bluuebunny/crossref_metadata_2025 huggingface dataset:
Antifreezing Proton Zwitterionic Hydrogel Electrolyte via Ionic Hopping and Grotthuss Transport Mechanism toward Solid Supercapacitor Working at −50 °C
Authors: Sun Weigang , Xu Zhen , Qiao Congde , Lv Bingxi , Gai Ligang , Ji Xingxiang , Jiang Haihui , Liu Libin
Published: July 2022

Hydrogel electrolyte is widely used in solid energy storage devices because of its high ionic conductivity, environmental friendliness, and non‐leakage property. However, hydrogel electrolyte is not resistant to freezing. Here, a high proton conductive zwitterionic hydrogel electrolyte with super conductivity of 1.51 mS cm–1 at −50 °C is fabricated by random copolymerization of acrylamide and zwitterionic monomer in the presence of 1 m H2SO4 and ethylene glycol (EG). The antifreezing performance and low temperature conductivity are ascribed to hydrogen bonds and ionic bonds between the components and water molecules in the system and can be tuned by changing the monomer ratio and EG contents. The proton hopping migration on the ionic group of the polymer chains and Grotthuss proton transport mechanism are responsible for the high proton conductivity while Grotthuss transport is dominated at the glassy state of the polymer chains. The electrolyte‐assembled supercapacitor (SC) offers high specific capacitance of 93.5 F g–1 at 25 °C and 62.0 F g–1 at −50 °C with a capacitance retention of 91.1% and 81.5% after 10 000 cycles, respectively. The SC can even work at −70 °C. The electrolyte outperforms most reported antifreezing hydrogel electrolytes and has high potential in low‐temperature devices.
Stabilizing Layered Structure in Aqueous Electrolyte via O2‐Type Oxygen Stacking
Authors: Xue Liang , Wang Chao , Liu Hanghui , Li Hao , Chen Tingting , Shi Zhengyi , Qiu Ce , Sun Mingqing , Huang Yin , Huang Jiangfeng , Sun Jingwen , Xiong Pan , Zhu Junwu , Xia Hui
Published: July 2022

Despite the high energy density of O3‐type layered cathode materials, the short cycle life in aqueous electrolyte hinders their practical applications in aqueous lithium‐ion batteries (ALIBs). In this work, it is demonstrated that the structural stability of layered LiCoO2 in aqueous electrolyte can be remarkably improved by altering the oxygen stacking from O3 to O2. As compared to the O3‐type LiCoO2, the O2‐type LiCoO2 exhibits significantly improved cycle performance in neutral aqueous electrolyte. It is found that the structural degradation caused by electrophilic attack of proton can be effectively mitigated in O2‐type layered structure. With O2 stacking, CoO6 octahedra in LiCoO2 possess stronger CoO bonds while Co migration from Co layer to Li layer is strongly hampered, resulting in enhanced structural stability against proton attack and prolonged cycle life in aqueous electrolyte. The findings in this work reveal that regulating oxygen stacking sequence is an effective strategy to improve the structural stability of layered materials for ALIBs.
Identifying and Differentiating Topological G‐Quadruplex Structures with DNA‐Encoded Plasmonic Gold Nanoparticles
Authors: Song Tingjie , Wang Xiaojing , Yao Dongbao , Liang Haojun , Lu Yi
Published: July 2022

DNA G‐quadruplexes (G4s) have been identified as critical elements in modulating genomic functions and many other biological processes. Their functions are highly dependent on the primary nucleotides and secondary folding structures. Therefore, to understand their functions, methods to identify and differentiate structures of G4 with speed and accuracy are required but limited. In this report, we have applied a synthetic G4 DNA‐encoded nanoparticle approach to identify and differentiate G4 DNA molecules with different topologies and nucleotide residues. We found that the resulting plasmonic properties of the gold nanoparticles, monitored by UV/Vis spectroscopy, are quite sensitive to different G4 structures, including stacking layers, loop sequences, capping bases on G4s, and topological structures. Through these systematic investigations, we demonstrate that this G4‐encoded gold nanoparticle approach can be used to profile the G4 structures and distinguish G4s from human telomeres. Such a method may have wide applications in G4 research.
Platinum‐Catalysed Selective Aerobic Oxidation of Methane to Formaldehyde in the Presence of Liquid Water
Authors: Mahlaba Sinqobile V. L. , Hytoolakhan Lal Mahomed Nasseela , Govender Alisa , Guo Junfeng , Leteba Gerard M. , Cilliers Pierre L. , van Steen Eric
Published: July 2022

The aerobic, selective oxidation of methane to C1‐oxygenates remains a challenge, due to the more facile, consecutive oxidation of formed products to CO2. Here, we report on the aerobic selective oxidation of methane under continuous flow conditions, over platinum‐based catalysts yielding formaldehyde with a high selectivity (reaching 90 % for Pt/TiO2 and 65 % over Pt/Al2O3) upon co‐feeding water. The presence of liquid water under reaction conditions increases the activity strongly attaining a methane conversion of 1–3 % over Pt/TiO2. Density‐functional theory (DFT) calculations show that the preferential formation of formaldehyde is linked to the stability of the di‐σ‐hydroxy‐methoxy species on platinum, the preferred carbon‐containing species on Pt(111) at a high chemical potential of water. Our findings provide novel insights into the reaction pathway for the Pt‐catalysed, aerobic selective oxidation of CH4.
Rational Design of Superconducting Metal Hydrides via Chemical Pressure Tuning**
Authors: Hilleke Katerina P. , Zurek Eva
Published: July 2022

The high critical superconducting temperatures (Tcs) of metal hydride phases with clathrate‐like hydrogen networks have generated great interest. Herein, we employ the Density Functional Theory‐Chemical Pressure (DFT‐CP) method to explain why certain electropositive elements adopt these structure types, whereas others distort the hydrogenic lattice, thereby decreasing the Tc. The progressive opening of the H24 polyhedra in MH6 phases is shown to arise from internal pressures exerted by large metal atoms, some of which may favor an even higher hydrogen content that loosens the metal atom coordination environments. The stability of the LaH10 and LaBH8 phases is tied to stuffing of their shared hydrogen network with either additional hydrogen or boron atoms. The predictive capabilities of DFT‐CP are finally applied to the Y−X−H system to identify possible ternary additions yielding a superconducting phase stable to low pressures.
Porphyrinbasiertes organisches Netzwerk bestehend aus nachhaltigen Kohlenstoffpunkten für die Photopolymerisation
Authors: Luo Xiongfei , Wan Jianyong , Meckbach Nicolai , Strehmel Veronika , Li Shujun , Chen Zhijun , Strehmel Bernd
Published: July 2022

Nachhaltige Kohlenstoffpunkte (CDs) auf der Basis von Furfural (F‐CD) führten nach Durchführung der Alder‐Longo‐Reaktion zu einem lichtempfindlichen Material. Die gebildete Porphyrineinheit verbindet die F‐CDs zu einem kovalenten organischen Netzwerk. Dieses heterogene Material (P‐CD) wurde mit XPS charakterisiert, was auf den Einbau der jeweiligen C‐, N‐ und O‐Einheiten hinweist. Zeitaufgelöste Fluoreszenz einschließlich der Globalanalyse zeigte einen Beitrag von drei verknüpften Komponenten zur Beschreibung der Gesamtdynamik des angeregten Zustands. Die elektrochemischen und photonischen Eigenschaften dieses heterogenen Materials ermöglichten eine Photopolymerisation mittels photo‐ATRP, bei der entweder CuBr2/TPMA, FeBr3/Br−oder ein metallfreier Ansatz die kontrollierte Polymerisation aktivierte. Kettenverlängerungsexperimente funktionierten in allen drei Fällen und zeigten die Aktivität der Endgruppe für die Aktivierung der kontrollierten Blockcopolymerisation unter Verwendung vonMMAund Styren als Monomere. Die traditionelle radikalische Polymerisation unter Einsatz eines Diaryliodoniumsalzes als Coinitiator scheiterte.
α‐Thianthrenium Carbonyl Species: The Equivalent of an α‐Carbonyl Carbocation
Authors: Jia Hao , Ritter Tobias
Published: July 2022

Here we report an α‐thianthrenium carbonyl species, as the equivalent of an α‐carbonyl carbocation, which is generated by the radical conjugate addition of a trifluoromethyl thianthrenium salt to Michael acceptors. The reactivity allows for the synthesis of Cα‐tetrasubstituted α‐ and β‐amino acid analogues via a Ritter reaction by addition of acetonitrile. Addition of hydroxide, methoxide, and even fluoride can afford α‐heteroatom substituted α‐phenylpropanoates.
Formation of Organic Acids and Carbonyl Compounds in n‐Butane Oxidation via γ‐Ketohydroperoxide Decomposition
Authors: Popolan‐Vaida Denisia M. , Eskola Arkke J. , Rotavera Brandon , Lockyear Jessica F. , Wang Zhandong , Sarathy S. Mani , Caravan Rebecca L. , Zádor Judit , Sheps Leonid , Lucassen Arnas , Moshammer Kai , Dagaut Philippe , Osborn David L. , Hansen Nils , Leone Stephen R. , Taatjes Craig A.
Published: July 2022

A crucial chain‐branching step in autoignition is the decomposition of ketohydroperoxides (KHP) to form an oxy radical and OH. Other pathways compete with chain‐branching, such as “Korcek” dissociation of γ‐KHP to a carbonyl and an acid. Here we characterize the formation of a γ‐KHP and its decomposition to formic acid+acetone products from observations of n‐butane oxidation in two complementary experiments. In jet‐stirred reactor measurements, KHP is observed above 590 K. The KHP concentration decreases with increasing temperature, whereas formic acid and acetone products increase. Observation of characteristic isotopologs acetone‐d3 and formic acid‐d0 in the oxidation of CH3CD2CD2CH3 is consistent with a Korcek mechanism. In laser‐initiated oxidation experiments of n‐butane, formic acid and acetone are produced on the timescale of KHP removal. Modelling the time‐resolved production of formic acid provides an estimated upper limit of 2 s−1 for the rate coefficient of KHP decomposition to formic acid+acetone.
Central Unit Fluorination of Non‐Fullerene Acceptors Enables Highly Efficient Organic Solar Cells with Over 18 % Efficiency
Authors: Chen Hongbin , Liang Huazhe , Guo Ziqi , Zhu Yu , Zhang Zhe , Li Zhixiang , Cao Xiangjian , Wang Haohui , Feng Wanying , Zou Yalu , Meng Lingxian , Xu Xiaoyun , Kan Bin , Li Chenxi , Yao Zhaoyang , Wan Xiangjian , Ma Zaifei , Chen Yongsheng
Published: July 2022

Halogenation of terminal of acceptors has been shown to give dramatic improvements in power conversion efficiencies (PCEs) of organic solar cells (OSCs). Similar significant results could be expected from the halogenation of the central units of state‐of‐the‐art Y‐series acceptors. Herein, a pair of acceptors, termed CH6 and CH4, featuring a conjugation‐extended phenazine central unit with and without fluorination, have been synthesized. The fluorinated CH6 has enhanced molecular interactions and crystallinity, superior fibrillar network morphology and improved charge generation and transport in blend films, thus affording a higher PCE of 18.33 % for CH6‐based binary OSCs compared to 16.49 % for the non‐fluorinated CH4. The new central site offers further opportunities for structural optimization of Y‐series molecules to afford better‐performed OSCs and reveals the effectiveness of fluorination on central units.
Carbonylative Cross‐Coupling Reaction of Allylic Alcohols and Organoalanes with 1 atm CO Enabled by Nickel Catalysis
Authors: Wang Chenglong , Wu Xianqing , Li Haiyan , Qu Jingping , Chen Yifeng
Published: July 2022

A nickel‐catalyzed three‐component carbonylative cross‐coupling reaction of allylic alcohols and organoalanes with CO at atmospheric pressure is reported, enabling the expedient formation of β,γ‐unsaturated ketones with broad scope. Particularly, the chemoselective allylic carbonylation of diols further highlights the practicability of this protocol. The leverage of organoalanes as both the coupling components and the activators for the alcohol functionalization is crucial for this method, thus no extraneous activators are required.
Constructing Interfacial Boron‐Nitrogen Moieties in Turbostratic Carbon for Electrochemical Hydrogen Peroxide Production
Authors: Tian Zhihong , Zhang Qingran , Thomsen Lars , Gao Nana , Pan Jian , Daiyan Rahman , Yun Jimmy , Brandt Jessica , López‐Salas Nieves , Lai Feili , Li Qiuye , Liu Tianxi , Amal Rose , Lu Xunyu , Antonietti Markus
Published: July 2022

The electrochemical oxygen reduction reaction (ORR) provides a green route for decentralized H2O2 synthesis, where a structure–selectivity relationship is pivotal for the control of a highly selective and active two‐electron pathway. Here, we report the fabrication of a boron and nitrogen co‐doped turbostratic carbon catalyst with tunable B−N−C configurations (CNB‐ZIL) by the assistance of a zwitterionic liquid (ZIL) for electrochemical hydrogen peroxide production. Combined spectroscopic analysis reveals a fine tailored B−N moiety in CNB‐ZIL, where interfacial B−N species in a homogeneous distribution tend to segregate into hexagonal boron nitride domains at higher pyrolysis temperatures. Based on the experimental observations, a correlation between the interfacial B−N moieties and HO2− selectivity is established. The CNB‐ZIL electrocatalysts with optimal interfacial B−N moieties exhibit a high HO2− selectivity with small overpotentials in alkaline media, giving a HO2− yield of ≈1787 mmol gcatalyst−1 h−1 at −1.4 V in a flow‐cell reactor.
A Porphyrin‐Based Organic Network Comprising Sustainable Carbon Dots for Photopolymerization
Authors: Luo Xiongfei , Wan Jianyong , Meckbach Nicolai , Strehmel Veronika , Li Shujun , Chen Zhijun , Strehmel Bernd
Published: July 2022

Sustainable carbon dots (CDs) based on furfuraldehyde (F‐CD) resulted in a photosensitive material after pursuing the Alder‐Longo reaction. The porphyrin moiety formed connects the F‐CDs in a covalent organic network. This heterogeneous material (P‐CD) was characterized by XPS indicating incorporation of the respective C, N and O moieties. Time resolved fluorescence including global analysis showed contribution of three linked components to the overall dynamics of the excited state. Electrochemical and photonic properties of this heterogeneous material facilitated photopolymerization in a photo‐ATRP setup where either CuBr2/TPMA, FeBr3/Br−or a metal free reaction setup activated controlled polymerization. Chain extension experiments worked in all three cases showing end group fidelity for activation of controlled block copolymerization usingMMAand styrene as monomers. Traditional radical polymerization using a diaryl iodonium salt as co‐initiator failed.
Chemoenzymatic Synthesis of a Rhamnose‐Functionalized Bispecific Nanobody as a Bispecific Antibody Mimic for Cancer Immunotherapy
Authors: Hong Haofei , Lin Han , Li Dan , Gong Liang , Zhou Kun , Li Yanchun , Yu Hangyan , Zhao Kai , Shi Jie , Zhou Zhifang , Huang Zhaohui , Wu Zhimeng
Published: July 2022

Bispecific antibodies (BsAbs) are next‐generation therapeutics for complex cancer treatment. Herein, we developed a dual‐targeting non‐IgG format of bsAbs by using a bispecific nanobody (bsNb) that can simultaneously target EGFR and HER2 on tumor cells. Site‐specific modification of the anti‐EGFR‐HER2 bsNb was conducted using the rhamnose (Rha) hapten via sortase A‐mediated ligation to reconstitute the missing crystallizable fragment (Fc) effector biological functions. Functionally similar to bsAbs, bsNb‐Rha conjugates retained dual‐targeting activity and exerted potent anticancer effects via the Fc‐domain‐mediated engagement of endogenous anti‐Rha antibodies. Further, an optimized bsNb‐Rha conjugate exhibited markedly improved pharmacokinetics and efficient inhibitory effects against xenograft tumor growth in vivo. Our strategy provides a general and cost‐effective platform to generate a new bsAb format for cancer immunotherapy.
Preparation of sulfur‐doped graphenes by Yucel's method and their corresponding polylactide‐based nanocomposites
Authors: Kahraman Yusuf , Gursu Hurmus , Arvas Melih Besir , Ersozoglu M. Giray , Nofar Mohammadreza , Sarac A. Sezai , Sahin Yucel
Published: July 2022

In this study, S‐doped graphene (SG) powders were produced in one‐step green and environmental‐friendly, quick, and cheap route of Yucel's method. Different sulfur functional groups were formed on graphene surfaces by changing the anodic potential range and were first used to prepare SG/polylactide (PLA) nanocomposites. The influence of applied potential on the structural properties of SG powders was explored through cyclic voltammetry (CV), X‐ray photoelectron spectroscopy (XPS), X‐ray diffractometry (XRD), thermogravimetric analysis (TGA), scanning electron microscope (SEM), and BET surface area analysis. S‐doped graphenes were subsequently melt mixed with polylactide at low contents of 0.1 and 0.5 wt% using a twin‐screw extruder. The interaction of SGs functional groups with PLA and its effect on the nanocomposites' final morphological, thermomechanical, and tensile properties was then studied. It was revealed that the tensile strength and modulus of the nanocomposites were noticeably increased with the addition of such low SGs contents. The applied potential and hence the structural properties of SGs differently influenced the final tensile properties of the nanocomposites. A maximum enhancement of around 100% in tensile strength was observed using only 0.1 wt% SG produced at the potential range of −1.5 and 2.3 V.
Synthesis of aromatic polyesters derived from bisphenol‐A and bis(hydroxyphenyl)butane with diacyl chloride monomers
Authors: Wang Zhoufeng , Ding Taoguo , Hu Junwei , Wang Bolin , Liu Yingying , Ding Guoxin
Published: July 2022

A series of aromatic polyesters were prepared by the reaction of bisphenol‐A and bis(hydroxyphenyl)butane with diacyl chloride monomers by phase transfer interfacial polycondensation in order to improve the processability of the bisphenol A‐based polyarylate. The microstructure, molecular weight, crystallinity, solubility, thermal properties, mechanical properties, and optical properties of the prepared copolyesters were investigated. Inherent viscosities of the copolyesters are in the range of 0.14–0.53 dl g−1, and their average molecular weights are 7362–44,413 g mol−1, respectively. The feed compositions and copolymer compositions were nearly identical. The results show that with the increase in the content of side ethyl units, the copolyester gradually transforms into an amorphous structure, which is also verified by the improvement in dissolution properties. When the copolyester backbone was introduced into the side ethyl units, the thermal decomposition temperature was less affected and varied in the range of about 10°C, while the value of glass transition temperature reduced from 196.5°C to 165.1°C. The mechanical properties of the polymers are similar to those of the industrial commodity U‐100. In addition, the copolyester films have good optical properties, and the transmittance reached the maximum value of 98.41% when the content of bis(hydroxyphenyl)‐butane was 10%.
Morphological, mechanical, and thermal properties of polyurethane nanocomposites co‐incorporated with micro‐Al2O3/nano‐Al2O3 for flexible thermal conductive component applications
Authors: Zhang Xuntao , Yang Jia , Yan Lei , Zhang Zhaoxin , Bian Jun , Lin Hailan , Chen Daiqiang
Published: July 2022

Thermoplastic polyurethane (TPU) nanocomposites (TPU/μmAl2O3‐ACA/nmAl2O3) with excellent mechanical, thermal stability and thermal conductivity were fabricated by co‐incorporating aluminate coupling agent DL‐411 chemically functionalized micron Al2O3 (μmAl2O3‐ACA) and nano‐Al2O3 (nmAl2O3) through melt blending method. FTIR analysis indicated that DL‐411 has been successfully grafted on the surface of μmAl2O3, which was beneficial to the homogeneous dispersion of Al2O3 particles and enhancements of interfacial interactions between Al2O3 particles and TPU matrix. Adding μmAl2O3‐ACA and nmAl2O3 simultaneously showed obvious synergistic effects on improving the mechanical properties of TPU nanocomposites. The optimum mechanical properties were obtained at the mass ratio of μmAl2O3‐ACA to nmAl2O3 of 3:1. Both μmAl2O3‐ACA and nmAl2O3 particles were homogeneously dispersed, constructing relatively perfect thermal conductivity networks, as verified by FESEM and PLM observations. The thermal conductivity (k) of TPU nanocomposites increased continuously with the addition of μmAl2O3‐ACA/nmAl2O3 particles, and the optimal k (0.28 W/m K) was achieved when the mass ratio of μmAl2O3‐ACA to nmAl2O3 was 3:1, which increased by 53% compared with pure TPU (k = 0.183 W/m K). TGA showed that, in contrast to those of pure TPU, the maximum decomposition temperature of TPU/μmAl2O3‐ACA/nmAl2O3 nanocomposites increased by 77.77°C, and the decomposition activation energy of TPU nanocomposite enhanced by 178%.
Recent Advances in the Chemistry of Heavier Group 14 Analogues of Carbonyls
Authors: Sun Tianyi , Li Jiazhong , Wang Hao
Published: July 2022

Heavier analogues of carbonyls, in the form of “R2E=O” (E=Si, Ge, Sn, Pb), feature a high polar E=O double bond. In contrast to carbonyl compounds, heavier analogues are extremely unstable and prone to proceed head‐to‐tail oligomerization. Thus, the isolation of such species under ambient conditions is a challenging synthetic target in main group chemistry. In recent years, much progress has been achieved in the synthesis and isolation of a variety of Lewis base/acid, Lewis base‐stabilized and even Lewis acid/base free heavier analogues. These compounds exhibit interesting reactivities, such as small molecule activation and metathesis reactions, indicating the potential of heavier analogues in synthetic chemistry. This review summarizes the recent achievements in the chemistry of Lewis base and/or acid stabilized heavier analogues of carbonyls, including synthetic approaches, structural parameters and reactivity of these isolable compounds.
Boron–Based Electrolytes for Rechargeable Magnesium Batteries: Biography and Perspective
Authors: Ren Wen , Cheng Mingxiang , Wang Yaru , Zhang Duo , Yang Yang , Yang Jun , Wang Jiulin , NuLi Yanna
Published: July 2022

Rechargeable magnesium batteries (RMBs) are a promising alternative in the post–lithium era for their high volumetric capacity, crustal abundance, and metallic safety. Electrolytes for RMBs have experienced a development process from the initial Grignard compound to today's diversified single magnesium salt. Among them, the boron‐based electrolyte plays a significant connecting link between the preceding and the following. This review retrospectively combed the origin and development course of boron–magnesium electrolyte and focuses on the application of three representatives: borohydride, boron‐center fluorinated alkoxylate, and closo–borane cluster. Fundamental understandings and typical concerns correlative with the Mg−B electrolyte designs are highlighted and briefly discussed. Finally, future direction and possible proposals for practical Mg−B electrolytes are put forward.
Improved production of heme using metabolically engineered Escherichia coli
Authors: Choi Kyeong Rok , Yu Hye Eun , Lee Hoseong , Lee Sang Yup
Published: July 2022

Heme has recently attracted much attention due to its promising applications in the food and healthcare industries. However, the current titers and productivities of heme produced by recombinant microorganisms are not high enough for a wide range of applications. In this study, the process for the fermentation of the metabolically engineered Escherichia coli HAEM7 strain was optimized for the high‐level production of heme. To improve the production of heme, different carbon sources, iron concentration in the medium, pH control strategies, induction points, and iron content in the feeding solution were examined. Moreover, strategies of increasing cell density, regular iron supplementation, and supply of excess feeding solution were developed to further improve the production of heme. In the optimized fermentation process, the HAEM7 strain produced 1.03 g/L heme with productivity of 21.5 mg/L/h. The fermentation process and strategies reported here will expedite establishing industry‐level production of heme.
Comparative pharmacokinetics of four major flavonoids in normal and chronic gastritis rats after oral administration of different combinations of Banxia Xiexin decoction
Authors: Zhou Zehua , Liu Wangzhenzu , Li Xue , Li Chan , An Rui , Liang Kun , Wang Xinhong
Published: July 2022

Chronic gastritis (CG) has become a major threat to human health. Banxia Xiexin Decoction (BXXXD) has been used clinically to treat gastritis by acting on the spleen and stomach for thousands of years. Baicalin, wogonoside, liquiritin and liquiritigenin are the main bioactive flavonoids of BXXXD. A rapid, sensitive and selective HPLC–triple quadrupole (TQ)–MS/MS method was developed to simultaneously quantify the four flavonoids in rat plasma in this study. With salidroside as internal standard (IS), plasma samples were extracted and separated on a Welch HPLC XB‐C18 column (2.1 × 50 mm, 1.8 μm) using gradient elution. The optimized gradient of the mobile phase consisted of water (containing 0.1% formic acid) (A) and methanol (B) was used. Detection was implemented in multiple reaction monitoring mode with an electrospray negative ionization source. The comparative pharmacokinetics of four analytes in normal and CG rats after oral administration of BXXXD or its different compatibilities were first investigated. The results indicated that the pharmacokinetic behaviors of analytes were obviously changed in CG rats. From the comparison between the whole prescription group and the compatibility groups, it was found that the pharmacokinetic behavior of analytes also changed to some extent. The pharmacokinetic alterations of analytes might be due to the pathological conditions of CG.
Efficacy and safety of pyrotinib‐containing regimen in the patients with HER2‐positive metastatic breast cancer: A multicenter real‐world study
Authors: Yin Sha , Chi Yajing , Du Yangyang , Wang Jingfen , Shan Changping , Yi Weiwei , Shang Mao , Man Xiaochu , Tan Qiaorui , Li Huihui
Published: July 2022

Background

Pyrotinib, a novel irreversible epidermal growth factor receptor 2 (EGFR)/HER2 dual tyrosine kinase inhibitor, has shown promising antitumor efficacy with tolerable toxicity in HER2‐positive metastatic breast cancer (MBC) in several clinical trials. However, the clinical trials do not usually well reflect the patients in real clinical settings. Despite several small‐sample studies in real world, the data on pyrotinib as first‐line and third‐or‐later‐line treatment and the efficacy comparison of pyrotinib combined with different regimens are still lacking. Therefore, this study aimed to investigate the efficacy and safety of pyrotinib for the HER2‐positive MBC in real world to replenish more comprehensive data.

Methods

A total of 172 HER2‐positive MBC patients treated with pyrotinib‐based therapy were recruited from multiple centers in nonclinical trial settings from September 2017 to June 2020.

Results

The median progression‐free survival (mPFS) of 172 patients was 8.83 months. The patients, receiving first‐line pyrotinib treatment, had the longest mPFS (20.93 months) compared with those receiving second‐line (8.67 months, p = 0.0339) and third‐or‐later‐line (7.13 months, p = 0.0075) treatments, respectively. Prior treatment with lapatinib (p = 0.012) and site of metastasis (visceral vs. nonvisceral) (p = 0.033) were the independent prognostic factors for PFS. The prior treatment with lapatinib compared with lapatinib‐native treatment (5.96 vs. 10.97 months, p = 0.0036) and those with visceral metastasis compared with nonvisceral metastasis (8.40 vs. 23.70 months, p = 0.0138) had worse mPFS. Among 146 patients evaluated for efficacy, 2.1%, 58.9%, and 32.9% showed complete response, partial response, and stable disease, respectively. Adverse events occurred in 92.4% of the patients with 33.3% Grade 3 and higher adverse events and diarrhea (57.0%), anemia (44.8%), and leukopenia (40.7%) as the most frequent ones.

Conclusions

Pyrotinib‐containing regimen could effectively treat HER2‐positive MBC with acceptable toxicity, including the patients who progressed after lapatinib treatment and with brain metastasis.
Physical activity, polygenic risk score, and colorectal cancer risk
Authors: Chen Xuechen , Guo Feng , Chang‐Claude Jenny , Hoffmeister Michael , Brenner Hermann
Published: July 2022

Introduction

Whether and to what extent the relationship between physical activity (PA) and colorectal cancer (CRC) differs according to CRC‐related genetic risk remains to be determined, and no studies to date have quantified how much genetically determined risk could be compensated for with active exercise.

Methods

Genetic risk was quantified by a polygenic risk score (PRS) summarizing the estimated effect of 140 CRC‐associated genetic variants. Associations of PA with CRC risk were estimated by multivariable logistic regression across PRS levels. We also compared the impact of PA and specific PA types to the PRS using “genetic risk equivalent (GRE)”, a novel approach to enhance effective risk communication.

Results

Among 5058 CRC patients and 4134 controls, we observed no significant association between overall PA level in quartiles and CRC risk. However, the highest versus lowest lifetime leisure time physical activity (LTPA) was associated with a 13% lower CRC risk [odds ratio 0.87, 95% confidence interval (CI) 0.77–1.00] independent of PRS levels (adjusted p value for interaction = 0.18). This effect was equivalent to the effect of having 11 percentiles lower PRS (GRE −10.6, 95% CI −20.7 to −0.6). The GRE (95% CI) for the highest lifetime sports tertile was −23.0 (−33.9 to −12.0).

Conclusions

LTPA was inversely associated with CRC risk irrespective of polygenic risk for CRC, which reinforces the importance of LTPA in CRC prevention among the general population. Adequate sports activity can compensate for a large share of polygenic risk for CRC.
The structural maintenance of chromosomes 5 is a possible biomarker for individualized treatment of colorectal cancer
Authors: Gong Xiaoxia , Tian Xiaowei , Xie Hao , Li Zhaoshui
Published: July 2022

Background

Although the understanding of resistance to oxaliplatin (OXA) chemotherapy in colorectal cancer (CRC) has been sought for many years, drug tolerance remains a major challenge for cancer therapy. Revealing the molecular mechanism of OXA resistance could help to explain the poor prognosis of patients.

Methods

Gene expression omnibus (GEO) database was searched, GSE83129, which contains RNA profiling in metastatic CRC patients treated first‐line with OXA, was chosen for the following analysis. Differential expressed genes (DEGs) between the adenocarcinoma and adjacent_normal team, respectively, in the OXA responders and no‐responders were analyzed. The Gene Ontology (GO) and hub genes in the protein–protein interaction (PPI) network were used for the molecular mechanism of OXA resistance. Tumor‐related databases were used for the clinical relevance of the structural maintenance of chromosomes 5 (SMC5) in CRC. The in vitro assays were used to detect the molecular function of SMC5 in CRC cells. Quantitative real‐time PCR (qRT‐PCR) and western blot were used to detect the expression of the structural maintenance of chromosomes 5/6 (SMC5/6) complex components upon OXA and raltitrexed (RTX) treatment. CCK‐8 was used to detect the cell viability of cells with different treatment.

Results

SMC5 was downregulated in CRC tissues of OXA no‐response patients. Lower expression of SMC5 was correlated with a poor prognosis in CRC patients, improved this gene expression, inhibited the CRC cell growth and invasion in vitro. Furthermore, SMC5 was downregulated upon OXA treatment in CRC cells, while RTX would reverse its expression, and the combination of these two drugs restored the SMC5 level to the normal situation. Finally, RTX treatment enhanced the OXA cytotoxicity.

Conclusion

SMC5 is a tumor suppressor, that low expression of this gene is benefit for the development of CRC. Combination treatment with RTX and OXA may be more suitable for those OXA no‐responders with lower SMC5.
Improved Antibody‐Specific Epitope Prediction Using AlphaFold and AbAdapt**
Authors: Xu Zichang , Davila Ana , Wilamowski Jan , Teraguchi Shunsuke , Standley Daron M.
Published: July 2022

Antibodies recognize their cognate antigens with high affinity and specificity, but the prediction of binding sites on the antigen (epitope) corresponding to a specific antibody remains a challenging problem. To address this problem, we developed AbAdapt, a pipeline that integrates antibody and antigen structural modeling with rigid docking in order to derive antibody‐antigen specific features for epitope prediction. In this study, we systematically assessed the impact of integrating the state‐of‐the‐art protein modeling method AlphaFold with the AbAdapt pipeline. By incorporating more accurate antibody models, we observed improvement in docking, paratope prediction, and prediction of antibody‐specific epitopes. We further applied AbAdapt‐AF in an anti‐receptor binding domain (RBD) antibody complex benchmark and found AbAdapt‐AF outperformed three alternative docking methods. Also, AbAdapt‐AF demonstrated higher epitope prediction accuracy than other tested epitope prediction tools in the anti‐RBD antibody complex benchmark. We anticipate that AbAdapt‐AF will facilitate prediction of antigen‐antibody interactions in a wide range of applications.
Higher pulmonary vein index on computed angiography and optimum surgical resection ensures smooth postoperative recovery in Fallot's tetralogy: Special emphasis on indices of evaluation and Monocusp preparation
Authors: Bhende Vishal V. , Sharma Tanishq S. , Mehta Deepakkumar V. , Subramaniam Krishnan Ganapathy , Kumar Amit , Thacker Jigar P. , Patel Viral B. , Panesar Gurpreet , Soni Kunal , Dhami Kartik B. , Majmudar Hardil P. , Patel Nirja , Pathan Sohilkhan R.
Published: July 2022

Tetralogy of Fallot (TOF) is a common cyanotic congenital heart disease. Its surgical correction requires ventricular septal defect (VSD) closure and right ventricular outflow tract obstruction (RVOTO) relief, with transannular patch enlargement (TAPE) of the pulmonary valve. The first successful repair of TOF was reported in 1954 and consisted of closure of the VSD through a large right ventriculotomy, and RVOTO relief with TAPE of the pulmonary valve. To predict the intraoperative requirements and postoperative course of patients with this condition, various evaluation indices are available that can provide a good indication of patient prognosis. We performed this study in a male child (age, 1 year, 9 months; weight 8.5 kgs.) who underwent intracardiac repair for TOF as a primary procedure. We calculated the pulmonary vein index (PVI), McGoon ratio, and Nakata index. The McGoon ratio was 1.97, Nakata index was 539.22 mm2/m2, and PVI was 368.12 mm2/m2. The child had an uneventful post‐operative course with no symptoms of low cardiac output syndrome. He was ventilated for 122 h. The length of intensive care unit and hospital stays were 11 and 14 days, respectively. The PVI is a novel indicator offering prognostic indications for pediatric cardiac patients who have undergone surgical correction of TOF.
Hydrosilylative Reduction of CO2 to Formate and Methanol Using a Cobalt Porphyrin‐Based Porous Organic Polymer
Authors: Hlatshwayo Zweli T. , Doremus Jared G. , McGrier Psaras L.
Published: July 2022

The hydrosilylation of carbon dioxide (CO2) has become a useful strategy for selectively producing fine chemicals and alternative fuels sources. However, the development of heterogeneous catalysts that complete this chemical transformation with high catalytic efficiencies are rare. Herein, the synthesis and characterization of a benzobisthiazole‐linked (BBT) Co(II)‐porphyrin‐based porous organic polymer (Co‐BBT‐POP) for hydrosilylative reduction of CO2 to potassium formate and methanol is reported. Co‐BBT‐POP can reduce CO2 to potassium formate in the presence of diphenylsilane (Ph2SiH2) and KF with a turnover number (TON) of 1627. In the presence of tris(pentafluorophenyl)borane (B(C6F5)3) and Ph2SiH2, Co‐BBT‐POP can convert CO2 to methanol with a TON of 4531. Co‐BBT‐POP exhibits great recyclability up to five cycles for both catalytic systems.
Enhanced Metal–Semiconductor Interaction for Photocatalytic Hydrogen‐Evolution Reaction
Authors: Lu Erjun , Zhang Zhixiang , Tao Junqian , Yu Zhiyang , Hou Yidong , Zhang Jinshui
Published: July 2022

The selective immobilization of noble metals right at the place where photogenerated electrons migrate through the photodeposition approach is a unique strategy to load cocatalysts on semiconductors for solar hydrogen production. However, a poor metal–semiconductor interaction is often formed, which not only hinders the interfacial charge transfer, but also results in the easy aggregation and shedding of cocatalysts during photocatalytic reactions. Herein, it is demonstrated that the photodeposited ultrafine metals, such as nanosized Au, can be well stabilized on TiO2 nanocrystallines without sintering by employing a sacrificial carbon coating annealing strategy to strengthen the metal‐support interaction. Benefiting from the improved interfacial contact between Au and TiO2 for fast charge transfer and the well‐preserved size‐dependent catalytic behavior of Au nanoparticles toward hydrogen evolution reaction, the annealed Au/TiO2 exhibits a significant enhanced activity toward photocatalytic H2 production with good durability.
Interplay and Competition Between Two Different Types of Redox‐Active Ligands in Cobalt Complexes: How to Allocate the Electrons?
Authors: Lohmeyer Lukas , Werr Marco , Kaifer Elisabeth , Himmel Hans‐Jörg
Published: July 2022

The field of molecular transition metal complexes with redox‐active ligands is dominated by compounds with one or two units of the same redox‐active ligand; complexes in which different redox‐active ligands are bound to the same metal are uncommon. This work reports the first molecular coordination compounds in which redox‐active bisguanidine or urea azine (biguanidine) ligands as well as oxolene ligands are bound to the same cobalt atom. The combination of two different redox‐active ligands leads to mono‐ as well as unprecedented dinuclear cobalt complexes, being multiple (four or six) center redox systems with intriguing electronic structures, all exhibiting radical ligands. By changing the redox potential of the ligands through derivatisation, the electronic structure of the complexes could be altered in a rational way.
Extended Bayesian endemic–epidemic models to incorporate mobility data into COVID‐19 forecasting
Authors: Douwes‐Schultz Dirk , Sun Shuo , Schmidt Alexandra M. , Moodie Erica E. M.
Published: July 2022

Forecasting the number of daily COVID‐19 cases is critical in the short‐term planning of hospital and other public resources. One potentially important piece of information for forecasting COVID‐19 cases is mobile device location data that measure the amount of time an individual spends at home. Endemic–epidemic (EE) time series models are recently proposed autoregressive models where the current mean case count is modelled as a weighted average of past case counts multiplied by an autoregressive rate, plus an endemic component. We extend EE models to include a distributed‐lag model in order to investigate the association between mobility and the number of reported COVID‐19 cases; we additionally include a weekly first‐order random walk to capture additional temporal variation. Further, we introduce a shifted negative binomial weighting scheme for the past counts that is more flexible than previously proposed weighting schemes. We perform inference under a Bayesian framework to incorporate parameter uncertainty into model forecasts. We illustrate our methods using data from four US counties.
Breast cancer recurrence after immediate and delayed postmastectomy breast reconstruction—A systematic review and meta‐analysis
Authors: Bargon Claudia A. , Young‐Afat Danny A. , Ikinci Mehmet , Braakenburg Assa , Rakhorst Hinne A. , Mureau Marc A.M. , Verkooijen Helena M. , Doeksen Annemiek
Published: July 2022

Background

Oncological safety of different types and timings of PMBR after breast cancer remains controversial. Lack of stratified risk assessment in literature makes current clinical and shared decision‐making complex. This is the first systematic review and meta‐analysis to evaluate differences in oncological outcomes after immediate versus delayed postmastectomy breast reconstruction (PMBR) for autologous and implant‐based PMBR separately.

Methods

A systematic literature search was performed in MEDLINE, Cochrane Library, and Embase. The Cochrane Collaboration Handbook and Meta‐analysis Of Observational Studies in Epidemiology checklist were followed for data abstraction. Variability in point estimates attributable to heterogeneity was assessed using I2‐statistic. (Loco)regional breast cancer recurrence rates, distant metastasis rates, and overall breast cancer recurrence rates were pooled in generalized linear mixed models using random effects.

Results

Fifty‐five studies, evaluating 14,217 patients, were included. When comparing immediate versus delayed autologous PMBR, weighted average proportions were: 0.03 (95% confidence interval [CI], 0.02–0.03) versus 0.02 (95% CI, 0.01–0.04), respectively, for local recurrences, 0.02 (95% CI, 0.01–0.03) versus 0.02 (95% CI, 0.01–0.03) for regional recurrences, and 0.04 (95% CI, 0.03–0.06) versus 0.01 (95% CI, 0.00–0.03) for locoregional recurrences. No statistically significant differences in weighted average proportions for local, regional and locoregional recurrence rates were observed between immediate and delayed autologous PMBR. Data did not allow comparing weighted average proportions of distant metastases and total breast cancer recurrences after autologous PMBR, and of all outcome measures after implant‐based PMBR.

Conclusions

Delayed autologous PMBR leads to similar (loco)regional breast cancer recurrence rates compared to immediate autologous PMBR. This study highlights the paucity of strong evidence on breast cancer recurrence after specific types and timings of PMBR.

Lay summery

Oncologic safety of different types and timings of postmastectomy breast reconstruction (PMBR) remains controversial.

Lack of stratified risk assessment in literature makes clinical and shared decision‐making complex.

This meta‐analysis showed that delayed autologous PMBR leads to similar (loco)regional recurrence rates as immediate autologous PMBR. Data did not allow comparing weighted average proportions of distant metastases and total breast cancer recurrence after autologous PMBR, and of all outcome measures after implant‐based PMBR.

Based on current evidence, oncological concerns do not seem a valid reason to withhold patients from certain reconstructive timings or techniques, and patients should equally be offered all reconstructive options they technically qualify for.
Hyper‐parametric improved machine learning models for solar radiation forecasting
Authors: Kumar Mantosh , Namrata Kumari , Kumari Neha
Published: July 2022

Spatiotemporal solar radiation forecasting is extremely challenging due to its dependence on metrological and environmental factors. Chaotic time‐varying and non‐linearity make the forecasting model more complex. To cater this crucial issue, the paper provides a comprehensive investigation of the deep learning framework for the prediction of the two components of solar irradiation, that is, Diffuse Horizontal Irradiance (DHI) and Direct Normal Irradiance (DNI). Through exploratory data analysis the three recent most prominent deep learning (DL) architecture have been developed and compared with the other classical machine learning (ML) models in terms of the statistical performance accuracy. In our study, DL architecture includes convolutional neural network (CNN) and recurrent neural network (RNN) whereas classical ML models include Random Forest (RF), Support Vector Regression (SVR), Multilayer Perceptron (MLP), Extreme Gradient Boosting (XGB), and K‐Nearest Neighbor (KNN). Additionally, three optimization techniques Grid Search (GS), Random Search (RS), and Bayesian Optimization (BO) have been incorporated for tuning the hyper parameters of the classical ML models to obtain the best results. Based on the rigorous comparative analysis it was found that the CNN model has outperformed all classical machine learning and DL models having lowest mean squared error and highest R‐Squared value with least computational time.
Molecular Dynamics Simulations of Nitric Oxide Scattering Off Graphene
Authors: Greenwood Thomas , Koehler Sven P. K.
Published: July 2022

We performed classical molecular dynamics simulations to model the scattering process of nitric oxide, NO, off graphene supported on gold. This is motivated by our desire to probe the energy transfer in collisions with graphene. Since many of these collision systems comprising of graphene and small molecules have been shown to scatter non‐reactively, classical molecular dynamics appear to describe such systems sufficiently. We directed thousands of trajectories of NO molecules onto graphene along the surface normal, while varying impact position, but also speed, orientation, and rotational excitation of the nitric oxide, and compare the results with experimental data. While experiment and theory do not match quantitatively, we observe agreement that the relative amount of kinetic energy lost during the collision increases with increasing initial kinetic energy of the NO. Furthermore, while at higher collision energies, all NO molecules lose some energy, and the vast majority of NO is scattered back, in contrast at low impact energies, the fraction of those nitric oxide molecules that are trapped at the surface increases, and some NO molecules even gain some kinetic energy during the collision process. The collision energy seems to preferentially go into the collective motion of the carbon atoms in the graphene sheet.