Light-Quality-Adapted Carotenoid Photoprotection in the Photosystem of Roseiflexus castenholzii.

The photosystem of filamentous anoxygenic phototroph Roseiflexus (Rfl.) castenholzii comprises a light-harvesting (LH) complex encircling a reaction center (RC), which intensely absorbs blue-green light by carotenoid (Car) and near-infrared light by bacteriochlorophyll (BChl). To explore the influence of light quality (color) on the photosynthetic activity, we compared the pigment compositions and triplet excitation dynamics of the LH-RCs from Rfl. castenholzii was adapted to blue-green light (bg-LH-RC) and to near-infrared light (nir-LH-RC). Both LH-RCs bind γ-carotene derivatives; however, compared to that of nir-LH-RC (12%), bg-LH-RC contains substantially higher keto-γ-carotene content (43%) and shows considerably faster BChl-to-Car triplet excitation transfer (10.9 ns vs 15.0 ns). For bg-LH-RC, but not nir-LH-RC, selective photoexcitation of Car and the 800 nm-absorbing BChl led to Car-to-Car triplet transfer and BChl-Car singlet fission reactions, respectively. The unique excitation dynamics of bg-LH-RC enhances its photoprotection, which is crucial for the survival of aquatic anoxygenic phototrophs from photooxidative stress.

Perovskite Solar Cell Performance Boosted by Regulating the Ion Migration and Charge Transport Dynamics via Dual-Interface Modification of Electron Transport Layer.

Engineering the buried interfaces of perovskite solar cells (PSCs) is crucial for optimizing the device performance. We herein report a novel strategy by modifying the ETL-FTO interface with MgO, as well as the interface between the perovskite layer (PVKL) and the SnO2 electron transfer layer (ETL) with formamidine bromide (FABr). The dual-interface ETL engineering substantially improved the photoelectric conversion efficiency (19.62 → 22.04%) and suppressed the hysteresis index (14.98 → 1.09%). The structure-activity relationship was explored by using transient photoelectric and time-of-flight secondary-ion mass spectroscopic analyses. It was found that the FABr treatment enhanced the PVKL crystallinity and the PVKL-ETL interaction and that the MgO modification dramatically retarded the ion migration, which together optimized the ETL function. The mechanism underlying the influence of ion distribution on the dynamics of ions and free carriers is discussed, which may be helpful for the rational design of high-performance PSCs.

Influence of Two- and Three-Dimensional Engineering on the Trap State Distribution and Photophysical Properties of Lead Halide Perovskite Polycrystals.

Constructing a two- and three-dimensional (2D/3D) heterojunction structure on the surface of a 3D perovskite film, termed 2D/3D engineering, is effective in elevating the stability of perovskite polycrystal-based photovoltaic and photoelectronic devices; however, it remains controversial whether this protocol is favorable or detrimental to the device performance. Here, we prepare a series of 2D/3D perovskite films by post-treating the perovskite polycrystalline film with different concentrations of phenethylammonium iodide (PEAI). Systematic spectroscopy and electrochemical studies illustrate that PEAI can penetrate the 3D perovskite network and eliminate the intrinsic trap states of perovskite polycrystals, while the 2D perovskite nanosheets enriched on the top of the polycrystalline film may introduce additional trap states, which manipulate the photoluminescence performance and dynamics of the as-prepared perovskite films in an opposite manner. Based on this finding, the strategy of optimizing the photophysical properties of the host 3D perovskite through 2D/3D engineering is elaborated, paving the way for fabricating high-performance and high-stability perovskite polycrystalline films.

Mesoporous TiO2 layer suppresses ion accumulation in perovskite solar cells.

Ion accumulation in perovskite solar cells can be highly suppressed by a mesoporous TiO2 layer. This is evidenced by the decrease of the ion-related electrostatic potential with increasing the thickness of the mesoporous layer, accounted for by the electron population in the shallow trap states of the TiO2 nanocrystals.

Abnormalities of bone marrow B cells and plasma cells in primary immune thrombocytopenia.

Primary immune thrombocytopenia (ITP) is an autoantibody-mediated hemorrhagic disorder in which B cells play an essential role. Previous studies have focused on peripheral blood (PB), but B cells in bone marrow (BM) have not been well characterized. We aimed to explore the profile of B-cell subsets and their cytokine environments in the BM of patients with ITP to further clarify the pathogenesis of the disease. B-cell subpopulations and their cytokine/chemokine receptors were detected by using flow cytometry. Plasma concentrations of cytokines/chemokines were measured by using enzyme-linked immunosorbent assay. Messenger RNA levels of B cell-related transcription factors were determined by using quantitative polymerase chain reaction. Regulatory B cell (Breg) function was assessed by quantifying their inhibitory effects on monocytes and T cells in vitro. Decreased proportions of total B cells, naive B cells, and defective Bregs were observed in patients with ITP compared with healthy controls (HCs), whereas an elevated frequency of long-lived plasma cells was found in BM of autoantibody-positive patients. No statistical difference was observed in plasmablasts or in short-lived plasma cells between patients with ITP and HCs. The immunosuppressive capacity of BM Bregs from patients with ITP was considerably weaker than HCs. An in vivo study using an active ITP murine model revealed that Breg transfusion could significantly alleviate thrombocytopenia. Moreover, overactivation of CXCL13-CXCR5 and BAFF/APRIL systems were found in ITP patient BM. Taken together, B-cell subsets in BM were skewed toward a proinflammatory profile in patients with ITP, suggesting the involvement of dysregulated BM B cells in the development of the disease.

Lewis Base-Mediated Perovskite Crystallization as Revealed by In Situ, Real-Time Optical Absorption Spectroscopy.

The strategy of Lewis base modification has been shown to be rather effective in fabricating high-quality perovskite crystals; however, the underlying mechanisms remain controversial owing to the lack of any systematic characterization of the crystallization process. Herein, we report a novel non-invasive optical technique, termed vertical reflection-type in situ, real-time absorption spectroscopy, to investigate the mechanisms of Lewis base-mediated optimization of perovskite crystallinity by visualizing the entire energetic landscape of crystal growth. We show that by virtue of the urea additive, a prototypical Lewis base, the growth kinetics is accelerated prominently by decreasing the activation energy from 73.7 to 41.7 kJ/mol. In addition, the self-passivation of structural disorder during thermal annealing is identified, which is shown to be further strengthened by urea modification toward a shallower distribution of trap states.

Influence of the MACl additive on grain boundaries, trap-state properties, and charge dynamics in perovskite solar cells.

Grain boundary trap passivation in perovskite films has become one of the most effective strategies for suppressing the charge recombination and enhancing the photovoltaic performance of perovskite solar cells, whereas the relevant trap-state properties and the charge carrier dynamics need to be further clarified. In this work, the CH3NH3Cl (MACl) additive is introduced into the MAI:PbI2 precursor solution to obtain perovskite films comprising various grain sizes with distinct grain boundaries and trap-state properties. The influence of grain boundary traps passivated with the MACl additive on trap-state properties and charge carrier transport/recombination dynamics is systematically studied with time-resolved spectroscopic and transient photoelectric characterization. Specifically, the MACl amount determines the content of the PbI2 residual in the final perovskite, leading to photoluminescence quenching induced by charge transfer. The trap-state distribution result reveals that the deep-level traps at the grain boundaries as the main sources of charge recombination centers are dramatically passivated. Low-temperature photoluminescence spectroscopy distinguishes and compares the trap-state emission related to different perovskite phases. Transient photoelectric measurements including photovoltage decay and charge extraction further demonstrate that the boundary trap passivation can effectively promote charge transport and inhibit charge recombination in devices treated with the optimized MACl amount. As a result, the corresponding device possesses superior photovoltaic parameters to the control device. This work proposes a systematic understanding of the grain boundary trap passivation strategy and provides a new insight into the development of high-performance perovskite solar cells.

Roles of cell fusion between mesenchymal stromal/stem cells and malignant cells in tumor growth and metastasis.

Invasion and metastasis are the basic characteristics and important markers of malignant tumors, which are also the main cause of death in cancer patients. Epithelial-mesenchymal transition (EMT) is recognized as the first step of tumor invasion and metastasis. Many studies have demonstrated that cell fusion is a common phenomenon and plays a critical role in cancer development and progression. At present, cancer stem cell fusion has been considered as a new mechanism of cancer metastasis. Mesenchymal stromal/stem cell (MSC) is a kind of adult stem cells with high self-renewal ability and multidifferentiation potential, which is used as a very promising fusogenic candidate in the tumor microenvironment and has a crucial role in cancer progression. Many research results have shown that MSCs are involved in the regulation of tumor growth and metastasis through cell fusion. However, the role of cell fusion between MSCs and malignant cells in tumor growth and metastasis is still controversial. Several studies have demonstrated that MSCs can enhance malignant characteristics, promoting tumor growth and metastasis by fusing with malignant cells, while other conflicting reports believe that MSCs can reduce tumorigenicity upon fusion with malignant cells. In this review, we summarize the recent research on cell fusion events between MSCs and malignant cells in tumor growth and metastasis. The elucidation of the molecular mechanisms between MSC fusion and tumor metastasis may provide an effective strategy for tumor biotherapy.

Kisspeptin-Activated Autophagy Independently Suppresses Non-Glucose-Stimulated Insulin Secretion from Pancreatic ß-Cells.

Previous studies have demonstrated the important role of kisspeptin in impaired glucose-stimulated insulin secretion (GSIS). In addition, it was reported that the activation of autophagy in pancreatic ß-cells decreases insulin secretion by selectively degrading insulin granules. However, it is currently unknown whether kisspeptin suppresses GSIS in ß-cells by activating autophagy. To investigate the involvement of autophagy in kisspeptin-regulated insulin secretion, we overexpressed Kiss1 in NIT-1 cells to mimic the long-term exposure of pancreatic ß-cells to kisspeptin during type 2 diabetes (T2D). Interestingly, our data showed that although kisspeptin potently decreases the intracellular proinsulin and insulin ((pro)insulin) content and insulin secretion of NIT-1 cells, autophagy inhibition using bafilomycin A1 and Atg5 siRNAs only rescues basal insulin secretion, not kisspeptin-impaired GSIS. We also generated a novel in vivo model to investigate the long-term exposure of kisspeptin by osmotic pump. The in vivo data demonstrated that kisspeptin lowers GSIS and (pro)insulin levels and also activated pancreatic autophagy in mice. Collectively, our data demonstrated that kisspeptin suppresses both GSIS and non-glucose-stimulated insulin secretion of pancreatic ß-cells, but only non-glucose-stimulated insulin secretion depends on activated autophagic degradation of (pro)insulin. Our study provides novel insights for the development of impaired insulin secretion during T2D progression.

Highly efficient and stable 2D-3D perovskite solar cells fabricated by interfacial modification.

Two-dimensional (2D) perovskites, which have excellent stability compared with three-dimensional (3D) perovskites owing to the effective protection of the hydrophobic organic ligands, have become a research hotspot and have made great developmental progress in recent years. Herein, an n-butylammonium iodide (BAI) post-treatment process was developed to fabricate a 2D-3D hybrid perovskite with a thin layer of 2D perovskite covered on the surface of the 3D CH3NH3PbI3 perovskite. The growth process of 2D perovskite is formed through the chemical reaction between BAI and the residual PbI2, which improves stability and reduces the number of crystal defects of 3D perovskite by optimizing stoichiometry. Compared with the 3D counterpart, the 2D-3D hybrid perovskite shows outstanding light and air stability when exposed to external environments. Moreover, structure conversion from 3D to 2D-3D can induce the passivation of defects in the 3D films. The power conversion efficiency of the 2D-3D solar cell exceeds 18% and retains 80% of the initial value after more than 2000 h of storage without encapsulation.

Charge carrier recombination dynamics in a bi-cationic perovskite solar cell.

The compositional engineering is of great importance to tune the electrical and optical properties of perovskite and improve the photovoltaic performance of perovskite solar cells. The exploration of the corresponding photoelectric conversion processes, especially the carrier recombination dynamics, will contribute to the optimization of the devices. In this work, perovskite with mixed methylammonium (MA) and formamidinium (FA) as organic cations, MA0.4FA0.6PbI3, is fabricated to study the influence of the bi-cation on the charge carrier recombination dynamics. X-ray diffraction analysis indicates the existence of the MAPbI3-FAPbI3 phase segregation in the bi-cationic perovskite crystal. The time-resolved photoluminescence dynamics presents a relatively fast carrier recombination process ascribed to the charge transfer from MAPbI3 to FAPbI3 in the bi-cationic perovskite film. The carrier recombination dynamics investigated by transient photovoltage measurements reveals a biphasic trap-assisted carrier recombination mechanism in the bi-cationic device, which involves carrier recombination in the MAPbI3 phase and FAPbI3 phase, respectively. The ultimate presentation of the carrier recombination process is closely related to the charge transfer between the two perovskite phases.

Effect of trap states on photocatalytic properties of boron-doped anatase TiO2 microspheres studied by time-resolved infrared spectroscopy.

The features of the electronic structure of semiconductor photocatalysts are fundamental to understanding the corresponding photocatalytic process. Besides the bandgap and edges, the behavior of photogenerated charge carriers and trap states can also greatly affect the photocatalytic process but it has been less considered during the material design. A previous study (G. Liu, J. Pan, L. Yin et al., Adv. Funct. Mater., 2012, 22, 3233-3238) showed that the interstitial boron on anatase {001} facets can change the photocatalytic preference from reductive H2 evolution to oxidative O2 evolution in the water splitting reaction, interpreted as the change in the band edges. In this work, we employed transient infrared absorption-excitation energy scanning spectroscopy and femtosecond time-resolved mid-infrared spectroscopy to investigate this phenomenon in view of the effect caused by the boron dopant on the photogenerated carrier kinetics and the energy level distribution of the trap states. We found that the surface boron doping eliminates significantly the trap states above the valence band, which improves its photocatalytic oxygen generation. On the other hand, surface boron doping also introduces a substantial amount of electron recombination centers (i.e., Bσ+ in the shell layer). Furthermore, surface boron doping also leads to an inefficient electron transfer from TiO2 to the co-catalyst Pt. Both of these effects give rise to its inferior photocatalytic capability in H2 evolution.

Characterization of the influences of morphology on the intrinsic properties of perovskite films by temperature-dependent and time-resolved spectroscopies.

Organic-inorganic halide perovskites have attracted enormous attention owing to their promising application in photovoltaic devices. The morphology of the perovskites is the key to driving the performance of perovskite devices, which necessitates a systematic study. In this work, two typical morphologies, i.e., flake and cube, of perovskite films are fabricated, and the temperature-dependent optical absorption and photoluminescence properties of the two types of perovskite film are systematically investigated. From the temperature-dependent spectra, both exciton and phase transition temperatures of the flake film are found to be about 10 K lower than those of the cube one. Meanwhile, the influences of the morphology on the exciton binding energy, optical phonon energy and polaron binding energy are quantitatively characterized. The exciton binding of the flake film is nearly three times smaller than that of the cube one, while the phonon coupling energy and the polaron binding energy of the former are about 5 meV and 2 meV larger than those of the latter. Furthermore, the results of photoluminescence lifetime and charge separation efficiency further reveal that the charge carrier kinetics in the two kinds of perovskite films is significantly different. The current study provides a theoretical framework to understand the fundamental physics of perovskites and to promote the design and enhancement of active materials for improved optoelectronic devices.

Multiple-Trapping Model for the Charge Recombination Dynamics in Mesoporous-Structured Perovskite Solar Cells.

The photovoltaic performance of organic-inorganic hybrid perovskite solar cells has reached a bottleneck after rapid development in last few years. Further breakthrough in this field requires deeper understanding of the underlying mechanism of the photoelectric conversion process in the device, especially the dynamics of charge-carrier recombination. Originating from dye-sensitized solar cells (DSSCs), mesoporous-structured perovskite solar cells (MPSCs) have shown many similarities to DSSCs with respect to their photoelectric dynamics. Herein, by applying the multiple-trapping model of the charge-recombination dynamic process for DSSCs in MPSCs, with rational modification, a novel physical model is proposed to describe the dynamics of charge recombination in MPSCs that exhibits good agreement with experimental data. Accordingly, the perovskite- and TiO2 -dominating charge-recombination processes are assigned and their relationships with the trap-state distribution are also discussed. An optimal balance between these two dynamic processes is required to improve the performance of mesoporous-structured perovskite devices.

Power output and carrier dynamics studies of perovskite solar cells under working conditions.

Perovskite solar cells have emerged as promising photovoltaic systems with superb power conversion efficiency. For the practical application of perovskite devices, the greatest concerns are the power output density and the related dynamics under working conditions. In this study, the working conditions of planar and mesoscopic perovskite solar cells are simulated and the power output density evolutions with the working voltage are highlighted. The planar device exhibits higher capability of outputting power than the mesoscopic one. The transient photoelectric conversion dynamics are investigated under the open circuit, short circuit and working conditions. It is found that the power output and dynamic processes are correlated intrinsically, which suggests that the power output is the competitive result of the charge carrier recombination and transport. The present work offers a unique view to elucidating the relationship between the power output and the charge carrier dynamics for perovskite solar cells in a comprehensive manner, which would be beneficial to their future practical applications.

Adverse Effects of Excess Residual PbI2 on Photovoltaic Performance, Charge Separation, and Trap-State Properties in Mesoporous Structured Perovskite Solar Cells.

Organic-inorganic halide perovskite solar cells have rapidly come to prominence in the photovoltaic field. In this context, CH3 NH3 PbI3 , as the most widely adopted active layer, has been attracting great attention. Generally, in a CH3 NH3 PbI3 layer, unreacted PbI2 inevitably coexists with the perovskite crystals, especially following a two-step fabrication process. There appears to be a consensus that an appropriate amount of unreacted PbI2 is beneficial to the overall photovoltaic performance of a device, the only disadvantageous aspect of excess residual PbI2 being viewed as its insulating nature. However, the further development of such perovskite-based devices requires a deeper understanding of the role of residual PbI2 . In this work, PbI2 -enriched and PbI2 -controlled perovskite films, as two extreme cases, have been prepared by modulating the crystallinity of a pre-deposited PbI2 film. The effects of excess residual PbI2 have been elucidated on the basis of spectroscopic and optoelectronic studies. The initial charge separation, the trap-state density, and the trap-state distribution have all been found to be adversely affected in PbI2 -enriched devices, to the detriment of photovoltaic performance. This leads to a biphasic recombination process and accelerates the charge carrier recombination dynamics.

The Influence of Morphology and PbI2 on the Intrinsic Trap State Distribution in Perovskite Films Determined by Using Temperature-Dependent Fluorescence Spectroscopy.

Perovskite films with different particle sizes and PbI2 contents were prepared by using a controlled single or sequential method. By means of temperature-dependent fluorescence spectroscopy, the energetic distribution of intrinsic intragap trap states in perovskite was quantitatively determined, and the radiative charge recombinations through the band edge and via trap states were studied. Furthermore, a series of thermodynamic parameters, such as the demarcation energy between radiative and nonradiative recombination regions, detrapping activation energy, and characteristic temperature, were extracted based on which of the possible radiative and nonradiative recombination mechanisms were proposed. In addition, the correlation between the morphology of the perovskite films, the PbI2 content, and the energetic distribution of the trap states was investigated. Finally, we discuss the structure-function relationship of perovskite films prepared by different methods.

Mechanism of biphasic charge recombination and accumulation in TiO2 mesoporous structured perovskite solar cells.

Organic-inorganic halide perovskite solar cells are becoming the next big thing in the photovoltaic field owing to their rapidly developing photoelectric conversion performance. Herein, mesoporous structured perovskite devices with various perovskite grain sizes are fabricated by a sequential dropping method, and the charge recombination dynamics is investigated by transient optical-electric measurements. All devices exhibit an overall power conversion efficiency around 15%. More importantly, a biphasic trap-limited charge recombination process is proposed and interpreted by taking into account the specific charge accumulation mechanism in perovskite solar cells. At low Fermi levels, photo-generated electrons predominately populate in the perovskite phase, while at high Fermi levels, most electrons occupy traps in mesoporous TiO2. As a result, the dynamics of charge recombination is, respectively, dominated by the perovskite phase and mesoporous TiO2 in these two cases. The present work would give a new perspective on the charge recombination process in meso-structured perovskite solar cells.

Oxatub[4]arene: a molecular "transformer" capable of hosting a wide range of organic cations.

The molecular "transformer", oxatub[4]arene, was found to be able to host a wide range of organic cations. The strong binding ability is believed to originate from its four interconvertible and deep-cavity conformers. The binding behavior of such adaptable receptors may provide implications for molecular recognition in nature.

Trap-limited charge recombination in intrinsic perovskite film and meso-superstructured perovskite solar cells and the passivation effect of the hole-transport material on trap states.

Charge recombination dynamics in intrinsic perovskite film and in meso-superstructured perovskite solar cells have been systematically studied, which are found to be mediated by the energetic distribution of intra-gap trap states as described by the trap-limited recombination theory. Besides, the passivation effect of the hole-transport material on trap states is discussed.