Reducing nonradiative recombination for highly efficient inverted perovskite solar cells via a synergistic bimolecular interface.

Reducing interface nonradiative recombination is important for realizing highly efficient perovskite solar cells. In this work, we develop a synergistic bimolecular interlayer (SBI) strategy via 4-methoxyphenylphosphonic acid (MPA) and 2-phenylethylammonium iodide (PEAI) to functionalize the perovskite interface. MPA induces an in-situ chemical reaction at the perovskite surface via forming strong P-O-Pb covalent bonds that diminish the surface defect density and upshift the surface Fermi level. PEAI further creates an additional negative surface dipole so that a more n-type perovskite surface is constructed, which enhances electron extraction at the top interface. With this cooperative surface treatment, we greatly minimize interface nonradiative recombination through both enhanced defect passivation and improved energetics. The resulting p-i-n device achieves a stabilized power conversion efficiency of 25.53% and one of the smallest nonradiative recombination induced Voc loss of only 59 mV reported to date. We also obtain a certified efficiency of 25.05%. This work sheds light on the synergistic interface engineering for further improvement of perovskite solar cells.

Atomic Ruthenium-Promoted Cadmium Sulfide for Photocatalytic Production of Amino Acids from Biomass Derivatives.

Amino acids are the building blocks of proteins and are widely used as important ingredients for other nitrogen-containing molecules. Here, we report the sustainable production of amino acids from biomass-derived hydroxy acids with high activity under visible-light irradiation and mild conditions, using atomic ruthenium-promoted cadmium sulfide (Ru1/CdS). On a metal basis, the optimized Ru1/CdS exhibits a maximal alanine formation rate of 26.0 molAla ⋅ gRu -1 ⋅ h-1, which is 1.7 times and more than two orders of magnitude higher than that of its nanoparticle counterpart and the conventional thermocatalytic process, respectively. Integrated spectroscopic analysis and density functional theory calculations attribute the high performance of Ru1/CdS to the facilitated charge separation and O-H bond dissociation of the α-hydroxy group, here of lactic acid. The operando nuclear magnetic resonance further infers a unique "double activation" mechanism of both the CH-OH and CH3-CH-OH structures in lactic acid, which significantly accelerates its photocatalytic amination toward alanine.

Carbon nitride nanosheet-supported CuO for efficient photocatalytic CO2 reduction with 100% CO selectivity.

The optimal ratio of reaction solutions resulted in excellent performance and product selectivity of CuO/g-C3N4 composites in the photocatalytic CO2 reduction reaction. A pH-dependent chemical exchange saturation transfer (CEST) imaging nuclear magnetic resonance (NMR) method was used to confirm that CuO modification improves the adsorption capacity of CO2.

Universal growth of perovskite thin monocrystals from high solute flux for sensitive self-driven X-ray detection.

Metal-halide perovskite thin monocrystals featuring efficient carrier collection and transport capabilities are well suited for radiation detectors, yet their growth in a generic, well-controlled manner remains challenging. Here, we reveal that mass transfer is one major limiting factor during solution growth of perovskite thin monocrystals. A general approach is developed to overcome synthetic limitation by using a high solute flux system, in which mass diffusion coefficient is improved from 1.7×10-10 to 5.4×10-10 m2 s-1 by suppressing monomer aggregation. The generality of this approach is validated by the synthesis of 29 types of perovskite thin monocrystals at 40-90 °C with the growth velocity up to 27.2 µm min-1. The as-grown perovskite monocrystals deliver a high X-ray sensitivity of 1.74×105 µC Gy-1 cm-2 without applied bias. The findings regarding limited mass transfer and high-flux crystallization are crucial towards advancing the preparation and application of perovskite thin monocrystals.

Ultrahigh Bifunctional Photocatalytic CO2 Reduction and H2 Evolution by Synergistic Interaction of Heteroatomic Pt-Ru Dimerization Sites.

Diatomic-site catalysts (DASCs) inherit the excellent performance of single-atom catalysts (SACs) by utilizing two adjacent atomic metal species to achieve functional complementarity and synergistic effects that improve the carbon dioxide reduction reaction (CO2RR) and H2 evolution reaction (HER) kinetics. Herein, we report a method to further improve the catalytic efficiency of Pt by using Pt and Ru single atoms randomly anchored on a g-C3N4 surface, yielding partial Pt-Ru dimers. The synthesized catalyst exhibits extraordinary photocatalytic activity and stability in both the CO2RR and HER processes. In-depth experimentation, the pH-dependent chemical exchange saturation transfer (CEST) imaging nuclear magnetic resonance (NMR) method, and theoretical analyses reveal that the excellent performance is attributed to orbital coupling between the Pt atoms and the neighboring Ru atoms (mainly dxy and dxz), which decreases the orbital energy levels and weakens the bond strength with intermediates, resulting in improved CO2RR and HER performance. This study successfully applies the pH-dependent CEST imaging NMR method to catalytic reactions, and CO2 adsorption is directly observed using CEST 2D imaging maps. This work presents significant potential for a variety of catalytic reaction applications by systematically designing bimetallic dimers with higher activity and stability.

Selectively Probing the Magnetic Resonance Signals of γ-Aminobutyric Acid in Human Brains In Vivo.

BACKGROUND: Gamma-aminobutyric acid (GABA) is an inhibitory neurotransmitter in human brains, playing a role in the pathogenesis of various psychiatric disorders. Current methods have some non-neglectable shortcomings and noninvasive and accurate detection of GABA in human brains is long-term challenge. PURPOSE: To develop a pulse sequence capable of selectively detecting and quantifying the 1 H signal of GABA in human brains based on optimal controlled spin singlet order. STUDY TYPE: Prospective. SUBJECTS/PHANTOM: A phantom of GABA (pH = 7.3 ± 0.1) and 11 healthy subjects (5 females and 6 males, body mass index: 21 ± 3 kg/m2 , age: 25 ± 4 years). FIELD STRENGTH/SEQUENCE: 7 Tesla, 3 Tesla, GABA-targeted magnetic resonance spectroscopy (GABA-MRS-7 T, GABA-MRS-3 T), magnetization prepared two rapid acquisition gradient echoes sequence. ASSESSMENT: By using the developed pulse sequences applied on the phantom and healthy subjects, the signals of GABA were successfully selectively probed. Quantification of the signals yields the concentration of GABA in the dorsal anterior cingulate cortex (dACC) in human brains. STATISTICAL TESTS: Frequency. RESULTS: The 1 H signals of GABA in the phantom and in the human brains of healthy subjects were successfully detected. The concentration of GABA in the dACC of human brains was 3.3 ± 1.5 mM. DATA CONCLUSION: The developed pulse sequences can be used to selectively probe the 1 H MR signals of GABA in human brains in vivo. EVIDENCE LEVEL: 1 TECHNICAL EFFICACY STAGE: 1.

Ferroelectricity and Thermochromism in a 2D Dion-Jacobson Organic-Inorganic Hybrid Perovskite.

2D organic-inorganic hybrid perovskites (OIHPs) have become one of the hottest research topics due to their excellent environmental stability and unique optoelectronic properties. Recently, the ferroelectricity and thermochromism of 2D OIHPs have attracted increasing interests. Integrating ferroelectricity and thermochromism into perovskites can significantly promote the development of multichannel intelligent devices. Here, a novel 2D Dion-Jacobson OIHP of the formula (3AMP)PbI4 (where 3AMP is 3-(aminomethyl)pyridinium) is reported, which has a remarkable spontaneous polarization value (Ps) of 15.6 µC cm-2 and interesting thermochromism. As far it is known, such a large Ps value is the highest for 2D OIHPs recorded so far. These findings will inspire further exploration and application of multifunctional perovskites.

Activation of Glycolysis by MCM10 Increases Stemness and Paclitaxel Resistance in Gastric Cancer Cells.

BACKGROUND/AIMS: Chemotherapy is an essential avenue for curing malignancies; however, tumor cells acquire resistance to chemotherapeutic agents, eventually leading to chemotherapy failure. At present, paclitaxel (PTX) resistance seriously hinders the therapeutic efficacy of gastric cancer (GC). Investigating the molecular mechanism of PTX resistance in GC is critical. This study attempted to delineate the impact of MCM10 on GC resistance to PTX and its mechanism in GC. MATERIALS AND METHODS: The expression of minichromosome maintenance complex component 10 (MCM10) in GC tissues, its enrichment pathways, and its correlation with glycolysis marker genes and stemness index (mRNAsi) were analyzed in a bioinformatics effort. Real-time quantitative polymerase chain reaction was used to assay the expression of MCM10 in cells. Cell counting kit-8 (CCK-8) was used to analyze cell viability and calculate the 50% inhibitor concentration (IC50) value. Western blot was used to measure the expression of MCM10, Hexokinase 2 (HK2) and stemness-related factors in cells. Sphere-forming assay was performed to study cell sphere-forming ability. Seahorse XF 96 was utilized to measure cell extracellular acidification and oxygen consumption rates. The content of glycolysisrelated products was tested with corresponding kits. RESULTS: MCM10 was significantly upregulated in GC and enriched in the glycolysis pathway, and it was positively correlated with both glycolysis-related genes and stemness index. High expression of MCM10 increased sphere-forming ability of drug-resistant cells and GC resistance to PTX. The stimulation of PTX resistance and drug-resistant cell stemness in GC by high MCM10 expression was mediated by the glycolysis pathway. CONCLUSION: MCM10 was upregulated in GC and drove stemness and PTX resistance in GC cells by activating glycolysis. These findings generated new insights into the development of PTX resistance in GC, implicating that targeting MCM10 may be a novel approach to improve GC sensitivity to PTX chemotherapy.

Probing distribution and dynamics of lithium ions in supermolecule ß-CD-PEO/Li+ solid polymer electrolytes via solid-state NMR.

In this work, the distribution and dynamics of Li+ ions in ß-CD-PEO/Li+ (ß-CD, ß-cyclodextrin; PEO, polyethylene-oxides) crystalline polymer electrolytes were investigated by solid-state NMR to enlighten the ionic conduction mechanism. Specifically, 7Li-6Li REDOR NMR and variable-contact-time 1H-6Li CP/MAS NMR were adopted for the study. The results demonstrate that Li+ ions coordinated by polymer chains have relatively compact spatial density and fast dynamics, which facilitate the improvement of the electrochemical properties. Additionally, the variation of the distribution and dynamics of the Li+ ions and the ionic conduction mechanism were studied and discussed by altering the amount of the Li+ ions. This work deepens our understanding of the distribution and dynamics of Li+ ions in ß-CD-PEO/Li+ crystals and demonstrates possible future applications of solid-state NMR on the study of the polymer electrolytes.

Using optimal controlled singlet spin order to accurately target molecular signal in MRI and MRS.

Magnetic resonance imaging (MRI) and magnetic resonance spectroscopy (MRS) have made great successes in clinical diagnosis, medical research, and neurological science. MRI provides high resolution anatomical images of tissues/organs, and MRS provides information of the functional molecules related to a specific tissue/organ. However, it is difficult for classic MRI/MRS to selectively image/probe a specific metabolite molecule other than the water or fat in tissues/organs. This greatly limits their applications on the study of the molecular mechanism(s) of metabolism and disease. Herein, we report a series of molecularly targeted MRI/MRS methods to target specific molecules. The optimal control method was used to efficiently prepare the singlet spin orders of varied multi-spin systems and in turn greatly expand the choice of the targeted molecules in the molecularly targeted MRI/MRS. Several molecules, such as N-acetyl-L-aspartic acid (NAA), dopamine (DA), and a tripeptide (alanine-glycine-glycine, AGG), have been used as targeted molecules for molecularly targeted MRI and MRS. We show in vivo NAA-targeted 1H MRS spectrum of a human brain. The high-resolution signal of NAA suggests a promising way to study important issues in molecular biology at the molecular level, e.g., measuring the local pH value of tissue in vivo, demonstrating the high potential of such methods in medicine.

Performance of Artificial Intelligence-Aided Diagnosis System for Clinically Significant Prostate Cancer with MRI: A Diagnostic Comparison Study.

BACKGROUND: The high level of expertise required for accurate interpretation of prostate MRI. PURPOSE: To develop and test an artificial intelligence (AI) system for diagnosis of clinically significant prostate cancer (CsPC) with MRI. STUDY TYPE: Retrospective. SUBJECTS: One thousand two hundred thirty patients from derivation cohort between Jan 2012 and Oct 2019, and 169 patients from a publicly available data (U-Net: 423 for training/validation and 49 for test and TrumpeNet: 820 for training/validation and 579 for test). FIELD STRENGTH/SEQUENCE: 3.0T/scanners, T2 -weighted imaging (T2 WI), diffusion-weighted imaging, and apparent diffusion coefficient map. ASSESSMENT: Close-loop AI system was trained with an Unet for prostate segmentation and a TrumpetNet for CsPC detection. Performance of AI was tested in 410 internal and 169 external sets against 24 radiologists categorizing into junior, general and subspecialist group. Gleason score >6 was identified as CsPC at pathology. STATISTICAL TESTS: Area under the receiver operating characteristic curve (AUC-ROC); Delong test; Meta-regression I2 analysis. RESULTS: In average, for internal test, AI had lower AUC-ROC than subspecialists (0.85 vs. 0.92, P < 0.05), and was comparable to junior (0.84, P = 0.76) and general group (0.86, P = 0.35). For external test, both AI (0.86) and subspecialist (0.86) had higher AUC than junior (0.80, P < 0.05) and general reader (0.83, P < 0.05). In individual, it revealed moderate diagnostic heterogeneity in 24 readers (Mantel-Haenszel I2  = 56.8%, P < 0.01), and AI outperformed 54.2% (13/24) of readers in summary ROC analysis. In multivariate test, Gleason score, zonal location, PI-RADS score and lesion size significantly impacted the accuracy of AI; while effect of data source, MR device and parameter settings on AI performance is insignificant (P > 0.05). DATA CONCLUSION: Our AI system can match and to some case exceed clinicians for the diagnosis of CsPC with prostate MRI. EVIDENCE LEVEL: 3 TECHNICAL EFFICACY: Stage 2.

Distinguishing glutamate and glutamine in in vivo 1 H MRS based on nuclear spin singlet order filtering.

PURPOSE: The signals of glutamate (Glu) and glutamine (Gln) are often significantly overlapped in routine 1 H-MR spectra of human brain in vivo. Selectively probing the signals of Glu and Gln in vivo is very important for the study of the metabolisms in which Glu and Gln are involved. METHODS: The Glu-/Gln- targeted pulse sequences are developed to selectively probe the signals of Glu and Gln. The core part of the Glu-/Gln- targeted pulse sequences lies on the preparation of the nuclear spin singlet orders (SSOs) of the five-spin systems of Glu and Gln. The optimal control method is used to prepare the SSOs of Glu and Gln with high efficiency. RESULTS: The Glu-/Gln- targeted pulse sequences have been applied on phantoms to selectively probe the signals of Glu and Gln. Moreover, in the in vivo experiments, the signals of Glu and Gln in human brains of healthy subjects have been successfully probed separately. CONCLUSION: The developed Glu-/Gln- targeted pulse sequences can be used to distinguish the 1 H-MR signals of Glu and Gln in human brains in vivo. The optimal control method provides an effective way to prepare the SSO of a specific spin system with high efficiency and in turn selectively probe the signals of a targeted molecule.

Predictive Value of Preoperative Dynamic Contrast-Enhanced MRI Imaging Features in Breast Cancer Patients with Postoperative Recurrence Time.

Although the implementation of surgery has reduced the mortality of breast cancer, postoperative recurrence is still an important problem bothering patients. DCE-GMRI can not only clearly display the morphological characteristics of breast lesions but also dynamically observe the blood perfusion of the lesions. On account of this, we explored the predictive value of preoperative dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) imaging features in breast cancer patients on postoperative recurrence time of breast cancer. The results showed that DCE-MRI images can clearly show the hemodynamic characteristics and morphological characteristics of tumor lesions, and have important value in predicting the recurrence time of breast cancer after surgery. The prognosis of early recurrence of breast cancer is worse. DCE-MRI can predict the time of postoperative recurrence and provide important clinical references.

Direct observation of geometric and sliding ferroelectricity in an amphidynamic crystal.

Sliding ferroelectricity is a recently observed polarity existing in two-dimensional materials. However, due to the weak polarization and poor electrical insulation in these materials, existing experimental evidences are indirect and mostly based on nanoscale transport properties or piezoresponse force microscopy. We report the direct observation of sliding ferroelectricity, using a high-quality amphidynamic single crystal (15-crown-5)Cd3Cl6, which possesses a large bandgap and so allows direct measurement of polarization-electric field hysteresis. This coordination polymer is a van der Waals material, which is composed of inorganic stators and organic rotators as determined by X-ray diffraction and NMR characterization. From density functional theory calculations, we find that after freezing the rotators, an electric dipole is generated in each layer driven by the geometric mechanism, while a comparable ferroelectric polarization originates from the interlayer sliding. The net polarization of these two components can be directly measured and manipulated. Our finding provides insight into low-dimensional ferroelectrics, especially control of the synchronous dynamics of rotating molecules and sliding layers in solids.

The construction of a two-dimensional organic-inorganic hybrid double perovskite ferroelastic with a high T c and narrow band gap.

Two-dimensional (2D) hybrid double perovskites have attracted extensive research interest for their fascinating physical properties, such as ferroelectricity, X-ray detection, light response and so on. In addition, ferroelastics, as an important branch of ferroic materials, exhibits wide prospects in mechanical switches, shape memory and templating electronic nanostructures. Here, we designed a 2D phase-transition double perovskite ferroelastic through a structurally progressive strategy. This evolution is core to our construction process from 0D to 1D and AgBi-based 2D. In this way, we successfully synthesized 2D lead-free ferroelastic (DPA)4AgBiBr8 (DPA = 2,2-dimethylpropan-1-aminium) with a high Curie temperature (T c), which shows a narrower band gap than 0D (DPA)4Bi2Br10 and 1D (DPA)5Pb2Br9. Moreover, the mechanism of structural phase transition and molecular motion are fully characterized by temperature dependent solid-state NMR and single crystal XRD. (DPA)4AgBiBr8 injects power into the discovery of new ferroelastics or the construction and dimensional adjustment in new hybrid double perovskites.

Unexpected Role of Short Chains in Entangled Polymer Networks.

The knowledge of chain entanglement is key to our understanding of the relation between the viscoelastic properties of polymeric material and their microscopic structure and dynamics. This work conducted a detailed study on the role of short chains in the entangled polymer network. A series of poly(ethylene oxide) (PEO) mixtures with bimodal molecular weight distribution were selected for this study. 1H double-quantum (DQ) NMR combined with the rheology measurement was used to investigate the entangled polymer network. We found that short-chain polymers have the potential to significantly alter the entangled polymer network formed by long-chain polymers. Additionally, both the amount of chain ends and the size of the short-chain polymer were found to have clear disentanglement influences on the entangled polymer network. Moreover, adding low molecular weight PEO to the entangle framework formed by the high molecular weight PEO, resulted in the formation of inhomogeneous entangled polymer networks. The effect of low molecular weight polymers on the entangled polymer networks in PEO melts provides a perspective on the molecular level effect of molecular weight distribution (MWD) on entanglement polymer networks.

Surface Passivation and Energetic Modification Suppress Nonradiative Recombination in Perovskite Solar Cells.

Surface passivation via post-treatment is an important strategy for improving power conversion efficiency and operational stability of perovskite solar cells. However, so far the interaction mechanisms between passivating additive and perovskite are not well understood. Here, we report the atomic-scale interaction of surface passivating additive 2,2-difluoroethylammonium bromine (2FEABr) on the MAPbI3. It is found that the bulky 2FEA+ cations tend to distribute at film surface, while the Br- anions diffuse from surface into bulk. A combination of 19F, 207Pb, and 2H solid-state NMR further reveal the Br- anions' partial substitution for the I- sites, the restricted motion of partial MA+ cations, and the firmed perovskite lattices, which would improve charge transport and stability of the perovskite films. Optical spectroscopy and ultraviolet photoelectron spectroscopy demonstrate that the 2FEABr induced surface passivation and energetic modification suppress the nonradiative recombination loss. These findings enable the efficiency of the p-i-n structured PSC significantly increasing from 19.44 to 21.06%, accompanied by excellent stability. Our work further establishes more knowledge link between passivating additive and PSC performance.

Self-Enhanced Acoustic Impedance Difference Strategy for Detecting the Acidic Tumor Microenvironment.

B-mode ultrasound imaging is a significant anatomic technique in clinic, which can display the anatomic variation in tissues. However, it is difficult to evaluate the functional state of organs and display the physiological information in organisms such as the tumor acidic microenvironment (TME). Herein, inspired by the phenomenon of sonographic acoustic shadow during detecting calculus in clinic, a strategy of self-enhanced acoustic impedance difference is proposed to monitor the acidic TME. BiF3@PDA@PEG (BPP) nanoparticles can self-aggregate in a specific response to the acidic TME to form huge "stones" BiF3@PDA, resulting in an increase of local tumor density, and further causing a significant acoustic impedance difference. In in vitro experiments, the enhanced ultrasound signals change from 15.2 to 196.4 dB, which can discriminate different pH values from 7.0 to 5.0, and the sensitivity can reach to 0.2 value. In in vivo experiments, the enhanced ultrasound signal is 107.7 dB after BPP self-aggregated, displaying the weak acidic TME that has a close relationship with the size and species of the tumor. More importantly, the accuracy is away from the interference of pressure because huge "stones" BiF3@PDA change little. However, SonoVue microbubbles will diffuse and rupture under pressure, which results in false positive signals. To sum up, this strategy will be helpful to the further development of ultrasound molecular imaging.

Multiple-targeting NMR signal selection by optimal control of nuclear spin singlet.

Selectively probing specific molecules in complex mixtures with nuclear magnetic resonance promises new insights into molecular structures or molecular interaction. Such a study often can be further facilitated when two or more objects in chemical moieties of interest can be precisely targeted. Herein, we proposed a novel method to implement the multiple-targeting signal selection by optimal control of the spin singlets of two or more targeted spin systems from one or more molecules. This method can endow the conventional nuclear magnetic resonance (NMR), magnetic resonance image (MRI) and magnetic resonance spectrum (MRS) with the multiple-targeting signal selectivity to selectively probe several targeted molecules and/or chemical groups simultaneously.

Rapid Identification of Adulteration in Edible Vegetable Oils Based on Low-Field Nuclear Magnetic Resonance Relaxation Fingerprints.

Most current approaches applied for the essential identification of adulteration in edible vegetable oils are of limited practical benefit because they require long analysis times, professional training, and costly instrumentation. The present work addresses this issue by developing a novel simple, accurate, and rapid identification approach based on the magnetic resonance relaxation fingerprints obtained from low-field nuclear magnetic resonance spectroscopy measurements of edible vegetable oils. The relaxation fingerprints obtained for six types of edible vegetable oil, including flaxseed oil, olive oil, soybean oil, corn oil, peanut oil, and sunflower oil, are demonstrated to have sufficiently unique characteristics to enable the identification of the individual types of oil in a sample. By using principal component analysis, three characteristic regions in the fingerprints were screened out to create a novel three-dimensional characteristic coordination system for oil discrimination and adulteration identification. Univariate analysis and partial least squares regression were used to successfully quantify the oil adulteration in adulterated binary oil samples, indicating the great potential of the present approach on both identification and quantification of edible oil adulteration.