bluuebunny/crossref_metadata_2025 huggingface dataset:
Field Effect Transistor Sensors Based on In‐Plane 1T′/2H/1T′ MoTe2 Heterophases with Superior Sensitivity and Output Signals
Authors: Zhang Shichao , Wu You , Gao Feng , Shang Huiming , Zhang Jia , Li Zhonghua , Fu YongQing , Hu PingAn
Published: August 2022

2D materials, with their extraordinary physical and chemical properties, have gained extensive interest for physical, chemical and biological sensing applications. However, 2D material‐based devices, such as field effect transistors (FETs) often show high contact resistance and low output signals, which severely affect their sensing performance. In this study, a new strategy is developed to combine metallic and semiconducting polymorphs of transition‐metal dichalcogenides (TMDCs) to solve this critical issue. Such a phase engineering methodology to integrate large‐scale and spatially assembled multilayers of 2H MoTe2 FETs with coplanar metallic 1T′ MoTe2 contacts is applied. Such in‐plane heterophase‐based FETs exhibit an ohmic contact behavior with an extremely low contact resistance due to the coplanar and seamless connections between 2H and 1T′ phases of MoTe2. These 1T′/2H/1T′ based FETs are successfully demonstrated for detecting NH3 with high current outputs increased up to microamp levels without using any conventional interdigital electrodes, which is compatible with the current CMOS circuits for practical applications. Furthermore, the as‐fabricated sensors can detect NH3 gas concentrations down to 5 ppm at room temperature. This study demonstrates a new strategy of applying the heterophase MoTe2‐based nanoelectronics for high‐performance sensing applications.
Orthogonal Growth for Fabricating Hydrogel Sensors and Circuit Boards with In Situ Post‐Tunable Performance
Authors: Fang Yuanlai , Chang Qi , Xiong Xinhong , Dong Shihua , Zhang Chenglin , Yang Li , Cui Jiaxi
Published: August 2022

Conductive hydrogels generally possess dual network structures consisting of hydrophilic cross‐linked polymer frameworks and conductive paths. The post‐modification of their structures and performance for fabricating devices with 3D conductive patterns is challenging because of their covalently cross‐linked complex matrices. Here, an orthogonal‐growth strategy is described for modulating all‐aspects of conductive hydrogels, including size, pattern, conductivity, and conductive path. In this strategy, the matrices controlling samples’ size and the functional components modulating samples’ conductivity can be orthogonally varied by feeding corresponding nutrients. Using poly(hydroxyethyl acrylate)‐polyaniline organohydrogels (PHEA‐PANI) as an example, it is demonstrated that the samples can incorporate the hydroxyethyl acrylate monomer to expand (21.9‐fold in weight is shown) or integrate aniline into the conductive networks to tune conductivity (from 0 to 42.6 mS cm‐1) without changing the sample size. Moreover, the growth of PANI is spatially selective. Exploiting the selective modulation of various parameters through this method, strain sensors with post‐modulated sensing performance and 3D hydrogel circuit boards are fabricated.
Isomeric Dithienothiophene‐Based Hole Transport Materials: Role of Sulphur Atoms Positions on Photovoltaic Performance of Inverted Perovskite Solar Cells
Authors: Yang Jie , Huang Jiachen , Zhang Chao , Sun Huiliang , Li Bolin , Wang Yimei , Feng Kui , Liao Qiaogan , Bai Qingqing , Niu Li , Wang Hua , Guo Xugang
Published: August 2022

Hole transport materials (HTMs) are of great significance to improve the efficiency and long‐term stability of perovskite solar cells (PVSCs). Herein, a series of new HTMs based on isomeric dithienothiophene (DTT) are designed and synthesized. Effects of sulphur (S) atoms positions on defect passivation and performance of PVSCs are systematically investigated through theoretical computation, X‐ray diffraction, X‐ray photoelectron spectroscopy, etc. The three molecules display noticeable isomeric effect in energy level, light absorption, and hole mobility. With S atoms varied from bottom‐bottom‐bottom in 3T‐1 to bottom‐bottom‐top in 3T‐2, then to bottom‐top‐bottom in 3T‐3, the grown perovskite crystallite on the corresponding HTMs shows more homeogenous film morphology and less pinhole traps. Meanwhile, nonradiative recombination losses can be suppressed and hole extraction efficiency at HTM/perovskite surface can be improved from 3T‐1 to 3T‐3. As a result, the remarkable improvement of short‐circuit current density nd open‐circuit voltage in inverted perovskite solar cells can be realized with increasing the sulphur atoms contribution to the molecular conjugation. More importantly, 3T‐3‐based dopant‐free HTM achieves a top power conversion efficiency of 19.23% in PVSCs with good device stability under green solvent processing. These results demonstrate the role of S atoms positions in HTMs on photovoltaic performance of PVSCs and the potential of DTT in developing eco‐friendly HTMs toward efficient PVSCs.
Dopant‐Free Phthalocyanine Hole Conductor with Thermal‐Induced Holistic Passivation for Stable Perovskite Solar Cells with 23% Efficiency
Authors: Qu Geping , Dong Lei , Qiao Ying , Khan Danish , Chen Qian , Xie Pengfei , Yu Xuemeng , Liu Xiaoyuan , Wang Yanggang , Chen Jiangzhao , Chen Xihan , Xu Zong‐Xiang
Published: August 2022

Simultaneous passivation of the defects at the surface and grain boundaries of perovskite films is crucial to achieve efficient and stable perovskite solar cells (PSCs). It is highly desirable to accomplish the above passivation through rational engineering of hole transport materials (HTMs) in combination with appropriate procedure optimization. Here, methylthiotriphenylamine‐substituted copper phthalocyanine (SMe‐TPA‐CuPc) is reported as a dopant‐free HTM for PSCs, exhibiting excellent efficiency, and stability. After thermal annealing, SMe‐TPA‐CuPc molecules diffused into the bulk of the perovskite film and effectively passivated the defects in the bulk and at the interface of the perovskite, owing to the strong interaction between the methylthio moiety and undercoordinated lead. The best‐performing annealed SMe‐TPA‐CuPc‐based device shows efficiency of 21.51%, which is higher than the unannealed SMe‐TPA‐CuPc‐based device (power‐conversion efficiency (PCE) of 20.75%) and reference doped spiro‐OMeTAD‐based device (PCE of 20.61%). Further modification of the perovskite of the annealed SMe‐TPA‐CuPc‐based device by the QAPyBF4 additive result in even higher efficiency of 23.0%. It also shows excellent stability, maintaining 96% of its initial efficiency after 3624 h aging at 85 °C. This work highlights the great potential of phthalocyanine‐based dopant‐free HTMs and the defect passivation by thermal‐induced molecular diffusion strategy for developing highly efficient and stable PSCs.
Bionic Design and Performance of Electrode for Bioelectrical Signal Monitoring
Authors: Yuan Cong , Ji Keju , Zhang Qian , Yuan Peng , Xu Yilin , Liu Jing , Huo Tingwei , Zhao Jiahui , Chen Jian , Song Yi , Long Yi , Dai Zhendong
Published: August 2022

Stable adhesion and comfort for long‐term use are the main challenges currently limiting wearable in real‐time health monitoring, especially in disturbed state such as exercise and sweating. Here, A biomimetic microneedles‐based adhesive electrode is designed, which utilizes the mechanical locking of the microneedle array and the adhesion property of the mimic tree frog foot pad microstructures on the rough and wet substrate to synergistically enhance the stable adhesion performance of electrode on the skin surface. This adhesion‐mechanical locking synergistic enhancement effect of the electrode through experiments is verified; the synergistic enhancement mechanism of the electrode is analyzed, and successfully electrocardiograph and electromyogram on human body skin is monitored. The electrode presented here provides a new path to solve the problem of stable signal acquisition under the condition of sweating and exercise, and realizing comfortable, low‐noise, and continuous health monitoring.
Synthesis of Novel Ruthenium‐Polymetallaynes and Their Application in Multistate Electrochromic Memory
Authors: Ho Po Yuen , Dmitrieva Evgenia , Sun Ningwei , Guskova Olga , Lissel Franziska S.‐C.
Published: August 2022

Multilevel (or multistate) electrochromic devices have the potential to achieve highly compact memory capacity while instantaneously transferring data between memory and processing units. In this article, three novel solution‐processable ruthenium‐polymetallaynes (i.e., P1, P2, and P3), in which the redox‐addressable Ru center is covalently embedded into a conjugated organic polymer, are discussed. In pursuit of higher functionality (e.g., stable multistate behavior, low operating voltage), the organic ligand bridging the metal centers is systematically varied. The previously reported P1 has a bithiophene (BT) bridging ligand with a high degree of rotational freedom. By replacing BT with cyclopenta‐dithiophene in P2 and dithieno‐pyrrole (DTP) in P3, both of which are more planar than BT, the degree of freedom is decreased. By using DTP, redox‐matching is achieved between the metal center and organic ligand, leading to extra stability of the mixed‐valence (MV) state in P3. In‐depth experimental (i.e., in situ electron paramagnetic resonance and UV–vis–NIR spectroelectrochemistry) and theoretical studies (i.e., DFT calculations) are carried out on the polymer thin‐films, showing enhanced metal–metal (M–M) interaction in P2 and P3 and stable Robin–Day class III MV compound in P3. These polymers are also first time fabricated into solid‐state electrochromic devices and the stability of each oxidation state is characterized by tracing the change of transmittance over time, showing satisfactory cyclic stability and retention behavior (≈90% retention after 30 min).
Low‐Power‐Consumption, Reversible 3D Optical Storage Based on Selectively Laser‐Induced Photoluminescence Degradation in CsPbBr3 Quantum Dots Doped Glass
Authors: Sun Shengzhi , Cheng Zhonghui , Song Juan , Yan Chaoyue , Man Tao , Dong Guoping , Qian Bin , Qiu Jianrong
Published: August 2022

In recent years, inorganic lead halide perovskite quantum dots have been used in various optoelectronic fields for their excellent luminescence properties, such as narrow emission bands, ultra‐wide tunable emission wavelength, and high quantum efficiency. In this paper, different from luminescence optimization in most research, luminescence degradation of perovskite quantum dots is addressed by femtosecond laser irradiation and successfully used for three‐dimensional data storage in CsPbBr3 quantum dots doped glass. Photoluminescence (PL) degradation can be finely modulated by adjusting the laser parameters. PL degradation mechanism, investigated by optical spectroscopy and morphology characterization, is attributed to laser‐induced decomposition, recrystallization, and defection of CsPbBr3 quantum dots. Laser‐induced PL degradation and the followed PL recovery by heat treatment are repeated for several cycles, showing good reversibility. Multilayer PL degradation patterns are written into the glass and read out without crosstalk, indicating high‐reliability 3D optical storage characteristics. Amazingly, PL degradation can be induced by just a low‐energy single laser pulse with estimated subpicosecond writing time per bit, demonstrating its potential in high‐speed, low‐power consumption 3D optical storage.
Synthesis of π‐Expanded Coumarins by Ligand‐Enabled Selective C−H Functionalization
Authors: Ren Peng , He Zhijie , Xing Tiantian , Manar Krishna K. , Sampson Jessica , Jin Jian , Wang Long , Carrow Brad P.
Published: August 2022

Herein, we report the synthesis of a series of π‐expanded coumarin derivatives by the selective C−H alkenylation of β‐naphthol in the presence of a palladium catalyst. The use of an anionic thioether ligand is critical for ensuring the high reactivity of this reaction; it enables low catalyst loadings, mild reaction conditions, and the use of acetic acid as a green solvent. This chemistry is widely applicable to naphthol‐based aromatic substrates bearing either electron‐donating or ‐withdrawing functional groups.

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Screening 0D Materials for 2D Nanoelectronics Applications
Authors: Bagheri Mohammad , Komsa Hannu‐Pekka
Published: August 2022

As nanoelectronic devices based on 2D materials are moving toward maturity, optimization of the properties of the active 2D material must be accompanied by equal attention to optimizing the properties of and the interfaces to the other materials around it, such as electrodes, gate dielectrics, and the substrate. While these are usually either 2D or 3D materials, recently K. Liu et al. [Nat. Electron. 4, 906 (2021)] reported on the use of 0D material, consisting of vdW‐bonded Sb2O3 clusters, as a highly promising insulating substrate and gate dielectric. Here, a computational screening study to find promising 0D materials for use in nanoelectronics applications, in conjunction with 2D materials in particular, is reported. By combining a database and literature searches, 16 materials belonging to 6 structural prototypes are found with high melting points and high band gaps, and a range of static dielectric constants. Additional first‐principles calculations are carried out to evaluate selected technologically relevant material properties, and it is confirmed that all these materials are van der Waals‐bonded, thus allowing for facile separation of 0D clusters from the 3D host and only weakly perturbing the electronic properties of the 2D material after deposition.
Gate‐Tunable Photovoltaic Behavior and Polarized Image Sensor Based on All‐2D TaIrTe4/MoS2 Van Der Waals Schottky Diode
Authors: Zhang Li , Han Xiaoning , Zhang Shihao , Wang Hanyu , Huang Ying , Zheng Zhaoqiang , Huo Nengjie , Gao Wei , Li Jingbo
Published: August 2022

2D Weyl semimetal shows potential applications in photodetection, polarization‐sensitive imaging, and Schottky barrier diodes, due to its unique band structure and topological nature. However, its inherently large dark current hinders further improvements of the Weyl semimetal‐based photodetector's performance. Herein, a Td‐TaIrTe4/n‐type MoS2 van der Waals (vdWs) heterojunction photodetector is reported. Owing to the effective lateral build‐in electric field of 145.3 meV, the Schottky diode shows a high rectification ratio of 6 × 103. Benefiting from the photovoltaic effect, a maximum responsivity (R) of 750 mA W−1 and an Ion/Ioff ratio of 104 under 635 nm illumination are achieved. What's more, the photovoltaic R can be enhanced to 890 mA W−1 at the Vg of 40 V. Because of the highly anisotropic crystalline structure of TaIrTe4 component, a high self‐powered photocurrent anisotropic ratio up to 4.19 is realized under 635 nm light at Vg = 40 V. Under self‐powered mode, a high‐resolution letter of “T” within 150 × 120 pixels can be displayed when the polarization direction is parallel to the armchair direction, while it becomes weak along the zigzag direction. This work provides a valuable route to fabricate anisotropic Weyl semimetal/semiconductor vdWs junction for highly integrated optoelectronics.
Quantification of slow‐release fertilizer on year‐round forage production
Authors: Han Kun‐Jun , Pitman William D. , Alison Wink M. , Twidwell Edward K. , Guidry Kurt M.
Published: August 2022

Overseeding annual ryegrass [Lolium perenne L. ssp. multiflorum (Lam.)] into warm‐season grass pasture is a common practice producing almost year‐round forage for cow–calf operations in the southern United States. Such an approach requires continuous soil nutrient availability throughout the season for consistent forage production. Coated fertilizers marketed as “slow‐release” may be an efficient and continuous plant nutrient source. Therefore, a study was conducted to investigate the impact of fertilization options targeting sustainable nutrient release on year‐round dry matter (DM) production. Research was conducted to determine fertilization effects of split application of uncoated inorganic fertilizer, slow‐release coated fertilizer, broiler litter, and zero‐fertilizer on forage production and nutritive value of annual ryegrass overseeded bahiagrass (Paspalum notatum Fluegge) pasture. The slow‐release coated fertilizer produced more total forage mass (30 Mg ha–1), which was of higher crude protein during spring (≥200 g dry matter [DM] kg–1), than the other treatments (<23 Mg ha–1 and 173 g DM kg–1, P < .05). The broiler litter and split application of uncoated inorganic fertilizer produced similar amounts of forage DM. The N uptake from the slow‐release coated fertilizer was higher than the other treatments until mid‐summer. Although early spring‐applied slow‐release fertilizer can enhance total forage production and quality indicators, high cost limits revenue above variable cost of this slow‐release fertilizer to levels similar to that of split‐applied uncoated inorganic N, with broiler litter providing the more economic supply of N to pastures with long growing seasons.
Life course reproductive dynamics associated with menopause in Ugandan women aged 40–49
Authors: Batista Murylo Sforcin , Tsitsiou Yvonne , Dar Sabeera , Ancillotti Giulia , Minhas Sonica , Varshney Natania
Published: August 2022

Background

Early menopausal onset can increase adverse health outcomes in later life; meanwhile, reproductive experiences before menopause may affect its timing. Framed by life course methodology, the study tested for independent and interdependent associations between reproductive history (contraception, age at first birth, parity, terminated pregnancy) and socioeconomic factors (education, wealth, rural–urban residence, cigarette use, marital status, age at first cohabitation) with the occurrence of early menopause.

Methods

The study population was ever‐married women aged 40–49 from the 2016 Demographic & Health Survey (N = 2748). Analytical methods involved probability‐ and age‐adjusted multivariate logistic regression models and predictive margins.

Results

Connections between reproductive and socioeconomic characteristics were key dynamics associated with menopause in ages 40–49. Contraception, parity, and ages at first birth and marriage were found to be independently associated with menopause in this age group. Evidence of interactions was found where no contraceptive use was associated with higher probabilities of menopause for first‐time mothers aged 12–15 and for women with no education.

Conclusions

Studying Ugandan women's reproductive histories highlighted the importance of regional knowledge about menopause. Though we hypothesized that risks would correlate in a chain, the results pointed to risks clustering around contraception, suggesting that improving contraceptive use and education for women could increase menopausal age. Furthermore, the positive association between low parity and early menopause supports the biological mechanism of faster oocyte depletion; however, high‐parity populations like Uganda tend to have a younger menopausal age than low‐parity populations. Declining mortality in the demographic transition could explain these inverse associations.
Collecting occupation and hazards information in primary care using O*NET
Authors: Ruco Arlinda , Pinto Andrew D. , Nisenbaum Rosane , Ho Julia W. , Bellicoso Emily , Hassen Nadha , Hanna Andrew , Muntaner Carles , Holness D. Linn
Published: August 2022

Objective

The objective of this study was to determine the feasibility of collecting occupation and occupational hazard data in a primary care setting, using the Occupational Information Network (O*NET) database to assist with classification.

Methods

We collected data from 204 employed adult primary care patients in Toronto, Canada, on their occupation and exposure to occupational hazards, and mapped their job titles to the O*NET database. We compared their self‐reported occupational hazard exposures with the likelihood of exposure on O*NET.

Results

Exposure to repetitive arm movement was reported by 78%, to vapors/gas/dust/fumes by 30%, to noise by 30%, and to heavy loads by 31%. Significant differences in exposure to vapors/gas/dust/fumes were associated with work precarity. We matched the majority of job titles (89%) to O*NET categories.

Conclusions

Collecting employment information in primary care setting was feasible, with the majority of job titles mapping onto O*NET classifications.
Duchenne expert physician perspectives on Duchenne newborn screening and early Duchenne care
Authors: Armstrong Niki , Schrader Rachel , Fischer Ryan , Crossnohere Norah
Published: August 2022

Duchenne muscular dystrophy (DMD) is a progressive, fatal neuromuscular disorder typically diagnosed between 4 and 5 years of age. DMD currently has five FDA approved therapies, which has led to increased interest in newborn screening (NBS) for DMD. Our objective was to explore the perspectives and predicted practices of physicians (primarily neurologists) who will likely be responsible for the follow‐up of infants identified with DMD through NBS. A short survey was developed and distributed to physicians who are responsible for providing care for patients with Duchenne at Certified Duchenne Care Centers across the USA. Twenty‐seven physicians responded to statements about benefit and readiness for dystrophinopathy NBS, which care recommendations they would make at initial infant visits, and when they would recommend initiating approved therapies. Most DMD physicians indicated they see benefit in NBS (82%) and believe the DMD care community is ready for NBS in dystrophinopathies (74%). The majority of physicians would recommend multiple interventions, including genetic counseling, maternal carrier testing, referral to early intervention services, screening siblings, discussion of clinical trials, exon skipping therapies, and assessment of social and language development at initial visits. The majority of physicians also indicated they would recommend initiating approved therapies much earlier than the typical age of diagnosis.
Characterizing Two‐Qubit Non‐Classical Correlations and Non‐Locality in Mixed Local Dephasing Noisy Channels
Authors: Rahman Atta Ur , Khedif Youssef , Javed Muhammad , Ali Hazrat , Daoud Mohammed
Published: August 2022

The dephasing effects of two independent local mixed static‐Ornstein Uhlenbeck (STC‐OUK) noisy channels on the dynamics of two‐qubit non‐classical correlations, non‐locality, and entanglement are addressed. Here, i) local quantum Fisher information; ii) local quantum uncertainty; iii) uncertainty‐induced non‐locality; iv) Bell non‐locality; and v) negativity to quantify two‐qubit non‐classical correlations, non‐locality and entanglement, respectively, and their loss under the influence of mixed noise are used. The findings show that measure (i) compared to measure (ii) remains more effective in demonstrating non‐classical correlations. For the two‐qubit state with maximum purity, measure (iii) remains less fragile to the mixed STC‐OUK noise than measure (iv) but gets more vulnerable as the initial purity of the two‐qubit state falls. It is intriguing that measures (i), (ii), and (v) completely freeze after a particular interval, yet measures (iii) and (iv) remains partially preserved indefinitely. When compared to other two‐qubit correlation quantifiers, measure (v) exhibits non‐Markovian behavior and the phenomenon of sudden death and birth. Markovian and non‐Markovian dynamical maps, and extended two‐qubit correlations, can be induced by optimizing the current configuration. Finally, under the influence of mixed dephasing effects, robust and strengthened quantum correlations beyond entanglement in the two‐qubit Werner state is shown.
Dynamics of Electron Pearcey– Gaussian Beams in a Constant Magnetic Field
Authors: He Xingyi , Huang Haoyu , Xu Chuangjie , Deng Xiaofang , Wu You , Tang Huilin , Xu Danlin , Luo Shengbao , Liu Jiatian , Wu Ruihuan , Deng Dongmei
Published: August 2022

A new kind of electron Pearcey‐Gaussian beam (EPGB) with auto‐focusing properties in the presence of an additional magnetic field is introduced, which is composed of the multiplication of the Pearcey function and the Gaussian function. The closed‐form expressions of the EPGBs are obtained. Based on different initial transverse velocities, different dynamics of the EPGBs are presented. The effect of the magnetic field toward the maximum focusing plane is also demonstrated. The analytical results are in excellent agreement with direct numerical simulations.
Tunneling in a Rippled Graphene Superlattice with Spin Dependence and a Mass Term
Authors: El‐hassouny Jaouad , Jellal Ahmed , Atmani El Houssine
Published: August 2022

The insertion of the band gap Δ in a rippled graphene superlattice leads to new outcomes, as demonstrated. The essential thing is the appearance of opposite‐spin transmissions, which increases with Δ and vanishes without it. Furthermore, compared to the scenario, the duration of the suppression of the transmission with the same spin is longer, with many peaks. The maximum value of transmissions with the same spin declines and remains around unity. Furthermore, for particular energy values, a shift in the behavior of the transmission channels is found. As a result, it is demonstrated that with Δ, transmission filtering becomes crucial. Finally, as a result of the band gap, distinct variations in total conductance are discovered.
The 100th Anniversary of Einstein's Nobel Prize: Facts and Fiction
Authors: Friedman Robert Marc
Published: August 2022

As the 100th anniversary approaches of Albert Einstein being awarded a Nobel Prize, questions remain about the motivation for the prize and about the absence of any specific mention of his theory of relativity. By revisiting and supplementing earlier scholarly studies, it will be shown that “Einstein did not receive, as often claimed, a prize for his theory of the photoelectric effect and that committee member Allvar Gullstrand's error in comprehending relativity was not the cause for rejecting this strongly nominated achievement.” Rather, in their evaluations of relativity, “Svante Arrhenius (1920) and Gullstrand (1921 & 1922) brought to the task bias, if not prejudice; they incorporated arguments from the German ultranationalist experimental physicists’ politically and racially motivated opposition to Einstein and his theories of relativity and gravitation. Only when Carl Wilhelm Oseen joined the committee in 1922, he nominated, evaluated, and proposed a prize for the discovery of the law of the photoelectric effect.” The precise wording and deliberate silence about Einstein's quantum theoretical derivation of the law owes to Oseen's insightful understanding of the challenges facing any effort to award a Nobel Prize to both Einstein and Niels Bohr.
Near‐Infrared Light‐Driven Photoredox Catalysis by Transition‐Metal‐Complex Nanodots
Authors: Wang Lele , Sa Rongjian , Wei Yingcong , Ma Xiongfeng , Lu Chenggang , Huang Haowei , Fron Eduard , Liu Ming , Wang Wei , Huang Shuping , Hofkens Johan , Roeffaers Maarten B. J. , Wang Yan‐jie , Wang Junhui , Long Jinlin , Fu Xianzhi , Yuan Rusheng
Published: August 2022

Developing light‐harvesting materials with broad spectral response is of fundamental importance in full‐spectrum solar energy conversion. We found that, when a series of earth‐abundant metal (Cu, Co, Ni and Fe) salts are dissolved in coordinating solvents uniformly dispersed nanodots (NDs) are formed rather than fully dissolving as molecular species. The previously unrecognized formation of this condensed state is ascribed to spontaneous aggregation of molecular transition‐metal‐complexes (TMCs) via weak intermolecular interactions, which results in redshifted and broadened absorption into the NIR region (200–1100 nm). Typical photoredox reactions, such as carbonylation and oxidative dehydrogenation, well demonstrate the feasibility of efficient utilization of NIR light (λ>780 nm) by TMCs NDs. Our finding provides a conceptually new strategy for extending the absorption towards low energy photons in solar energy harvesting and conversion via photoredox transformations.
Lipid Mass Tags via Aziridination for Probing Unsaturated Lipid Isomers and Accurate Relative Quantification**
Authors: Yang Tingyuan , Tang Shuli , Kuo Syuan‐Ting , Freitas Dallas , Edwards Madison , Wang Hongying , Sun Yuxiang , Yan Xin
Published: August 2022

Knowing concentrations of lipids is essential for understanding their physiological functions and discovering new disease biomarkers. However, it is highly challenging to accurately quantify lipids due to structural diversity and multiple isomeric forms of lipids. To address these critical gaps, we have developed a novel aziridine‐based isobaric tag labelling strategy that allows (i) determination of lipid double‐bond positional isomers, (ii) accurate relative quantification of unsaturated lipids, and (iii) improvement of ionization efficiencies of nonpolar lipids. The power of this method is demonstrated in characterization and quantification of various categories of lipids such as fatty acids, phosphoglycerol lipids, cholesteryl esters (CE), and glycerides. 17 CE lipid isomers were identified and quantified simultaneously from Alzheimer's disease (AD) mouse serum without using lipid standards. Among them, 6 CE isomers showed significant changes in concentrations in AD serum.
Nickel‐Catalyzed Urea Electrolysis: From Nitrite and Cyanate as Major Products to Nitrogen Evolution
Authors: Tatarchuk Stephen W. , Medvedev Jury J. , Li Feng , Tobolovskaya Yulia , Klinkova Anna
Published: August 2022

The electrochemical urea oxidation reaction (UOR) to N2 represents an efficient route to simultaneous nitrogen removal from N‐enriched waste and production of renewable fuels at the cathode. However, the overoxidation of urea to NOx− usually dominates over its oxidation to N2 at Ni(OH)2‐based anodes. Furthermore, detailed reaction mechanisms of UOR remain unclear, hindering the rational catalyst design. We found that UOR to NOx− on Ni(OH)2 is accompanied by the formation of near stoichiometric amount of cyanate (NCO−), which enabled the elucidation of UOR mechanisms. Based on our experimental and computational findings, we show that the formation of NOx− and N2 follows two distinct vacancy‐dependent pathways. We also demonstrate that the reaction selectivity can be steered towards N2 formation by altering the composition of the catalyst, e.g., doping the catalyst with copper (Ni0.8Cu0.2(OH)2) increases the faradaic efficiency of N2 from 30 % to 55 %.
Low‐temperature Water‐gas Shift Reaction Enhanced by Oxygen Vacancies in Pt‐loaded Porous Single‐crystalline Oxide Monoliths
Authors: Xi Shaobo , Zhang Jie , Xie Kui
Published: August 2022

Water‐gas shift (WGS) reaction at low temperature plays an important role in hydrogen production from fossil fuels and hydrogen purification for proton‐exchange membrane fuel cells. However, the activation of H2O is a critical reaction step that greatly limits the overall performance during WGS reaction. Here we fabricate porous single‐crystalline (PSC) MoO3monoliths at 1 cm scale and deposit atomic‐layered Pt clusters at the lattice surface to create the interfacial system toward the low‐temperature WGS reaction. The single‐crystalline nature stabilizes the oxygen vacancies (VO) at lattice and facilitates the effective activation of H2O at the interface. We show the highest Pt‐normalized activity of 0.86 molCO molPt−1 s−1for the ultra‐low temperature WGS reaction at 120 °C. The single‐crystalline features with enhanced fluxion in porous architectures lead to outstanding performance without visible degradation even after continuous operation for 100 hours.
N‐heterocyclic carbene (NHC) boosted photoluminescence: Synthesis, structures, and photophysical properties of bpy/phen‐Au(III)‐NHC complexes
Authors: Maity Lakshmikanta , Barik Sahadev , Biswas Raju , Natarajan Ramalingam , Dinda Joydev
Published: August 2022

Herein, we first present synthesis, structures, luminescent properties, and electrochemistry of gold(III)‐N‐heterocyclic carbene (NHC) complexes fasten with 2,2′‐bipyridine (bpy) or 1,10′‐phenanthroline (phen). Starting from the proligand 3‐[pyridin‐3‐yl]imidazo[1,5‐a]pyridin‐4‐ylium hexafluorophosphate (1·HPF6), two novel complexes, namely, [Au(1)(bpy)Cl][PF6]2 (2) and [Au(1)2(phen)][PF6]3 (3), have been synthesized and characterized by several spectroscopic techniques. Finally, the solid‐state structures of 2, 3, and precursors [Au(bpy)Cl2][PF6] and [Au(phen)Cl2][PF6] have been determined by single‐crystal X‐ray diffraction studies. The absorption, emission, and lifetime properties of 2 and 3 have been compared with the precursors [Au(bpy)Cl2][PF6] and [Au(phen)Cl2][PF6] to observe the influence of NHC. Though the precursors [Au(bpy)Cl2][PF6] and [Au(phen)Cl2][PF6] are non‐luminescent, yet complexes 2 and 3 are luminescent. A combination of the chromophoric and π‐acid bpy/phen ligand in Au(III) complexes with the strong σ‐donor NHC ligand significantly enhanced the emission properties of the complexes. The blue emission of 2 and 3 in 390–500 nm regions has been tentatively ascribed to arise from intraligand and metal‐to‐ligand charge transfer (MLCT) transitions; also, partial contributions are expected from hydrogen‐bonding interactions. Cyclic voltammetric studies revealed Au(III) → Au(I) and Au(I) → Au(0) reductions at ~ −0.35 to ‐0.29 V and ~ −1.20 to ‐1.15 V, and the potentials are compared with precursors.
A comprehensive approach to pecan nut valorization: Extraction and characterization of soluble and insoluble‐bound phenolics
Authors: Rodrigues Naira Poerner , Pechina Bruno Diniz Rocha , Sarkis Júlia Ribeiro
Published: August 2022

Pecan nuts are known for having high‐phenolic content and antioxidant capacity. In the present work, exhaustive extraction and LC–MS analysis of the soluble (SP) and insoluble‐bound phenolics (IBP) from pecan nut cake were performed. Its SP fraction (1.72 mg/g) is composed of ellagic acid, its glycosylated derivatives and gallic acid. The IBP fraction (2.20 mg/g) includes hydrolysable tannins derived from ellagic and gallic acids and proanthocyanidins from (epi)catechin and (epi)gallocatechin monomers; comprising 56% of the total phenolic content in pecan. Ellagic acid is the main phenolic found in both extracts corresponding to 1.96 mg/g of pecan nut cake. In addition, the extraction of the main SP found in pecan nut cake (ellagic acid and its derivatives) was optimized. The optimal conditions for SP extraction (40% ethanol, 85°C, and 60 ml/g) were able to extract 77% of the total ellagic acid found in pecan nut cake. In addition, the optimized condition for SP extraction (without the heated acid and methanol applied in IBP extraction) released a substantial quantity of ellagic acid and its glycosylated derivatives that are likely noncovalently absorbed in the pecan matrix. Therefore, the extraction process proposed in the present work shows considerably high efficiency using aqueous ethanol and high temperatures for the obtention of phenolics, particularly of ellagic acid, from pecan nut cake.
Synthesis of thiol‐functionalized resin and its adsorption of heavy metal ions
Authors: Zhu Meiling , Wang Xiaolin , Huang Yun , Yue Ling , Zhong Shihua , Zeng Lihua
Published: August 2022

In this study, the thiol‐functionalized resin (PMA‐SH) was prepared directly by a one‐step reaction of polymethyl acrylate resin (PMA) and 1,2‐ethanedithiol, and it was applied to the adsorption of Pb2+, Ni2+, and Hg2+ in aqueous solution. The effects of initial concentration, temperature, contact time, and electrolyte on the adsorption of Pb2+, Ni2+, and Hg2+ were investigated. At 308 K, the saturated adsorption capacity of PMA‐SH on Pb2+, Ni2+, and Hg2+ is found to be 0.94, 0.88, and 0.41 mmol/g, respectively. In addition, the experimental adsorption data were consistent with the Redlich–Peterson model and pseudo‐second‐order kinetic model. Overall, PMA‐SH exhibited good reuse performance as well as excellent adsorption performance for Pb2+, Ni2+, and Hg2+.
Glucose‐sensitive structural color change of cholesteric liquid crystal formed by hydroxypropyl cellulose with phenylboronic acid moieties
Authors: Miyagi Kazuma , Takano Toshiyuki , Teramoto Yoshikuni
Published: August 2022

Developing durable and simple glucose sensing materials is essential to enable the general population an easy method for testing their glucose levels under different environmental conditions. Hence, materials that enable enzyme‐free and intuitive glucose sensing are required. In this study, a system based on an aqueous solution, which enables simple colorimetric glucose detection without the use of enzymes, was developed. The solutions were prepared by dissolving hydroxypropyl cellulose with phenylboronic acid (PBA) moieties (PBA‐HPC) in water. The aqueous solutions with a high concentration of PBA‐HPC formed a lyotropic cholesteric liquid crystal (ChLC) and exhibited structural color originating from the selective reflection of circularly polarized light. PBA‐HPC ChLC aqueous solutions exhibited a color change in response to the increase in the glucose concentration in the solutions. This can be attributed to the change in the side‐chain structure of the PBA‐HPC caused by the formation of a complex between the PBA moieties and glucose, which induced a change in the cholesteric helical pitch. Thus, the proposed system can be used as a durable and simple enzyme‐free glucose sensing material.
Development of scaffolds based in blends of poly(N‐vinylcaprolactam) and poly(N‐vinylcaprolactam‐co‐butylacrylate) with poly(3‐hexylthiophene) for tissue engineering: Synthesis, processing, characterization, and biological assay
Authors: Nahra Sara R. , Oliveira Maurício P. , de Macedo Erenilda Ferreira , Hurtado Carolina Ramos , Tada Dayane B. , Guerrini Lília M. , Antonielli Eduardo , de Almeida Ribeiro Oliveira Gerlon , Lião Luciano Morais , Cristovan Fernando H.
Published: August 2022

Conductive polymers can stimulate the adhesion and proliferation of several cell types being an interesting material to be applied in the field of tissue engineering. In this application, the addition of a thermosensitive polymer has been pointed out as an attractive strategy to improve mechanical strength and to provide conformation changes at temperature close to human body temperature. The main goal of this work was to evaluate the physical–chemical properties and promotion of cell proliferation and possible application as scaffolds for tissue engineering of blends of poly(N‐vinylcaprolactam) (PNVCL) and poly(N‐vinylcaprolactam‐co‐butylacrylate) (PNVCL‐co‐ABu) with poly(3‐hexylthiophene) (P3HT). Both polymers were synthesized and their chemical structures were confirmed by Fourier Transform Infrared (FT‐IR) and nuclear magnetic resonance (NMR) analyses. The materials were processed in films form for structural characterization, impedance measurements, and thermogravimetric analysis. The in vitro biological assays were performed using the materials as electrospun mats. The FT‐IR was also used to characterize the blends. The addition of P3HT did not change thermal stability and showed low conductivity values of the blends. Comparing the in vitro behavior of the blends and the polymers it was possible to conclude that the presence of P3HT improved cytocompatibility and promoted cell proliferation.
Needle to needle robot‐assisted manufacture of cell therapy products
Authors: Ochs Jelena , Hanga Mariana P. , Shaw Georgina , Duffy Niamh , Kulik Michael , Tissin Nokilaj , Reibert Daniel , Biermann Ferdinand , Moutsatsou Panagiota , Ratnayake Shibani , Nienow Alvin , Koenig Niels , Schmitt Robert , Rafiq Qasim , Hewitt Christopher J. , Barry Frank , Murphy J. Mary
Published: August 2022

Advanced therapeutic medicinal products (ATMPs) have emerged as novel therapies for untreatable diseases, generating the need for large volumes of high‐quality, clinically‐compliant GMP cells to replace costly, high‐risk and limited scale manual expansion processes. We present the design of a fully automated, robot‐assisted platform incorporating the use of multiliter stirred tank bioreactors for scalable production of adherent human stem cells. The design addresses a needle‐to‐needle closed process incorporating automated bone marrow collection, cell isolation, expansion, and collection into cryovials for patient delivery. AUTOSTEM, a modular, adaptable, fully closed system ensures no direct operator interaction with biological material; all commands are performed through a graphic interface. Seeding of source material, process monitoring, feeding, sampling, harvesting and cryopreservation are automated within the closed platform, comprising two clean room levels enabling both open and closed processes. A bioprocess based on human MSCs expanded on microcarriers was used for proof of concept. Utilizing equivalent culture parameters, the AUTOSTEM robot‐assisted platform successfully performed cell expansion at the liter scale, generating results comparable to manual production, while maintaining cell quality postprocessing.
Efficacy and safety of lenvatinib in patients with recurrent hepatocellular carcinoma after liver transplantation
Authors: Bang Kyunghye , Casadei‐Gardini Andrea , Yoo Changhoon , Iavarone Massimo , Ryu Min‐Hee , Park Sook Ryun , Kim Hyung‐Don , Yoon Young‐In , Jung Dong‐Hwan , Park Gil‐Chun , Ahn Chul‐Soo , Moon Deok‐Bog , Hwang Shin , Kim Ki‐Hun , Song Gi‐Won , Mazzarelli Chiara , Alimenti Eleonora , Chan Stephen L. , De Giorgio Massimo , Ryoo Baek‐Yeol , Lee Sung‐Gyu
Published: August 2022

Introduction

Lenvatinib is approved for the treatment of patients with metastatic or recurrent hepatocellular carcinoma (HCC); however, clinical outcomes of lenvatinib therapy in patients with post‐liver transplantation (LT) HCC recurrence remain unclear. We investigated the efficacy and safety of lenvatinib in patients with post‐LT HCC recurrence.

Methods

This multinational, multicenter, retrospective study included 45 patients with recurrent HCC after LT who received lenvatinib at six institutions in three countries (Korea, Italy, and Hong Kong) from June 2017 to October 2021.

Results

At the time of lenvatinib initiation, 95.6% (n = 43) of patients had Child–Pugh A status, and 35 (77.8%) and 10 (22.2%) participants were classified as having albumin–bilirubin (ALBI) grades 1 and 2, respectively. The objective response rate was 20.0%. With a median follow‐up duration of 12.9 months (95% confidence interval [CI]: 11.2–14.7), the median progression‐free survival and overall survival (OS) were 7.6 (95% CI: 5.3–9.8) months, and 14.5 (95% CI: 0.8–28.2) months, respectively. Patients with ALBI grade 1 showed significantly better OS (52.3 months, [95% CI: not assessable]) than patients with ALBI grade 2 (11.1 months [95% CI: 0.0–30.4 months], p = 0.003). The most common adverse events were hypertension (n = 25, 55.6%), fatigue (n = 17, 37.8%), and anorexia (n = 14, 31.1%).

Conclusion

Lenvatinib showed consistent efficacy and toxicity profiles in patients with post‐LT HCC recurrence that were comparable to those reported from previous studies among non‐LT HCC patients. The baseline ALBI grade correlated with better OS in post‐LT lenvatinib‐treated patients.
Single‐Layer 2D Ni−BDC MOF Obtained in Supercritical CO2‐Assisted Aqueous Solution
Authors: Chang Hongwei , Zhou Yannan , Zheng Xiaoli , Liu Wei , Xu Qun
Published: August 2022

The development of an efficient strategy for fabricating two‐dimensional metal‐organic framework (MOF) nanosheets with high yield and high stability is desirable. Herein, we demonstrate for the first time that large, single‐layer 2D nickel‐benzene dicarboxylate (Ni−BDC) MOF nanosheets can be fabricated with the assistance of supercritical (SC) CO2 in a pure aqueous system. Detailed experimental evidence reveals that the SC CO2 molecule can exchange with the lattice‐coordinated H2O molecules, side‐on coordinate with the metal Ni1 sites on the Ni−BDC surface, and finally break the interlayer hydrogen bond to exfoliate the bulk Ni−BDC into a 2D MOF. More importantly, a thin SC CO2 layer building up at the water−Ni−BDC interfaces can transform the pristine hydrophilic interface into a super‐hydrophobic one. This super‐hydrophobic layer at the water‐MOF interface can effectively prevent dissociation, thus promoting the stability of Ni−BDC in aqueous system.
Rhodium‐Catalyzed Acrylate Synthesis from Carbon Dioxide and Ethylene by using a Guanidine‐Based Pincer Ligand: Perturbing Occupied d‐Orbitals by pπ‐dπ Repulsion Makes a Difference
Authors: Takegasa Shinnosuke , Lee Ming Min , Tokuhiro Kei , Nakano Ryo , Yamashita Makoto
Published: August 2022

Rhodium‐catalyzed acrylate synthesis from CO2 and ethylene was accomplished by using a guanidine‐based NCN pincer ligand. The repulsion between pπ‐electron of guanidine sidearms and occupied dπ orbital of rhodium center raised the level of d‐electrons close to those of formerly known d8‐ruthenium catalyst, thereby promoting the metallalactone formation from carbon dioxide and ethylene. This work fills the absence of group‐9 metal based catalyst for the acrylate synthesis and provides a designing approach for pincer‐ligated d8‐metal catalysts to utilize pπ‐dπ interaction for promoting desirable redox processes.
Development and application of counter‐current feed injection technology in riser reactors
Authors: Yan Zihan , Fan Yiping , Lu Chunxi , Liu Mengxi , Chen Sheng , Xu Chunming , Bi Xiaotao
Published: August 2022

A counter‐current feed injection scheme is proposed to improve the jet‐solid mixing and reaction in the injection zone of riser reactors. By analyzing the characteristics of the coupled flow field, combined with experiments and numerical simulation, the advantages of the new injection technology are investigated. Experimental results show that the particles distribute more uniformly when the feed is injected downward, which is good for the mixing and reaction of the jet with particles. By simulating the reaction in an industrial fluid catalytic cracking (FCC) riser, it is found that the yields of gasoline and liquefied petroleum gas (LPG) are increased significantly by using the counter‐current feed injection structure. Simultaneously, the formation of coke is reduced considerably. On this basis, a riser‐fluidized bed coupled reactor was designed by adopting the proposed counter‐current feed injection technology to solve the coking problem in an industrial pyridine synthesis system. Results from the side‐stream sampling show that the carbon content of the catalyst reduces significantly, indicating a decrease in coke formation. By now, the improved industrial reactor has been in stable operation for 2 years, showing good reliability.
Coalescence‐induced jumping of microdroplets on superhydrophobic surfaces—A numerical study
Authors: Konstantinidis Konstantinos , Göhl Johan , Mark Andreas , Sasic Srdjan
Published: August 2022

We develop a numerical framework for simulating the coalescence and jumping of microdroplets on superhydrophobic surfaces. The framework combines the volume of fluid (VOF) method with models for advancing and receding contact angles on a number of superhydrophobic surfaces. We demonstrate the temporal and spatial convergence of the framework and show agreement between our numerical results and other experimental studies. The capillary‐inertial scaling is investigated together with the existence of a cut‐off behaviour frequently observed in the lower size‐range of that regime. We investigate findings in some of the previous studies that the cut‐off behaviour can be attributed to viscosity effects and dissipation due to interaction with surface microstructures. We exemplify specific features related to the jumping process and the corresponding energy budget analysis when microdroplets coalesce and jump. We have tested droplets of a radius as small as 0.5 μm that are still jumping but recorded a decrease in the jumping velocity and the degree of energy conversion compared to the jumping of larger droplets. We argue and prove that strong capillary forces originating from the high curvature oscillations dissipate the energy of the system significantly faster in the case of microdroplets.