Breaking the bottleneck of lead-free perovskite solar cells through dimensionality modulation.

The emerging perovskite solar cell (PSC) technology has attracted significant attention due to its superior power conversion efficiency (PCE) among the thin-film photovoltaic technologies. However, the toxicity of lead and poor stability of lead halide materials hinder their commercialization. In this case, after a decade of effort, various categories of lead-free perovskites and perovskite-like materials have been developed, including tin halide perovskites, double perovskites, defect-structured perovskites, and rudorffites. However, the performance of the corresponding devices still falls short of expectations, especially their PCE. The limitations mainly originate from either the unstable lattice structure of these materials, which causes the distortion of their octahedra, or their low dimensionality (e.g., structural and electronic dimensionality)-correlated poor carrier transport and self-trapping effect, accelerating nonradiative recombination. Therefore, understanding the relationship between the structures and performance in these emerging candidates and leveraging these insights to design or modify new lead-free perovskites is of great significance. Herein, we review the variety of dimensionalities in different categories of lead-free perovskites and perovskite-like materials and conclude that dimensionality is an important aspect among the crucial indexes that determine the performance of lead-free PSCs. In addition, we summarize the modulation of both structural and electronic dimensionality, and the corresponding enhanced optoelectronic properties in different categories. Finally, perspectives on the future development of lead-free perovskites and perovskite-like materials for photovoltaic applications are provided. We hope that this review will provide researchers with a concise overview of these emerging materials and help them leverage dimensionality to break the bottleneck in photovoltaic applications.

Heteroepitaxial Growth to Construct Hexagonal/Hexagonal ß-NaYF4:Yb,Tm/Cs4PbBr6 Multi-Code Emitting Core/Shell Nanocrystals.

Synthesis of upconversion nanoparticles (UCNPs)-metal halide perovskites (MHPs) heterostructure is garnered immense attentions due to their unparalleled photophysical properties. However, the obvious difference in their structural forms makes it a huge challenge. Herein, hexagonal ß-NaYF4 and hexagonal Cs4PbBr6 are filtrated to construct the UCNP/MHP heterostructural luminescent material. The similarity in their crystal structures facilitate the heteroepitaxial growth of Cs4PbBr6 on the surface of ß-NaYF4 NPs, leading to the formation of high-quality ß-NaYF4:Yb,Tm/Cs4PbBr6 core/shell nanocrystals (NCs). Interestingly, this heterostructure endows the core/shell NCs with typically narrow-band green emission centered at 524 nm under 980 nm excitation, which should be attributed to the Förster resonance energy transfer (FRET) from Tm3+ to Cs4PbBr6. It is noteworthy that the FRET efficiency of ß-NaYF4:Yb,Tm/Cs4PbBr6 core/shell NCs (58.33%) is much higher than that of the physically mixed sample (1.84%). In addition, the reduced defect density, lattice anchoring effect, as well as diluted ionic bonding proportion induced by the core/shell structure further increase the excellent water-resistance and thermal cycling stability of Cs4PbBr6. These findings open up a new way to construct UCNP/MHP heterostructure with better multi-code luminescence performance and stability and promote its wide optoelectronic applications.

Regulating Water Adsorption Sites of Keto-Enamine COF by Base Exfoliation and Deprotonation for Enhanced Humidity Response.

Covalent organic framework (COF) has received much attention owing to its unique framework structure formed by diverse organic units. However, challenges, including low conductivity, structure instability, and limited control of adsorption and desorption processes, stimulate the modification of COF in electronic sensors. Herein, inspired by the alterable structure of COF in different solvents, a facile base exfoliation and deprotonation method is proposed to regulate the water adsorption sites and improve the intrinsic conductivity of TpPa-1 COF. TpPa-1 COF powders are exfoliated to nanosheets to increase water adsorption, while the deprotonation is utilized to adjust the affinity of water molecules on TpPa-1 COF framework, contributing to water accumulation in the 1D pores. The as-fabricated TpPa-1 COF sensor exhibits a decreased recovery time from 419 to 49 s, forming a linear relation between relative humidity (RH) value and humidity response. The excellent chemical stability of the covalent bond of TpPa-1 COF contributes to the excellent stable device performance in 30 days, promoting further integration and data analysis in respiration monitoring.

Temporin-GHaK Exhibits Antineoplastic Activity against Human Lung Adenocarcinoma by Inhibiting the Wnt Signaling Pathway through miRNA-4516.

(1) Background: GHaK is derived from the antimicrobial peptide temporin-GHa by substituting the amino acid H with K to enhance its bactericidal activity. The present research aims to broaden the pharmacological potential of GHaK by exploring its antineoplastic activity against human lung adenocarcinoma. (2) Methods: The cell viability, migration, invasion, apoptosis, and cell cycle of A549 and PC-9 cells were tested after GHaK treatment. miRNA sequencing, RT-PCR, Western blotting, and luciferase reporter gene assay were further performed to reveal the potential mechanism. (3) Results: GHaK significantly suppressed cell viability, migration, and invasion; induced apoptosis; and caused cell cycle arrest in the G2/M and S phase in PC-9 and A549 cells, respectively. The miRNA sequencing results show a total of 161 up-regulated and 115 down-regulated miRNAs. Furthermore, the study identified six up-regulated miRNAs (miR-4516, miR-4284, miR-204-5p, miR-12136, miR-4463, and miR-1296-3p) and their inhibitory effects on the expressions of target genes (Wnt 8B, FZD2, DVL3, and FOSL1) caused by miR-4516 directly interacting with Wnt 8B. Western blotting revealed the down-regulation of p-GSK-3ß, along with a decreased expressions of cyclin A1 and CDK2 in A549 cells and cyclin B1 and CDK1 in PC-9 cells. (4) Conclusions: Temporin-GHaK exhibits antineoplastic activity against human lung adenocarcinoma by inhibiting the Wnt signaling pathway through miRNA-4516.

IL-27-induced, MSC-derived Exosomes Promote MMP3 Expression Through the miR-206/L3MBTL4 Axis in Synovial Fibroblasts.

Context: In rheumatoid arthritis (RA), hyperproliferative fibroblast-like synoviocytes (FLS) can secrete a variety of tissue hydrolases, such as matrix metalloproteinases (MMPs), causing the destruction of chondrocytes. Mesenchymal stem cells (MSCs) can directly affect FLS through extracellular vesicles (EVs). Interleukin-27 (IL-27) is a pleiotropic immune regulator frequently overexpressed in RA. Objective: The study intended to examine the effects of IL-27-induced exosomes from bone-marrow mesenchymal stem cells (BM-MSCs) and to determine if they promote the secretion of MMP3 in synovial cells. Design: The research team performed a genetic study. Setting: The study took place at the First Affiliated Hospital of Hainan Medical University in Haikou City, Hainan, China. Outcome Measures: The research team: (1) determined if IL-27 expression had occurred in the synovial fluid; (2) co-cultured IL-27-induced MSCs with FLS to detect the expression of MMP3 in the FLS; (3) Under IL-27 induction, MSC-derived exosomes with IL-27R knockdown were collected to detect the expression of microRNAs(miRNAs) associated with RA; (4) screened the miRNAs to determine the most significant differences in expression; (5) determined the miRNA target genes in arthritis, using Western blot (WB) and qRT-PCR; and (6) Dual luciferase and ChIP experiments confirm regulation of MMP3 by L3MBTL4. Results: IL-27 was highly expressed in RA, and the IL-27-induced, MSC-derived exosomes promoted the expression of MMP3 in FLS. The IL-27-induced MSC-derived exosomes significantly upregulated the expression of miR-206-3p, and the miR-206-3p target, miR-206/ lethal(3) malignant brain tumor-like protein 4 (L3MBTL4), regulated the MMP3 transcription. The IL-27-induced, MSC-derived exosomes promoted MMP3 expression in the FLS through the miR-206-3p/L3MBTL4 axis, thereby promoting chondrocyte degradation and aggravating RA. Conclusions: IL-27 can induce the expression of miR-206 in MSCs, and miR-206 can be transported into FLS through MSC-EVs to promote FLS migration and MMP3 expression and aggravate articular cartilage damage. Patients with RA who have a high IL-27 expression may not be suitable to receive treatment with MSCs, and clinicians can use MSCs that knock down or delete IL-27R to treat RA patients who have a high IL-27 expression.

Study of Intermolecular Reconfiguration of Flexible COF-5 Film and Its Ultra-high Chemiresistive Humidity Sensitivity.

Recently, abundant active materials are developed to achieve the wearable detection of human body humidity. However, the limited response signal and sensitivity restrict further application due to their moderate affinity to water. Herein, we propose a flexible COF-5 film synthesized by a brief vapor-assisted method at room temperature. Intermediates are calculated by DFT simulation to investigate the interaction between COF-5 and water. The adsorption and desorption of water molecule result in a reversible deformation of COF layers while creating new conductive path by π-π stacking. The as-prepared COF-5 films are applied to the flexible humidity sensors, exhibiting a resistance change in 4 orders of magnitude with remarkable linear relation between log function of resistance and relative humidity (RH) in 11 %-98 % RH range. Applications including respiratory monitoring and non-contact switch are tested, providing a promising prospect for the detection of human body humidity.

Doped Bilayer Tin(IV) Oxide Electron Transport Layer for High Open-Circuit Voltage Planar Perovskite Solar Cells with Reduced Hysteresis.

Tin oxide (SnO2 ) is an emerging electron transport layer (ETL) material in halide perovskite solar cells (PSCs). Among current limitations, open-circuit voltage (VOC ) loss is one of the major factors to be addressed for further improvement. Here a bilayer ETL consisting of two SnO2 nanoparticle layers doped with different amounts of ammonium chloride is proposed. As demonstrated by photoelectron spectroscopy and photophysical studies, the main effect of the novel ETL is to modify the energy level alignment at the SnO2 /perovskite interface, which leads to decreased carrier recombination, enhanced electron transfer, and reduced voltage loss. Moreover, X-ray diffraction reveals reduced strain in perovskite layers grown on bilayer ETLs with respect to single-layer ETLs, further contributing to a decrease of carrier recombination processes. Finally, the bilayer approach enables the more reproducible preparation of smooth and pinhole-free ETLs as compared to single-step deposition ETLs. PSCs with the doped bilayer SnO2 ETL demonstrate strongly increased VOC values of up to 1.21 V with a power conversion efficiency of 21.75% while showing negligible hysteresis and enhanced stability. Moreover, the SnO2 bilayer can be processed at low temperature (70 °C), and has therefore a high potential for use in tandem devices or flexible PSCs.

High Efficiency Mesoscopic Solar Cells Using CsPbI3 Perovskite Quantum Dots Enabled by Chemical Interface Engineering.

All-inorganic α-CsPbI3 perovskite quantum dots (QDs) are attracting great interest as solar cell absorbers due to their appealing light harvesting properties and enhanced stability due to the absence of volatile organic constituents. Moreover, ex situ synthesized QDs significantly reduce the variability of the perovskite layer deposition process. However, the incorporation of α-CsPbI3 QDs into mesoporous TiO2 (m-TiO2) is highly challenging, but these constitute the best performing electron transport materials in state-of-the-art perovskite solar cells. Herein, the m-TiO2 surface is engineered using an electron-rich cesium-ion containing methyl acetate solution. As one effect of this treatment, the solid-liquid interfacial tension at the TiO2 surface is reduced and the wettability is improved, facilitating the migration of the QDs into m-TiO2. As a second effect, Cs+ ions passivate the QD surface and promote the charge transfer at the m-TiO2/QD interface, leading to an enhancement of the electron injection rate by a factor of 3. In combination with an ethanol-environment smoothing route that significantly reduces the surface roughness of the m-TiO2/QD layer, optimized devices exhibit highly reproducible power conversion efficiencies exceeding 13%. The best cell with an efficiency of 14.32% (reverse scan) reaches a short-circuit current density of 17.77 mA cm-2, which is an outstanding value for QD-based perovskite solar cells.

Association of plasma apolipoprotein CIII, high sensitivity C-reactive protein and tumor necrosis factor-α contributes to the clinical features of coronary heart disease in Li and Han ethnic groups in China.

BACKGROUND: Apolipoprotein CIII (apoCIII) is an independent risk for coronary heart disease (CHD). In this study, we investigated the associations among plasma apoCIII, hs-CRP and TNF-α levels and their roles in the clinical features of CHD in the Li and Han ethnic groups in China. METHODS: A cohort of 474 participants was recruited (238 atherosclerotic patients and 236 healthy controls) from the Li and Han ethnic groups. Blood samples were obtained to evaluate apoCIII, TNF-α, hs-CRP and lipid profiles. Chi-squared, t-tests, and Kruskal-Wallis or Wilcoxon-Mann-Whitney tests, Pearson or Spearman correlation tests and multiple unconditional logistic regression were employed to analyze lipid profiles and variations in plasma apoCIII, TNF-α, hs-CRP in subgroups of CHD and their contributions to CHD using SPSS version 20.0 software. RESULTS: Compared to healthy participants, unfavorable lipid profiles were identified in CHD patients with enhanced systolic pressure, diastolic pressure, fasting blood sugar (FBS), TG, TC, LDL-C, apoB, Lp(a) (P < 0.05, TC and Lp(a); P < 0.01, FBS, TG, LDL-C, apoB); and lower HDL-C and apoAI (P < 0.05). Plasma apoCIII, TNF-α and hs-CRP levels were higher in CHD individuals (16.77 ± 5.98 mg/dL vs. 10.91 ± 4.97 mg/dL; 17.23 ± 6.34 pg/mL vs. 9.49 ± 3.88 pg/mL; 9.55 ± 7.32 mg/L vs. 2.14 ± 1.56 mg/L; P < 0.01 vs. healthy participants). Identical patterns were obtained in the Li and Han groups (16.46 ± 6.08 mg/dL vs. 11.72 ± 5.16 mg/dL; 15.71 ± 5.52 pg/mL vs. 9.74 ± 4.31 pg/mL; 8.21 ± 7.09 mg/L vs. 2.15 ± 1.51 mg/L in Li people; 17.05 ± 5.90 mg/dL vs. 10.07 ± 4.63 mg/dL; 18.59 ± 6.73 pg/mL vs. 9.23 ± 3.38 pg/mL; 10.75 ± 7.44 mg/L vs. 2.12 ± 1.63 mg/L in Han people; P < 0.01). Paired comparisons of subgroups with stable angina, unstable angina, and acute myocardial infarction (AMI) revealed significant variation in plasma levels of apoCIII, TNF-α and hs-CRP (P < 0.01), but not among subgroups with mild, moderate and severe stenosis (P > 0.05). Plasma apoCIII, TNF-α and hs-CRP contributed to the development of CHD (OR = 2.554, 7.252, 6.035, P < 0.01) with paired correlations in CHD patients (apoCIII vs. TNF-α, r = 0.425; apoCIII vs. hs-CRP, r = 0.319; TNF-α vs. hs-CRP, r = 0.400, P < 0.01). CONCLUSIONS: Association among plasma apoCIII, hs-CRP and TNF-α interacts with unfavorable lipid profiles to contribute to the clinical features of CHD with stable angina, unstable angina, and AMI in the Li and Han ethnic groups in China.

Association of the S2 allele of the SstI polymorphism in the apoC3 gene with plasma apoCIII interacts with unfavorable lipid profiles to contribute to atherosclerosis in the Li ethnic group in China.

BACKGROUND: The SstI polymorphism in the apolipoprotein 3 gene (apoC3) has been identified in many ethnic groups. In addition, the S2 allele of the SstI polymorphism is shown to be associated with increased plasma triglyceride (TG) levels. Plasma apoCIII is an important atherogenic factor, which interrupts lipid metabolism and is positively associated with plasma TG levels. However, the existence of the SstI polymorphism in the Li ethnic group in China remains to be confirmed. The relationship between the S2 allele of the SstI polymorphism and plasma apoCIII or TG and their roles in atherosclerosis are also unknown. METHODS: A cohort of 628 participants was recruited (316 atherosclerotic patients and 312 healthy controls) from both the Li and Han ethnic groups. Blood samples were obtained to evaluate the SstI polymorphism in the apoC3 and lipid profiles. Chi-squared and t-tests and multiple unconditional logistic regression were employed to analyze the genotypic and allelic frequencies and lipid profiles using SPSS version 20.0 software. RESULTS: The SstI polymorphism in the apoC3 was identified in the Li ethnic group. The S2 allele and plasma apoCIII and TG levels were associated with the development of atherosclerosis (P < 0.01, S2 allele and apoCIII; P < 0.05, TG) in the Li ethnic group. The S2 allele was associated with increased plasma apoCIII levels in the atherosclerotic group (P < 0.01), but with increased plasma apoCIII and TG levels in control group (both P < 0.01). In addition to the increases in the S2 allele frequency and plasma TG and apoCIII levels, atherosclerotic patients in the Li ethnic group also exhibited increased apoB, decreased HDL-C and apoAI and a lower apoAI:apoB ratio (all P < 0.01). CONCLUSIONS: Our results indicate that the S2 allele of the SstI polymorphism in the apoC3 gene is associated with plasma apoCIII levels in the Li population. In combination with unfavorable lipid profiles, this might contribute to susceptibility to atherosclerosis.

TpPa-1 COFs-Enhanced Zwitterion Hydrogel for Efficient Harvesting of Atmospheric Water.

Zwitterionic hydrogel, serving as carriers for hygroscopic salts, holds significant potential in atmospheric water harvesting. However, their further application is limited by structural collapse in high-concentration salt solution and poor photothermal conversion performance. Herein, the graded pore structure of poly-3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate (PDMAPS) zwitterionic hydrogel/TpPa-1 covalent organic frameworks (COFs)/LiCl composite (named as PCL composite hydrogel) is proposed, which leads to the accelerated diffusion effect for water molecules. As a result, the vapor adsorption capacity of the optimal composite hydrogel (PCL-42) reaches 2.88 g g-1 within 12 hours under conditions of 25 °C and 90 % RH. Simultaneously, the maximum temperature of PCL-42 composite could reach 53.9 °C after 9 minutes under a simulated solar intensity of 1.0 kW m-2, releasing 91 % of the adsorbed water in 3 hours, providing a promising prospect for efficient solar-driven atmospheric water harvesting. One cycle could collect 7.55 g of fresh water under outdoor conditions, and the maximum daily water production may reach 2.71 kg kg-1. The reason lies in that TpPa-1 COFs lead hydrogel to form a gradient pore structure, which may accelerate the transport of water molecules, increase the loading capacity of LiCl and enhance the photothermal property.

Anlotinib inhibits growth of human esophageal cancer TE-1 cells by negative regulating PI3K/Akt signaling pathway.

Anlotinib is effective in treatment of many kinds of malignant cancer, but its antineoplastic effects on esophageal cancer remains unclear. This study aims to investigate its impact on esophageal cancer and the underlying mechanisms. Anlotiniband 5-fluorouracil + cisplatin (5-FU + DDP) was administered separately to human esophageal cancer TE- 1 cells tumor xenograft mouse models every 3 days. Tumor size and body weight were measured before each treatment and at the end of the experiment. In vitro studies were conducted using TE- 1 cells to examine the effects of Anlotinib. Cell viability, migration, proliferation, apoptosis, cell cycle, their regulatory proteins and the transcriptomic changes were analyzed. Anlotinib reduced tumor size, tumor weight, and the ratio of tumor weight to body weight in vivo. It decreased the viability of TE- 1 cells, with a 50% growth-inhibitory concentration of 9.454 µM for 24 h, induced apoptosis, and arrested TE- 1 cell cycle in the S phase. It inhibited migration and proliferation while negatively regulating the PI3K/Akt signaling pathway. Enhanced expressions of P21, Bax, and lowered expressions of cyclin A1, cyclin B1, CDK1, PI3K, Akt, p-Akt, and Bcl-2 were observed after Anlotinib treatment. Anlotinib exhibits antineoplastic activity against human esophageal cancer TE- 1 cells by negatively regulating the PI3K/Akt signaling pathway, consequently altering the expressions of proteins related to proliferation, apoptosis, and the cell cycle.

Passivation of 2D Cs2PbI2Cl2 Nanosheets for Efficient and Stable CsPbI3 Quantum Dot Solar Cells.

Inorganic CsPbI3 perovskite quantum dots (PQDs) possess remarkable optical properties, making them highly promising for photovoltaic applications. However, the inadequate stability resulting from internal structural instability and the complex external surface chemical environment of CsPbI3 PQDs has hindered the development of CsPbI3 PQD solar cells (PQDSCs). In this work, the capping layer composed of inorganic two-dimensional (2D) Ruddlesden-Popper (RP) phase Cs2PbI2Cl2 nanosheets (NSs) is introduced, which may be effectively treated to improve the surface properties of the CsPbI3 PQD film. This modification serves to passivate defects by filling cesium and iodine vacancies while optimizing the energy band arrangement and preventing humidity intrusion, leading to the meliorative stability and photovoltaic performance. The optimized CsPbI3 PQDSCs achieve an enhanced power conversion efficiency (PCE) of 14.73%, with the superb stability of only a 16% efficiency loss after being exposed to ambient conditions (30 ± 5% RH) for 432 h.

Venetoclax Clinical Pharmacokinetics After Administration of Crushed, Ground or Whole Tablets.

PURPOSE: Venetoclax is a potent, orally bioavailable BCL-2 inhibitor used in the treatment of some hematological malignancies. Crushing tablets may be necessary to help with the administration of venetoclax to patients with swallowing difficulties or patients requiring nasogastric tube feeding. The study was conducted to assess the bioavailability of crushed and finely ground venetoclax tablets relative to whole tablets. METHODS: An open-label, randomized, 3-way, crossover study in 15 healthy adult females was conducted. Venetoclax tablets were administered orally in a crushed, ground or intact form on Day 1 of each period with water following a high-fat breakfast. Pharmacokinetic samples were collected up to 72 hours postdosing. FINDINGS: The crushed and ground tablets met the bioequivalence criteria (0.80-1.25) relative to the intact tablets with respect to area under the concentration-time curve to time of the last measurable concentration (AUCt) and to infinite time (AUCinf) but exhibited a slightly lower maximum plasma concentration (Cmax). This was not considered clinically significant as only venetoclax overall exposure (AUC) has been shown to correlate with clinical efficacy. There was no change in the physical appearance and the evaluated physicochemical properties of crushed and ground venetoclax tablets after 72 hours of storage at 25°C/60% relative humidity. IMPLICATIONS: Crushing or grinding venetoclax tablets before administration could be considered as a viable alternative method of administration for patients who have difficulty swallowing whole venetoclax tablets or patients requiring nasogastric tube feeding. GOV IDENTIFIERS: NCT05909553, registered June 12, 2023.

A crystal capping layer for formation of black-phase FAPbI3 perovskite in humid air.

Black-phase formamidinium lead iodide (α-FAPbI3) perovskites are the desired phase for photovoltaic applications, but water can trigger formation of photoinactive impurity phases such as δ-FAPbI3. We show that the classic solvent system for perovskite fabrication exacerbates this reproducibility challenge. The conventional coordinative solvent dimethyl sulfoxide (DMSO) promoted δ-FAPbI3 formation under high relative humidity (RH) conditions because of its hygroscopic nature. We introduced chlorine-containing organic molecules to form a capping layer that blocked moisture penetration while preserving DMSO-based complexes to regulate crystal growth. We report power conversion efficiencies of >24.5% for perovskite solar cells fabricated across an RH range of 20 to 60%, and 23.4% at 80% RH. The unencapsulated device retained 96% of its initial performance in air (with 40 to 60% RH) after 500-hour maximum power point operation.

Modulation of the canonical Wnt activity by androgen signaling in prostate epithelial basal stem cells.

Both the canonical Wnt and androgen receptor (AR) signaling pathways are important for prostate organogenesis and homeostasis. How they crosstalk to regulate prostate stem cell behaviors remains unclear. Here, we show in lineage-tracing mouse models that although Wnt is essential for basal stem cell multipotency, ectopic Wnt activity promotes basal cell over-proliferation and squamous phenotypes, which are counteracted by elevated levels of androgen. In prostate basal cell organoids, dihydrotestosterone (DHT) antagonizes R-spondin-stimulated growth in a concentration-dependent manner. DHT down-regulates the expressions of a Wnt reporter and target genes, and RNA sequencing (RNA-seq) analyses identify Wnt signaling as a key altered pathway. Mechanistically, DHT enhances AR and ß-catenin protein binding, and CUT&RUN analyses reveal that ectopic AR sequesters ß-catenin away from its Wnt-related cistrome. Our results suggest that an intermediate level of Wnt activity in prostate basal stem cells, achieved via AR-ß-catenin interaction, is essential for normal prostate homeostasis.

Surface polarization-induced emission and stability enhancement of CsPbX3 nanocrystals.

Recently, the polarization effect has been receiving tremendous attention, as it can result in improved stability and charge transfer efficiency of metal-halide perovskites (MHPs). However, realizing the polarization effect on CsPbX3 NCs still remains a challenge. Here, metal ions with small radii (such as Mg2+, Li+, Ni2+, etc.) are introduced on the surface of CsPbX3 NCs, which facilitate the arising of electric dipole and surface polarization. The surface polarization effect promotes redistribution of the surface electron density, leading to reinforced surface ligand bonding, reduced surface defects, near unity photoluminescence quantum yields (PLQYs), and enhanced stability. Moreover, further introduction of hydroiodic acid results in the in situ formation of tert-butyl iodide (TBI), which facilitates the successful synthesis of pure iodine-based CsPbI3 NCs with high PLQY (95.3%) and stability under ambient conditions. The results of this work provide sufficient evidence to exhibit the crucial role of the surface polarization effect, which promotes the synthesis of high-quality MHPs and their applications in the fields of optoelectronic devices.

Photocatalytic CO2 reduction using La-Ni bimetallic sites within a covalent organic framework.

The precise construction of photocatalysts with diatomic sites that simultaneously foster light absorption and catalytic activity is a formidable challenge, as both processes follow distinct pathways. Herein, an electrostatically driven self-assembly approach is used, where phenanthroline is used to synthesize bifunctional LaNi sites within covalent organic framework. The La and Ni site acts as optically and catalytically active center for photocarriers generation and highly selective CO2-to-CO reduction, respectively. Theory calculations and in-situ characterization reveal the directional charge transfer between La-Ni double-atomic sites, leading to decreased reaction energy barriers of *COOH intermediate and enhanced CO2-to-CO conversion. As a result, without any additional photosensitizers, a 15.2 times enhancement of the CO2 reduction rate (605.8 µmol·g-1·h-1) over that of a benchmark covalent organic framework colloid (39.9 µmol·g-1·h-1) and improved CO selectivity (98.2%) are achieved. This work presents a potential strategy for integrating optically and catalytically active centers to enhance photocatalytic CO2 reduction.

COF-5/CoAl-LDH Nanocomposite Heterojunction for Enhanced Visible-Light-Driven CO2 Reduction.

Photocatalytic conversion of CO2 into value-added chemical fuels is an attractive route to mitigate global warming and the energy crisis. Reasonable design of optical properties and electronic behavior of the photocatalyst are essential to improve their catalytic activity. Herein, the 1D/2D heterojunction by direct in-situ synthesis of the covalent organic framework (COF)-5 colloid on the surface of CoAl layered double hydroxide (LDH) was used as the prospective photocatalyst for CO2 reduction. COF-5/CoAl-LDH nanocomposite achieved 265.4 µmol g-1 of CO with 94.6 % selectivity over CH4 evolution in 5 h under visible light irradiation, which was 4.8 and 2.3 times higher than those of COF-5 colloid and CoAl-LDH, respectively. The enhanced catalytic activity was derived from the increased visible-light activity and the construction of type II-2 heterojunction, which greatly optimized visible light harvesting and accelerated the efficient separation of the photoinduced holes and electrons. This work paves the way for rational design of heterojunction catalysts in photocatalytic CO2 reduction.

A 3D-printed transfusion platform reveals beneficial effects of normoglycemic erythrocyte storage solutions and a novel rejuvenating solution.

A set of 3D-printed analytical devices were developed to investigate erythrocytes (ERYs) processed in conventional and modified storage solutions used in transfusion medicine. During storage, prior to transfusion into a patient recipient, ERYs undergo many chemical and physical changes that are not completely understood. However, these changes are thought to contribute to an increase in post-transfusion complications, and even an increase in mortality rates. Here, a reusable fluidic device (fabricated with additive manufacturing technologies) enabled the evaluation of ERYs prior to, and after, introduction into a stream of flowing fresh ERYs, thus representing components of an in vivo ERY transfusion on an in vitro platform. Specifically, ERYs stored in conventional and glucose-modified solutions were assayed by chemiluminescence for their ability to release flow-induced ATP. The ERY's deformability was also determined throughout the storage duration using a novel membrane transport approach housed in a 3D-printed scaffold. Results show that hyperglycemic conditions permanently alter ERY deformability, which may explain the reduced ATP release, as this phenomenon is related to cell deformability. Importantly, the reduced deformability and ATP release were reversible in an in vitro model of transfusion; specifically, when stored cells were introduced into a flowing stream of healthy cells, the ERY-derived release of ATP and cell deformability both returned to states similar to that of non-stored cells. However, after 1-2 weeks of storage, the deleterious effects of the storage were permanent. These results suggest that currently approved hyperglycemic storage solutions are having adverse effects on stored ERYs used in transfusion medicine and that normoglycemic storage may reduce the storage lesion, especially for cells stored for longer than 14 days.