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At least 703 records · Page 39

Regio‐Regular Polymer Acceptors Enabled by Determined Fluorination on End Groups for All‐Polymer Solar Cells with 15.2 % Efficiency

Abstract Polymerization sites of small molecule acceptors (SMAs) play vital roles in determining device performance of all‐polymer solar cells (all‐PSCs). Different from our recent work about fluoro‐ and bromo‐ co‐modified end group of IC‐FBr (a mixture of IC‐FBr1 and IC‐FBr2), in this paper, we synthesized and purified two regiospecific fluoro‐ and bromo‐ substituted end groups (IC‐FBr‐ o & IC‐FBr‐ m ), which were then employed to construct two regio‐regular polymer acceptors named PYF‐T‐ o and PYF‐T‐ m , respectively . In comparison with its isomeric counterparts named PYF‐T‐ m with different conjugated coupling sites, PYF‐T‐ o exhibits stronger and bathochromic absorption to achieve better photon harvesting. Meanwhile, PYF‐T‐ o adopts more ordered inter‐chain packing and suitable phase separation after blending with the donor polymer PM6, which resulted in suppressed charge recombination and efficient charge transport. Strikingly, we observed a dramatic performance difference between the two isomeric polymer acceptors PYF‐T‐ o and PYF‐T‐ m . While devices based on PM6:PYF‐T‐ o can yield power conversion efficiency (PCE) of 15.2 %, devices based on PM6:PYF‐T‐ m only show poor efficiencies of 1.4 %. This work demonstrates the success of configuration‐unique fluorinated end groups in designing high‐performance regular polymer acceptors, which provides guidelines towards developing all‐PSCs with better efficiencies.

Yu, Han↗

Combined Precursor Engineering and Grain Anchoring Leading to MA‐Free, Phase‐Pure, and Stable α‐Formamidinium Lead Iodide Perovskites for Efficient Solar Cells

Abstract α‐Formamidinium lead iodide (α‐FAPbI 3 ) is one of the most promising candidate materials for high‐efficiency and thermally stable perovskite solar cells (PSCs) owing to its outstanding optoelectrical properties and high thermal stability. However, achieving a stable form of α‐FAPbI 3 where both the composition and the phase are pure is very challenging. Herein, we report on a combined strategy of precursor engineering and grain anchoring to successfully prepare methylammonium (MA)‐free and phase‐pure stable α‐FAPbI 3 films. The incorporation of volatile FA‐based additives in the precursor solutions completely suppresses the formation of non‐perovskite δ‐FAPbI 3 during film crystallization. Grains of the desired α‐phase are anchored together and stabilized when 4‐ tert ‐butylbenzylammonium iodide is permeated into the α‐FAPbI 3 film interior via grain boundaries. This cooperative scheme leads to a significantly increased efficiency close to 21 % for FAPbI 3 perovskite solar cells. Moreover, the stabilized PSCs exhibit improved thermal stability and maintained ≈90 % of their initial efficiency after storage at 50 °C for over 1600 hours.

Ling, Xufeng↗

The Function of Two Radical‐SAM Enzymes, HcgA and HcgG, in the Biosynthesis of the [Fe]‐Hydrogenase Cofactor

Abstract In the biosynthesis of the iron‐guanylylpyridinol (FeGP) cofactor, 6‐carboxymethyl‐5‐methyl‐4‐hydroxy‐2‐pyridinol ( 1 ) is 3‐methylated to form 2 , then 4‐guanylylated to form 3 , and converted into the full cofactor. HcgA‐G proteins catalyze the biosynthetic reactions. Herein, we report the function of two radical S ‐adenosyl methionine enzymes, HcgA and HcgG, as uncovered by in vitro complementation experiments and the use of purified enzymes. In vitro biosynthesis using the cell extract from the Methanococcus maripaludis Δ hcgA strain was complemented with HcgA or precursors 1 , 2 or 3 . The results suggested that HcgA catalyzes the biosynthetic reaction that forms 1 . We demonstrated the formation of 1 by HcgA using the 3 kDa cell extract filtrate as the substrate. Biosynthesis in the Δ hcgG system was recovered by HcgG but not by 3 , which indicated that HcgG catalyzes the reactions after the biosynthesis of 3 . The data indicated that HcgG contributes to the formation of CO and completes biosynthesis of the FeGP cofactor.

Arriaza‐Gallardo, Francisco J.↗

Modifikation eines Cu‐Pd‐Schaufelrad‐Metall‐Organischen Gerüsts für die selektive CO 2 ‐Elektroreduktion

Abstract Die Optimierung der Bindungsenergie zwischen dem Intermediat und dem aktiven Zentrum ist ein entscheidender Faktor, um die katalytische Produktselektivität und Aktivität bei der elektrochemischen Kohlendioxidreduktion (CO 2 RR) zu steuern. Es ist bekannt, dass Kupferatome als aktive Zentren CO 2 zu Kohlenwasserstoffen und Sauerstoffverbindungen reduzieren, jedoch unter schlechter Produktselektivität leiden, da mehrere Intermediate nur moderate Bindungsenergien aufweisen. Hier berichten wir über eine Ionenaustauschstrategie zur Konstruktion von Cu−Pd‐Schaufelrad‐Dimeren innerhalb von Cu‐basierten metallorganischen Gerüsten (MOFs), [Cu 3‐x Pdx(BTC) 2 ] (BTC=1,3,5‐Benzoltricarbonsäure), ohne die strukturellen Eigenschaften des MOFs zu verändern. Im Vergleich zum reinen Cu‐MOF ([Cu 3 (BTC) 2 ], HKUST‐1) verlagert der Cu−Pd‐MOF die Produkte der CO 2 ‐Elektroreduktion von einer Vielzahl chemischer Spezies hin zu einer selektiven CO‐Erzeugung. Eine in situ‐Röntgenabsorptions‐Feinstrukturanalyse der Oxidationsstufe des Katalysators und der lokalen Geometrie, kombiniert mit theoretischen Berechnungen, zeigt, dass die Einfügung von Pd in die Knotenpunkte der Cu‐Schaufelradstruktur des MOFs die Adsorption des Schlüsselintermediats COOH* am Cu‐Zentrum fördert. Dies ermöglicht CO‐selektive katalytische Mechanismen und verbessert somit unser Verständnis über das Zusammenspiel von Struktur und Aktivität bei der elektrochemischen CO 2 ‐Reduktion unter Verwendung molekularer Katalysatoren.

Zhang, Ruirui↗

Twisted Tin‐Chloride Perovskite Single‐Crystal Heterostructures

Self-assembly affords simpler synthetic routes to heterostructures compared with manual layer-by-layer stacking, yet controlling interlayer twist angles in a bulk solid remains an outstanding challenge. We report two new single-crystal heterostructures: (Sn 2 Cl 2 )(CYS) 2 SnCl 4 (CYS = + NH 3 (CH 2 ) 2 S – ; Sn_CYS) and (Sn 2 Cl 2 )(SeCYS) 2 SnCl 4 (SeCYS = + NH 3 (CH 2 ) 2 Se – ; Sn_SeCYS) synthesized in solution, with alternating perovskite and intergrowth layers. Notably, compared to the recently reported lead analog, (Pb 2 Cl 2 )(CYS) 2 PbCl 4 (Pb_CYS), the tin heterostructures feature a twist between the perovskite and intergrowth layers. We trace this twist to local distortions at the Sn centers, which change the interfacial lattice-matching requirements compared to those of the Pb analog. Electronic band structure calculations show that the striking differences in the relative energies of perovskite- and intergrowth-derived bands in Sn_CYS and Pb_CYS arise from structural and not compositional differences. The structural anisotropy of Sn_CYS is also reflected in a large in-plane photoluminescence linear anisotropy ratio. Interfacial strain further affords differential incorporation of Pb into the perovskite and intergrowth layers of the Sn heterostructures, resulting in redshifted optical absorption onsets. Thus, we posit that local structural distortions may be exploited to manipulate the twist angle and interfacial strain in bulk heterostructures, providing a new handle for tuning the band alignments of bulk quantum-well electronic structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deactivation of Cu-Exchanged Automotive-Emission NH 3 -SCR Catalysts Elucidated with Nanoscale Resolution Using Scanning Transmission X-ray Microscopy

To gain insight into the underlying mechanisms of catalyst durability for the selective catalytic reduction (SCR) of NO x with an ammonia reductant, we employed scanning transmission X-ray microscopy (STXM) to study Cu-exchanged zeolites with the CHA and MFI framework structures before and after simulated 135 000-mile aging. X-ray absorption near-edge structure (XANES) measurements were performed at the Al K- and Cu L-edges. The local environment of framework Al, the oxidation state of Cu, and geometric changes were analyzed, showing a multi-factor-induced catalytic deactivation. In Cu-exchanged MFI, a transformation of Cu II to Cu I and Cu x O y was observed. We also found a spatial correlation between extra-framework Al and deactivated Cu species near the surface of the zeolite as well as a weak positive correlation between the amount of CuI and tri-coordinated Al. By inspecting both Al and Cu in fresh and aged Cu-exchanged zeolites, we conclude that the importance of the preservation of isolated Cu II sites trumps that of Brønsted acid sites for NH 3 -SCR activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photo–thermo Catalytic Oxidation over a TiO 2 ‐WO 3 ‐Supported Platinum Catalyst

Abstract Photo–thermo catalysis, which integrates photocatalysis on semiconductors with thermocatalysis on supported nonplasmonic metals, has emerged as an attractive approach to improve catalytic performance. However, an understanding of the mechanisms in operation is missing from both the thermo‐ and photocatalytic perspectives. Deep insights into photo–thermo catalysis are achieved via the catalytic oxidation of propane (C 3 H 8 ) over a Pt/TiO 2 ‐WO 3 catalyst that severely suffers from oxygen poisoning at high O 2 /C 3 H 8 ratios. After introducing UV/Vis light, the reaction temperature required to achieve 70 % conversion of C 3 H 8 lowers to a record‐breaking 90 °C from 324 °C and the apparent activation energy drops from 130 kJ mol −1 to 11 kJ mol −1 . Furthermore, the reaction order of O 2 is −1.4 in dark but reverses to 0.1 under light, thereby suppressing oxygen poisoning of the Pt catalyst. An underlying mechanism is proposed based on direct evidence of the in‐situ‐captured reaction intermediates.

Kang, Leilei↗

Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts

Although hexagonal boron nitride (h-BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas-phase methyl radicals (CH 3 . ) in the ODHP reaction over boron-based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV-PIMS), which uncovers the existence of gas-phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C-H activation of propane, while C 2 and C 1 products can be formed via both surface-mediated and gas-phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nickel–Mediated Trifluoromethylation of Phenol Derivatives by Aryl C–O Bond Activation

The increasing pharmaceutical importance of trifluoromethylarenes has stimulated the development of more efficient trifluoromethylation reactions. Tremendous efforts have focused on copper– and palladium–mediated/catalyzed trifluoromethylation of aryl halides. In contrast, no general method exists for the conversion of widely available inert electrophiles, such as phenol derivatives, into the corresponding trifluoromethylated arenes. Reported herein is a practical nickel–mediated trifluoromethylation of phenol derivatives with readily available trimethyl(trifluoromethyl)silane (TMSCF 3 ). The strategy relies on PMe 3 –promoted oxidative addition and transmetalation, and CCl 3 CN–induced reductive elimination. Here, the broad utility of this transformation has been demonstrated through the direct incorporation of trifluoromethyl into aromatic and heteroaromatic systems, including biorelevant compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Regio‐Regular Polymer Acceptors Enabled by Determined Fluorination on End Groups for All‐Polymer Solar Cells with 15.2 % Efficiency

Abstract Polymerization sites of small molecule acceptors (SMAs) play vital roles in determining device performance of all‐polymer solar cells (all‐PSCs). Different from our recent work about fluoro‐ and bromo‐ co‐modified end group of IC‐FBr (a mixture of IC‐FBr1 and IC‐FBr2), in this paper, we synthesized and purified two regiospecific fluoro‐ and bromo‐ substituted end groups (IC‐FBr‐ o & IC‐FBr‐ m ), which were then employed to construct two regio‐regular polymer acceptors named PYF‐T‐ o and PYF‐T‐ m , respectively . In comparison with its isomeric counterparts named PYF‐T‐ m with different conjugated coupling sites, PYF‐T‐ o exhibits stronger and bathochromic absorption to achieve better photon harvesting. Meanwhile, PYF‐T‐ o adopts more ordered inter‐chain packing and suitable phase separation after blending with the donor polymer PM6, which resulted in suppressed charge recombination and efficient charge transport. Strikingly, we observed a dramatic performance difference between the two isomeric polymer acceptors PYF‐T‐ o and PYF‐T‐ m . While devices based on PM6:PYF‐T‐ o can yield power conversion efficiency (PCE) of 15.2 %, devices based on PM6:PYF‐T‐ m only show poor efficiencies of 1.4 %. This work demonstrates the success of configuration‐unique fluorinated end groups in designing high‐performance regular polymer acceptors, which provides guidelines towards developing all‐PSCs with better efficiencies.

Yu, Han↗

Combined Precursor Engineering and Grain Anchoring Leading to MA-Free, Phase-Pure, and Stable α-Formamidinium Lead Iodide Perovskites for Efficient Solar Cells

a-Formamidinium lead iodide (a-FAPbI 3 ) is one of the most promising candidate materials for high-efficiency and thermally stable perovskite solar cells (PSCs) owing to its outstanding optoelectrical properties and high thermal stability. However, achieving a stable form of a-FAPbI 3 where both the composition and the phase are pure is very challenging. In this work, we report on a combined strategy of precursor engineering and grain anchoring to successfully prepare methylammonium (MA)-free and phase-pure stable a-FAPbI 3 films. The incorporation of volatile FA-based additives in the precursor solutions completely suppresses the formation of non-perovskite d-FAPbI 3 during film crystallization. Grains of the desired a-phase are anchored together and stabilized when 4-tert-butylbenzylammonium iodide is permeated into the a-FAPbI 3 film interior via grain boundaries. This cooperative scheme leads to a significantly increased efficiency close to 21% for FAPbI 3 perovskite solar cells. Moreover, the stabilized PSCs exhibit improved thermal stability and maintained ~90 % of their initial efficiency after storage at 50 degrees C for over 1600 hours.

14 SOLAR ENERGY↗

The Function of Two Radical‐SAM Enzymes, HcgA and HcgG, in the Biosynthesis of the [Fe]‐Hydrogenase Cofactor

Abstract In the biosynthesis of the iron‐guanylylpyridinol (FeGP) cofactor, 6‐carboxymethyl‐5‐methyl‐4‐hydroxy‐2‐pyridinol ( 1 ) is 3‐methylated to form 2 , then 4‐guanylylated to form 3 , and converted into the full cofactor. HcgA‐G proteins catalyze the biosynthetic reactions. Herein, we report the function of two radical S ‐adenosyl methionine enzymes, HcgA and HcgG, as uncovered by in vitro complementation experiments and the use of purified enzymes. In vitro biosynthesis using the cell extract from the Methanococcus maripaludis Δ hcgA strain was complemented with HcgA or precursors 1 , 2 or 3 . The results suggested that HcgA catalyzes the biosynthetic reaction that forms 1 . We demonstrated the formation of 1 by HcgA using the 3 kDa cell extract filtrate as the substrate. Biosynthesis in the Δ hcgG system was recovered by HcgG but not by 3 , which indicated that HcgG catalyzes the reactions after the biosynthesis of 3 . The data indicated that HcgG contributes to the formation of CO and completes biosynthesis of the FeGP cofactor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design of Multicomponent Peptide Fibrils with Ordered and Programmable Compositional Patterns

Advanced applications of biomacromolecular assemblies require a stringent degree of control over molecular arrangement, which is a challenge to current synthetic methods. Here we used a neighbor-controlled patterning strategy to build multicomponent peptide fibrils with an unprecedented capacity to manipulate local composition and peptide positions. Eight peptides were designed to have regulable nearest neighbors upon co-assembly, which, by simulation, afforded 412 different patterns within fibrils, with varied compositions and/or peptide positions. The fibrils with six prescribed patterns were experimentally constructed with high accuracy. The controlled patterning also applies to functionalities appended to the peptides, as exemplified by arranging carbohydrate ligands at nanoscale precision for protein recognition. Importantly, this study offers a route to molecular editing of inner structures of peptide assemblies, prefiguring the uniqueness and richness of patterning-based material design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preserving Structurally Labile Peptide Nanosheets After Molecular Functionalization of the Self-Assembling Peptides

A significant challenge in creating supramolecular materials is that conjugating molecular functionalities to building blocks often results in dissociation or undesired morphological transformation of their assemblies. Here we present a facile strategy to preserve structurally labile peptide assemblies after molecular modification of the self-assembling peptides. Sheet-forming peptides are designed to afford a staggered alignment with the segments bearing chemical modification sites protruding from the sheet surfaces. The staggered assembly allows for simultaneous separation of attached molecules from each other and from the underlying assembly motifs. Strikingly, using PEGs as the external molecules, PEG 400 - and PEG 700 -peptide conjugates directly self-associate into nanosheets with the PEG chains localized on the sheet surfaces. In contrast, the sheet formation based on in-register lateral packing of peptides does not recur upon the peptide PEGylation. This strategy allows for fabrication of densely modified assemblies with a variety of molecules, as demonstrated using biotin (hydrophobic molecule), c(RGDfK) (cyclic pentapeptide), and nucleic acid aptamer (negatively charged ssDNA). The staggered co-assembly also enables extended tunability of the amount/density of surface molecules, as exemplified by screening ligand-appended assemblies for cell targeting. In conclusion, this study paves the way for functionalization of historically challenging fragile assemblies while maintaining their overall morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering a Cu‐Pd Paddle‐Wheel Metal–Organic Framework for Selective CO 2 Electroreduction

Optimizing the binding energy between the intermediate and the active site is a key factor for tuning catalytic product selectivity and activity in the electrochemical carbon dioxide reduction reaction. Copper active sites are known to reduce CO 2 to hydrocarbons and oxygenates, but suffer from poor product selectivity due to the moderate binding energies of several of the reaction intermediates. Here, we report an ion exchange strategy to construct Cu−Pd paddle wheel dimers within Cu-based metal–organic frameworks (MOFs), [Cu 3-x Pd x (BTC) 2 ] (BTC=benzentricarboxylate), without altering the overall MOF structural properties. Compared to the pristine Cu MOF ([Cu 3 (BTC) 2 ], HKUST-1), the Cu−Pd MOF shifts CO 2 electroreduction products from diverse chemical species to selective CO generation. In situ X-ray absorption fine structure analysis of the catalyst oxidation state and local geometry, combined with theoretical calculations, reveal that the incorporation of Pd within the Cu−Pd paddle wheel node structure of the MOF promotes adsorption of the key intermediate COOH* at the Cu site. This permits CO-selective catalytic mechanisms and thus advances our understanding of the interplay between structure and activity toward electrochemical CO 2 reduction using molecular catalysts.

CO2 electroreduction reaction↗

Symmetry‐Breaking Strategy Yields Dopant‐Free Small Molecule Hole Transport Materials for Inorganic Perovskite Solar Cells with 20.58% Efficiency and Outstanding Stability

Abstract Inorganic perovskites are known for their excellent photothermal stability; however, the photothermal stability of all‐inorganic n‐i‐p perovskite solar cells (PSCs) is compromised due to ion diffusion and free radical‐induced degradation caused by the use of doped spiro‐OMeTAD hole transport materials (HTMs). In this study, two isomeric donor–acceptor–donor (D–A–D) type small molecules, namely HBT and HiBT, were developed and used as dopant‐free HTMs, using 2,1,3‐benzothiadiazole or benzo[d][1,2,3]thiadiazole as acceptor moieties. The HiBT molecule, with its symmetry‐breaking features, exhibits a large dipole moment, enhanced coordination‐active sites, and a well‐aligned energy level structure, all of which contribute to passivating perovskite surface defects and improving free charge separation. As a result, inorganic CsPbI 3 PSCs with HiBT HTM achieved an impressive power conversion efficiency (PCE) of 20.58%, the highest reported for dopant‐free HTM‐based inorganic PSCs. Moreover, the enhanced hydrophobic properties of HiBT molecules, coupled with their ability to passivate perovskite surface defects, contribute to significantly improved device stability. The unencapsulated devices based on HiBT HTM retained over 83% and 80% of their initial efficiency after being stored at 85 °C for 50 days and undergoing maximum power point (MPP) tracking at 85 °C for 1100 h, respectively. These results highlight that the symmetry‐breaking strategy is an exceptionally effective approach for designing efficient, dopant‐free small molecule HTMs, significantly contributing to both the high efficiency and enhanced stability of all‐inorganic PSCs.

Chemistry↗

Photocatalytic Overall Water Splitting at the Integrated Rh–MoRhO x Cluster Heterostructure on InGaN/GaN Nanowires

The quest for efficient solar-driven water splitting, a promising avenue for clean fuel production, faces challenges due to limited solar energy conversion efficiency. Traditional approaches study the overall water splitting as two spatially separate half reactions on two unrelated sites, hindering full utilization of photogenerated charge and water molecules. To overcome these limitations, an integrated cluster heterostructure catalyst on InGaN/GaN semiconductor nanowires is proposed for the effective utilization of photogenerated charge carriers and water molecules on the same redox localization. By establishing the fast charge extraction kinetics based on InGaN/GaN nanowires, the integration of Rh and MoRhOx clusters on the nanowire surface enables simultaneous and fast hydrogen/oxygen evolution reactions at the cluster heterostructure. Furthermore, the integrated strategy can enhance the charge redistribution across the heterostructure between the two clusters, further optimizing adsorption of reaction intermediates on each cluster for boosted photocatalytic water splitting activity. Consequently, the integrated heterostructure triggers a 40-fold increased hydrogen production efficiency in an artificial leaf system. This study provides valuable insights for the rational design of advanced heterostructured photocatalysts for water splitting and beyond.

GaN nanowire↗

A nomogram for prediction of stage III/IV gastric cancer outcome after surgery: A multicenter population‐based study

Abstract Most patients with gastric cancer (GC) are first diagnosed at stage III‐IV and surgery resection remains the primary therapeutic modality for these patients. However, clinical staging used for prediction of those patients provides limited information. We collected clinicopathological data and disease‐progression information from 508 patients with stage III‐IV GC at three Chinese hospitals and 1298 patients from the Surveillance, Epidemiology, and End Results database. Based on the stepwise multivariate regression model, we constructed a novel nomogram to predict overall survival (OS). The performance of discrimination for this model was measured using Harrell's concordance index (C‐index) and receiver‐operating characteristic curve (ROC), and was validated using calibration plots. Multivariate Cox regression analyses showed that tumor size, age at diagnosis, N stage, tumor grade, and distant metastases were outstanding independent prognostic factors of stage III‐IV GC. We developed a nomogram based on these five prognostic predictors. In the training set, the C‐index of the nomogram was 0.645 (95% CI: 0.611‐0.679), which was higher than that of the American Joint Committee on Cancer TNM system alone (sixth TNM: 0.544; seventh TNM: 0.575; eighth TNM: 0.568). Similar results were observed in validation cohort. Moreover, calibration blots demonstrated good consistency between the actual and predicted OS probabilities. According to the nomogram, GC individuals could be classified into three groups (low‐, middle‐, and high‐risk) ( P < .001). Our nomogram complements the current staging system for prediction of individual prognosis with stage III‐IV GC, and may be helpful for making individualized treatment decisions.

Gao, Zhiying↗