNA damage, promoting cell cycle arrest and mitochondria dysfunction, and inducing cellular apoptosis.

In vitro antitumor activity of novel benzimidazole-based Cu(II) complexes.

Four benzimidazole-based Cu(II) complexes: Cu2(p-2-bmp)2Br4 (1), Cu2(p-2-bmp)2Cl4 (2), Cu2(p-2-bmb)2(DMF)2Br4·(CHCl3) (3), and Cu(p-2-bmb)(NO3)2·(CHCl3) (4) were isolated and characterized, where p-2-bmp is 1-((2-(pyridine-2-yl)-1H-benzoimidazol-1-yl)methyl)-1H-pyridine and p-2-bmb is 1-((2-(pyridin-2-yl)-1-benzoimidazol-1-yl)methyl)-1H-benzotriazole. Complexes 1 and 2 have binuclear configurations, 3 has a mononuclear structure, and 4has a one-dimensional (1-D) chain skeleton. To evaluate their potential anticancer effects on human carcinoma cells, anti-proliferation, DNA binding and cleavage, and apoptosis elicitation were examined. Compared with complexes 2, 3, and 4, complex 1 exhibited potent in vitro cytotoxicity toward four cell lines (MCF7, EC109, SH-SY5Y and QBC939), with SH-SY5Y cells demonstrating the most sensitivity. Therefore, further in-depth investigations were performed using complex 1. Absorption titration experiments, circular dichroism spectroscopic studies, and ethidium bromide displacement assays suggested that complex 1 binds to DNA through intercalation, significantly cleaves supercoiled pBR322 DNA, and inhibits DNA transcription. Cell cycle analysis revealed that SH-SY5Y cells were arrested in the G2/M phase after treatment with complex 1. Membrane permeability analysis and nuclear staining of SH-SY5Y cells showed that complex 1 could induce apoptosis.

One-pot preparation of ternary reduced graphene oxide nanosheets/Fe2O3/polypyrrole hydrogels as efficient Fenton catalysts.

Ternary reduced graphene oxide nanosheets (rGSs)/Fe2O3/polypyrrole (PPy) hydrogels with Fe2O3 nanoparticles (NPs) embedded between rGSs and PPy layer were prepared in one-pot. The ternary hydrogels exhibited an interconnected and porous three-dimensional network with co-existence of macropores and mesopores. Fe2O3 NPs uniformly dispersed on rGS surface with the diameter of 8.8nm. Control experiments were carried out to investigate the roles of components in formation of ternary hydrogels. During heterogeneous Fenton degradation of methylene blue (MB) dyes, the ternary hydrogels exhibited much better removal efficiency than the reference samples, not only because rGSs and PPy layer altered the adsorption, dispersity and diameter of Fe2O3 NPs; but also owing to the structural merits of ternary hydrogels. The effects of operating conditions, such as initial MB concentrations, dosages of catalysts and H2O2, were carefully investigated. With the help of Fe2O3 NPs, ternary rGSs/Fe2O3/PPy hydrogels could be easily separated via a magnet. In recycling experiments, they showed superior reusability.

Preparation of Magnetically Recyclable Yolk/Shell Fex Oy /PdPt@CeO2 Nanoreactors with Enhanced Catalytic Activity.

Noble metal nanoparticles (NPs) have recently received considerable attention from researchers working in the field of catalysis. However, the development of new methods allowing these materials to reach their maximum catalytic properties remains challenging. Nanoreactors could lead to dramatic improvements in activity with the help of the intrinsic confinement effect. In this study, we designed a series of yolk/shell Fex Oy /PdPt@CeO2 composites, where the Fex Oy NPs acted as a movable core, allowing for the uniform distribution of the PdPt alloys on the inner surface of the CeO2 shell. The high porosity and existence of hollow voids in the CeO2 shell allowed these Fex Oy /PdPt@CeO2 composites to be used as nanoreactors in catalytic reactions. As well this confinement effect, we identified two structural features that led to enhanced catalytic activity, including (i) the replacement of monometallic NPs with a bimetallic PdPt alloy and (ii) the replacement of a chemically inert support with a reactive CeO2 shell. The resulting nanoassembled catalysts displayed higher activities toward the catalytic reduction of dyes than the reference samples. Moreover, these catalysts were readily recovered and reused because of the magnetic Fex Oy core.

One-step preparation of magnetic recyclable quinary graphene hydrogels with high catalytic activity.

Metal nanoparticles (NPs) displayed overwhelming superiority in catalysis towards the corresponding bulk-phase materials; nevertheless, how to further improve catalytic activity was still an ongoing subject. Herein, we have combined one-step redox reaction and following freeze-dried technology to construct the quinary reduced graphene oxide nanosheets (rGS)/Fe2O3-PdPt/polypyrrole (PPy) hydrogels. Compared with traditional catalysts, their catalytic property was improved via two ways: construction of three-dimensional (3D) rGS hydrogels instead of two-dimensional rGS and synthesis of bimetallic alloys instead of monometallic NPs. The highly dispersed PdPt with diameter as small as 3.2nm uniformly loaded on hydrogel surface. Due to special interconnected and porous structure, the reactants were easily adsorbed in hydrogels and contacted with PdPt alloys. To explain the contributions of bimetallic alloys and 3D rGS structure on enhanced catalytic activity, the catalytic property of quinary hydrogels was compared with reference samples. Besides superior activity, they also displayed good reusability, since hydrogels could be magnetically recycled owing to the existence of Fe2O3 NPs.

Preparation of raspberry-like γ-Fe2O3/crackled nitrogen-doped carbon capsules and their application as supports to improve catalytic activity.

In this manuscript, we have introduced a novel method to improve the catalytic activity of metal nanoparticles via optimizing the support structure. To this end, raspberry-like γ-Fe2O3/crackled nitrogen-doped carbon (CNC) capsules were prepared by a two-step method. Compared with traditional magnetic capsules, in γ-Fe2O3/CNC capsules, the γ-Fe2O3 nanoparticles were embedded in a CNC shell; therefore, they neither occupied the anchoring sites for metal nanoparticles nor came into contact with them, which was beneficial for increasing the metal nanoparticle loading. Numerous tiny cracks appeared on the porous CNC shell, which effectively improved the mass diffusion and transport in catalytic reactions. Additionally, the coordination interaction could be generated between the precursor metal ions and doped-nitrogen atoms in the capsule shell. With the help of these structural merits, γ-Fe2O3/CNC capsules were ideal supports for Pd nanoparticles, because they were beneficial for improving the Pd loading, reducing the nanoparticle size, increasing their dispersity and maximizing the catalytic performance of Pd nanoparticles anchored on the inner shell surface. As expected, γ-Fe2O3/CNC@Pd catalysts exhibited a dramatically enhanced catalytic activity towards hydrophilic 4-nitrophenol and hydrophobic nitrobenzene. The reaction rate constant k was compared with recent work and the corresponding reference samples. Moreover, they could be easily recycled by using a magnet and reused without an obvious loss of catalytic activity.

A simple way to prepare reduced graphene oxide nanosheets/Fe2O3-Pd/N-doped carbon nanosheets and their application in catalysis.

The catalysts with Pd and γ-Fe2O3 nanoparticles embedded between reduced graphene oxide nanosheets (rGS) and N-doped carbon nanosheets (NCS) were prepared through a two-step method. Firstly, graphene oxide nanosheets (GS)/prussian blue (PB)-Pd/polypyrrole (PPy) composites were synthesized by using pyrrole monomer as reductant, K3Fe(CN)6 and PdCl2 as oxidants in the presence of GS via a redox reaction. Subsequently, the as-obtained GS/PB-Pd/PPy composites were calcinated in N2 atmosphere. During the heat-treatment, carbonization of PPy to NCS, conversion of nonmagnetic PB to magnetic γ-Fe2O3 nanoparticles, and reduction of GS to rGS were finished, simultaneously. rGS/Fe2O3-Pd/NCS composites exhibited good catalytic activity toward reduction of 4-nitrophenol. The rate constant k and turnover frequency were calculated and compared with recent reports. Owing to γ-Fe2O3 nanoparticles, the rGS/Fe2O3-Pd/NCS composites could be quickly separated by magnet and reused without obvious decrease in activity.

A combination system for prediction of Chinese Materia Medica properties.

Identifying and explaining the property of Chinese Materia Medica (CMM) is an important and urgent mission in recent CMM researches. In the present work, we built a combination system for predicting the cold/hot property of CMM based on chemical material basis. A novel strategy, weight center treatment, was used to solve the problem that the chemical description was unable to be applied to CMM. As the results of prediction, the accuracy of 83.3% and 81.0% for the training and the test set, respectively, indicates that this system is a useful tool to predict the property of unidentified folk herbs and foreign herbs. It will characterize these herbs with traditional Chinese medicine properties so as to design new CMM formulas for better therapeutics. Moreover, we found some interesting explanation about the property of CMM based on chemical information by using the selected descriptors. It will give new insight into the CMM property from the standpoint of chemistry.