bluuebunny/crossref_metadata_2025 huggingface dataset:
Mass Spectrometry of Organocobalt Derivatives
Authors: Koszinowski Konrad
Published: January 2022

Being one of the most powerful and versatile analytical techniques, mass spectrometry has greatly contributed to the analysis of organocobalt derivatives. After a short discussion of the ionization methods most relevant to the investigation of these species, this chapter reviews the application of mass spectrometry to the analysis of the title compounds. First, these applications include the characterization of preformed organocobalt derivatives, such as cobalt complexes with σ‐bound organyl groups, cobalt complexes with organic π‐donor ligands, and carbonyl‐containing cobalt clusters. In these cases, mass spectrometry is typically used as a routine technique, together with additional analytical methods. Second, mass spectrometry, particularly its electrospray‐ionization (ESI) variant, can also be employed for the detection and identification of in situ formed organocobalt derivatives. While ESI mass spectrometry is limited to the analysis of charged species, this method has succeeded in the observation of several quasi‐neutral organocobalt intermediates bearing a charged tag. From the time profiles of the ESI signal intensities of these intermediates, valuable information on the reaction kinectics could also be obtained. Finally, mass spectrometry has been extensively applied to the gas‐phase preparation and analysis of organocobalt derivatives. In the highly diluted gas phase, even very reactive organocobalt ions can be generated and further examined. Tandem‐spectrometry permits the mass selection of these ions and thereby greatly facilitates their analysis. Thus, gas‐phase experiments probing the uni‐ and bimolecular reactivity of organocobalt ions have afforded seminal thermochemical and mechanistic information. Coupling tandem mass spectrometry with gas‐phase spectroscopy has moreover furnished insight into the structures of organocobalt ions.
Brain stereotactic radiosurgery using MR‐guided online adaptive planning for daily setup variation: An end‐to‐end test
Authors: Han Eun Young , Wang He , Briere Tina Marie , Yeboa Debra Nana , Boursianis Themistoklis , Kalaitzakis Georgios , Pappas Evangelos , Castillo Pamela , Yang Jinzhong
Published: January 2022

Online magnetic resonance (MR)‐guided radiotherapy is expected to benefit brain stereotactic radiosurgery (SRS) due to superior soft tissue contrast and capability of daily adaptive planning. The purpose of this study was to investigate daily adaptive plan quality with setup variations and to perform an end‐to‐end test for brain SRS with multiple metastases treated with a 1.5‐Tesla MR‐Linac (MRL). The RTsafe PseudoPatient Prime brain phantom was used with a delineation insert that includes two predefined structures mimicking gadolinium contrast‐enhanced brain lesions. Daily adaptive plans were generated using six preset and six random setup variations. Two adaptive plans per daily MR image were generated using the adapt‐to‐position (ATP) and adapt‐to‐shape (ATS) workflows. An adaptive patient plan was generated on a diagnostic MR image with simulated translational and rotational daily setup variation and was compared with the reference plan. All adaptive plans were compared with the reference plan using the target coverage, Paddick conformity index, gradient index (GI), Brain V12 or V20, optimization time and total monitor units. Target doses were measured as an end‐to‐end test with two ionization chambers inserted into the phantom. With preset translational variations, V12 from the ATS plan was 17% lower than that of the ATP plan. With a larger daily setup variation, GI and V12 of the ATS plan were 10% and 16% lower than those of the ATP plan, respectively. Compared to the ATP plans, the plan quality index of the ATS plans was more consistent with the reference plan, and within 5% in both phantom and patient plans. The differences between the measured and planned target doses were within 1% for both treatment workflows. Treating brain SRS using an MRL is feasible and could achieve satisfactory dosimetric goals. Setup uncertainties could be accounted for using online plan adaptation. The ATS workflow achieved better dosimetric results than the ATP workflow at the cost of longer optimization time.
Virtual treatment options make a case, and private investment is responding
Authors: Enos Gary
Published: January 2022

Problems in attracting patients to traditional addiction treatment and retaining them in care, an issue compounded by the challenges of the pandemic, have caused an explosion of interest in virtual applications for substance use prevention, treatment and recovery. Startups that for several years now have received some innovation funding from government sources are increasingly catching the eye of heavy hitters in private investment. This became clear last October when Workit Health announced a $118 million investment round that included participants such as CVS Health Ventures and the BCBS Venture Fund.
Untying the Bundles of Solution‐Synthesized Graphene Nanoribbons for Highly Capacitive Micro‐Supercapacitors
Authors: Liu Zhaoyang , Hu Yunbin , Zheng Wenhao , Wang Can , Baaziz Walid , Richard Fanny , Ersen Ovidiu , Bonn Mischa , Wang Hai I. , Narita Akimitsu , Ciesielski Artur , Müllen Klaus , Samorì Paolo
Published: January 2022

The precise bottom‐up synthesis of graphene nanoribbons (GNRs) with controlled width and edge structures may compensate for graphene's limitations, such as the absence of an electronic bandgap. At the same time, GNRs maintain graphene's unique lattice structure in one dimension and provide more open‐edge structures compared to graphene, thus allowing faster ion diffusion, which makes GNRs highly promising for energy storage systems. However, the current solution‐synthesized GNRs suffer from severe aggregation due to the strong π–π interactions, which limits their potential applications. Thus, it is indispensable to develop a facile and scalable approach to exfoliate the GNRs from the postsynthetic aggregates, yielding individual nanoribbons. Here, a high‐shear‐mixing approach is demonstrated to untie the GNR bundles into practically individual GNRs, by introducing suitable molecular interactions. The micro‐supercapacitor (MSC) electrode based on solution‐processed GNR film exhibits an excellent volumetric capacitance of 355 F cm−3 and a high power density of 550 W cm−3, reaching the state‐of‐the‐art performance of graphene and related carbon materials, and thus demonstrating the great potential of GNRs as electrode materials for future energy storage.
Facilitating In Situ Tumor Imaging with a Tetrahedral DNA Framework‐Enhanced Hybridization Chain Reaction Probe
Authors: Zhang Bowen , Tian Taoran , Xiao Dexuan , Gao Shaojingya , Cai Xiaoxiao , Lin Yunfeng
Published: January 2022

Rapid and efficient tools for early cancer detection have diagnostic and therapeutic value. Given that the DNA hairpin‐based hybridization chain reaction (HCR) is effective in detecting various biological targets, a tetrahedral framework DNA‐enhanced (TDN‐enhanced) HCR detection system (T‐probe system) is introduced for cancer‐related targets and its versatility is demonstrated by detecting intracellular target miRNA 21 and cellular membrane target nucleolin. Benefiting from the spatial confinement of the TDN, the T‐probe system demonstrates a high detection rate. It increases the reaction efficiency of nude hairpins in vitro while accurately and rapidly recognizing both membrane and intracellular cancer‐related targets in living cells. Furthermore, it exhibits superior fluorescence in vivo within 15 s of peripheral‐tumor injection and 10 min of tail‐vein injection. The T‐probe system efficiently and accurately images tumor‐related biomarkers in vitro and in vivo, thereby demonstrating great potential for clinical diagnosis and therapeutic applications.
A Clot‐Homing Near‐Infrared Probe for In Vivo Imaging of Murine Thromboembolic Models
Authors: Chen Dan , Liu Peiwen , Liu Yurong , Wang Zhiyou , Zhou Yang , Jiang Longguang , Yuan Cai , Li Yongkun , Lin Wei , Huang Mingdong
Published: January 2022

Direct thrombus imaging contributes to early detection of thrombosis, and animal models with clinical relevance are vital in the development of new thrombolytics. Here, a facile clot‐homing strategy is developed based on the finding that blood clot is negatively charged. Positively charged pentalysine moiety is coupled with phthalocyanine‐based fluorophore , and its applications in murine thromboembolic models are described. The probe efficiently stains the cryosection of intracranial thrombi retrieved from patients with cardioembolic stroke. In vitro, the fibrin‐rich clot is labeled by the probe at sub‐nanomolar concentration. The probe‐labeled clot is formed into microparticles (1–5 µm) and intravenously injected into mice for pulmonary embolism modeling. In vivo imaging demonstrates fast accumulation and retention of fluorescent clot microparticles in pulmonary vessels. Recombinant tissue‐type plasminogen activator (rtPA) administration greatly reduces near‐infrared signal in the lungs in a time‐dependent manner. This probe is also tested in a stroke model. Middle cerebral artery is occluded by autologous thrombi formed under electric stimulation. In vivo imaging shows that the probe efficiently homes to thrombus at early stage. Hence, this probe has great potential in real‐time imaging of thromboembolism in clinically relevant models, promoting bench‐to‐bedside translation. This clot‐homing principle can be used in other applications.
Highly Precise, Continuous, Long‐Term Monitoring of Skin Electrical Resistance by Nanomesh Electrodes
Authors: Miyamoto Akihito , Kawasaki Hiroshi , Lee Sunghoon , Yokota Tomoyuki , Amagai Masayuki , Someya Takao
Published: January 2022

The transepidermal water loss has been widely used as a method for directly evaluating the barrier function of the stratum corneum of the skin. However, transepidermal water loss could not be measured continuously for a long period of time, and there were no reports of continuous monitoring of skin barrier functions. Here, a method is reported to continuously monitor the skin electrical resistance by nanomesh electrodes for a long period of time while maintaining the natural skin condition that does not inhibit water evaporation. Simultaneous measurements of the skin electrical resistance by nanomesh electrodes and transepidermal water loss exhibits a linear fit with a high negative correlation. Furthermore, dynamics of skin physiological functions are successfully visualized by monitoring of the skin electrical resistance by nanomesh electrodes for 30 h in daily life.
Harnessing the Quantum Behavior of Spins on Surfaces
Authors: Chen Yi , Bae Yujeong , Heinrich Andreas J.
Published: January 2022

The desire to control and measure individual quantum systems such as atoms and ions in a vacuum has led to significant scientific and engineering developments in the past decades that form the basis of today's quantum information science. Single atoms and molecules on surfaces, on the other hand, are heavily investigated by physicists, chemists, and material scientists in search of novel electronic and magnetic functionalities. These two paths crossed in 2015 when it was first clearly demonstrated that individual spins on a surface can be coherently controlled and read out in an all‐electrical fashion. The enabling technique is a combination of scanning tunneling microscopy (STM) and electron spin resonance, which offers unprecedented coherent controllability at the Angstrom length scale. This review aims to illustrate the essential ingredients that allow the quantum operations of single spins on surfaces. Three domains of applications of surface spins, namely quantum sensing, quantum control, and quantum simulation, are discussed with physical principles explained and examples presented. Enabled by the atomically‐precise fabrication capability of STM, single spins on surfaces might one day lead to the realization of quantum nanodevices and artificial quantum materials at the atomic scale.
Neisseria meningitidis Opca Protein/MnO2 Hybrid Nanoparticles for Overcoming the Blood–Brain Barrier to Treat Glioblastoma
Authors: Dong Cheng‐Yuan , Huang Qian‐Xiao , Cheng Han , Zheng Di‐Wei , Hong Sheng , Yan Yu , Niu Mei‐Ting , Xu Jian‐Guo , Zhang Xian‐Zheng
Published: January 2022

The major hurdle in glioblastoma therapy is the low efficacy of drugs crossing the blood–brain barrier (BBB). Neisseria meningitidis is known to specifically enrich in the central nervous system through the guidance of an outer membrane invasion protein named Opca. Here, by loading a chemotherapeutic drug methotrexate (MTX) in hollow manganese dioxide (MnO2) nanoparticles with surface modification of the Opca protein of Neisseria meningitidis, a bionic nanotherapeutic system (MTX@MnO2‐Opca) is demonstrated to effectively overcome the BBB. The presence of the Opca protein enables the drug to cross the BBB and penetrate into tumor tissues. After accumulating in glioblastoma, the nanotherapeutic system catalyzes the decomposition of excess H2O2 in the tumor tissue and thereby generates O2, which alleviates tumor hypoxia and enhances the effect of chemotherapy in the treatment of glioblastoma. This bionic nanotherapeutic system may exhibit great potential in the treatment of glioblastoma.
Orientated Growth of Ultrathin Tellurium by van der Waals Epitaxy
Authors: Zhao Chunsong , Batiz Humberto , Yasar Bengisu , Ji Wenbo , Scott Mary C. , Chrzan Daryl C. , Javey Ali
Published: January 2022

Tellurium, as an elemental van der Waals semiconductor, has intriguing anisotropic physical properties owing to its inherent 1D crystal structure. To exploit the anisotropic and thickness‐dependent behavior, it is important to realize orientated growth of ultrathin tellurium. Here, van der Waals epitaxial growth of Te on the surface of 2D transition metal dichalcogenides is systematically investigated. Orientated growth of Te with a thickness down to 5 nm is realized on three‐fold symmetric substrates (WSe2, WS2, MoSe2, and MoS2), where the atomic chains of Te are aligned with the armchair directions of substrates. 1D/2D moiré superlattices are observed for the Te/WSe2 heterostructure. This method is extended to the growth of SeTe alloys, providing flexibility for band engineering. Finally, growth of textured Te film is demonstrated on the lower‐symmetry surface of WTe2.
Nickel Quantum Dots Anchored in Biomass‐Derived Nitrogen‐Doped Carbon as Bifunctional Electrocatalysts for Overall Water Splitting
Authors: Chen Shuang , Min Xin , Zhao Yajing , Wu Xiaoxian , Zhang Dan , Hou Xifeng , Wu Xiaowen , Liu Yan'gai , Huang Zhaohui , Abdelkader Amr. M. , Xi Kai , Fang Minghao
Published: January 2022

Quantum dots (QD), mixed with carbon materials, have gained increasing interest in the last few years as electrocatalysts due to their outstanding properties, such as excellent catalytic activity and good thermodynamic stabilities. However, most QD‐carbon hybrids show lower catalytic activities than that theoretically predicted due to the aggregation of the QD‐carbon nanostructures during processing. Herein, biomass is used as a carbon source to prepare QD carbon nanostructures (Ni@CN) to address the aforementioned issue. The cells walls and membranes in the biomass materials are usually rich in sites that could regulate the deposition and growth of Ni from a salt precursor by a simple solution impregnation method. Due to the abundance of the seeding sits and the limited supply of Ni+, the Ni particles size is restricted to the QD level with 3–4 nm. The formed Ni compounds QD are strongly linked to the cells walls and membranes, which could be maintained after subsequent heat treatment. The prepared 3D architecture has high catalytic activity, large surface area, strong physical integration, and rapid charge transfer capability, which collectively enhances the performance toward oxygen evolution reaction and hydrogen evolution reaction, opening the door to empower the next‐generation green fuel conversion for carbon neutral.
rGO‐ZnSnO3 Nanostructure‐Embedded Triboelectric Polymer‐Based Hybridized Nanogenerators
Authors: Manchi Punnarao , Graham Sontyana Adonijah , Patnam Harishkumarreddy , Paranjape Mandar Vasant , Yu Jae Su
Published: January 2022

Piezoelectric/ferroelectric zinc tin oxide (ZnSnO3) nanocubes (NCs) are synthesized via a hydrothermal synthesis process. Piezoelectric materials exhibit a superior dielectric property, strong electric dipole moment, and higher piezoelectric coefficient, which results in an improved electrical output of the nanogenerator. The synthesized ZnSnO3 NCs are embedded in triboelectric polydimethylsiloxane (PDMS) polymer to employ the synergistic effect of ZnSnO3/PDMS composite polymer matrix (CPM), which creates a hybrid nanogenerator (HNG). The proposed HNG reveals a high electrical performance due to the improved dielectric constant as well as the synergistic effect of piezoelectricity and triboelectricity. Besides, a conductive filler material such as reduced graphene oxide (rGO) is synthesized using a modified Hummer's method and is further utilized to prepare an rGO‐ZnSnO3/PDMS CPM for improving the electrical output performance of the HNG. Furthermore, the ZnSnO3 NCs and rGO‐ZnSnO3 with different amounts are embedded into PDMS polymeric film to optimize the electrical performance of the HNG. The durability test of the proposed HNG device along with the robustness is investigated. Finally, the proposed HNG device is employed to harvest mechanical movements from daily life human activities to power various portable electronics.
Applications of Lead‐Free Cs2AgBiBr6 Single Crystals in Photodetectors and Self‐Powered Photodetectors by Symmetric/Asymmetric Electrodes
Authors: Hao Dandan , Liu Dapeng , Zhang Shiqi , Li Li , Yang Ben , Huang Jia
Published: January 2022

Lead halide hybrid perovskites have been intensively explored as light‐harvesting materials owing to their unique optoelectrical characteristics and simple deposition method. However, the toxicity and instability problems are still hindering their further development and applications. Herein, stable lead‐free double perovskite Cs2AgBiBr6 single crystals (SCs) with outstanding photoelectric properties are prepared. When symmetric Au electrodes are used, the resulting photodetectors (PDs) can have broad spectral response, high responsivity of 4.88 A W−1, external quantum efficiency of 1100%, and detectivity of 1.22 × 1013 Jones, respectively. More interestingly, when asymmetric electrodes (Au and Ag) are used, the authors obtain the first reported self‐driven PD based on the lead‐free perovskite SC, to the best of the authors’ knowledge. The device exhibits good photoresponse properties at a bias of 0 V. Both devices hold short response time at µs scale, which are among the best reported lead‐free perovskite PDs. Both devices demonstrate decent stabilities in air without encapsulation. All results demonstrate that Cs2AgBiBr6 SCs have great potential in the application of optoelectronic devices.
Dispersive Temporal Interferometry toward Single‐Shot Probing Ultrashort Time Signal with Attosecond Resolution
Authors: Xian Tianhao , Wang Wenchao , Zhan Li
Published: January 2022

With the intensive research on ultrafast dynamics in physics and chemistry, the single‐shot measurement of ultrashort time change has become increasingly important. The most advanced oscilloscope with the time‐lens technique possesses subpicosecond resolution, while the interferometer can single‐shot probe time event within one optical cycle. However, the single‐shot measurement of time difference beyond optical cycle but less than time‐lens’ resolution is still inaccessible. Herein, a technique, the dispersive temporal interferometer (DTI), to break through the gap between interferometer and time lens on single‐shot time measurement, is reported. The concept is an analogy to the spatial interference: a pulse passes two paths to assemble into a pulse pair, and temporal interference arises after large dispersion, which can single‐shot record the imposed time change. Experimentally, it is measured that its resolution is sub‐20 as (0.004 optical cycle) over a range of larger than 2 ps (400 optical cycle), with a range‐to‐resolution ratio of 105 and sampling rate of 42.8 MHz. Moreover, a DTI‐based gyroscope with sensitivity of 348 as/(deg s−1) is fabricated to demonstrate its applications in optical sensors. This technique can precisely single‐shot monitor ultrashort time change in attosecond resolution and has a prosperous application prospect in capturing ultrafast process.
Reverse osmosis and pervaporation of organic liquids using organosilica membranes: Performance analysis and predictions
Authors: Dong Guanying , Zhang Yatao , Sato Takaaki , Nagasawa Hiroki , Kanezashi Masakoto , Tsuru Toshinori
Published: January 2022

This study systematically investigated and modeled the organic solvent reverse osmosis (OSRO) and pervaporation (PV) performances of bis(triethoxysiyl)acetylene (BTESA)‐derived microporous organosilica membranes with different microstructures and permeation properties. BTESA membranes calcined at a low temperature of 100°C exhibited great promise for utility in the challenging OSRO separation of methanol/organic azeotropes such as methanol/toluene and methanol/methyl tert‐butyl ether and demonstrated ultrahigh values for both permeating flux and rejection together with good operation stability. In addition, a generalized solution‐diffusion model enabled a suitable description of the permeation behaviors of organic solvent molecules through the BTESA membranes irrespective of the use of either OSRO or PV modalities, which allowed us to predict the OSRO performance via PV, and vice versa.
Engineering Dual Single‐Atom Sites on 2D Ultrathin N‐doped Carbon Nanosheets Attaining Ultra‐Low‐Temperature Zinc‐Air Battery
Authors: Cui Tingting , Wang Yun‐Peng , Ye Tong , Wu Jiao , Chen Zhiqiang , Li Jiong , Lei Yongpeng , Wang Dingsheng , Li Yadong
Published: January 2022

Herein, a novel dual single‐atom catalyst comprising adjacent Fe‐N4 and Mn‐N4 sites on 2D ultrathin N‐doped carbon nanosheets with porous structure (FeMn‐DSAC) was constructed as the cathode for a flexible low‐temperature Zn‐air battery (ZAB). FeMn‐DSAC exhibits remarkable bifunctional activities for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Control experiments and density functional theory calculations reveal that the catalytic activity arises from the cooperative effect of the Fe/Mn dual‐sites aiding *OOH dissociation as well as the porous 2D nanosheet structure promoting active sits exposure and mass transfer during the reaction process. The excellent bifunctional activity of FeMn‐DSAC enables the ZAB to operate efficiently at ultra‐low temperature of −40 °C, delivering 30 mW cm−2 peak power density and retaining up to 86 % specific capacity from the room temperature counterpart.
Surface Modification of Nano‐Cu2O for Controlling CO2 Electrochemical Reduction to Ethylene and Syngas
Authors: Luo Haiqiang , Li Bo , Ma Jian‐Gong , Cheng Peng
Published: January 2022

In the surroundings of carbon neutrality, nano‐Cu2O is considered a promising catalyst for the electrochemical CO2 reduction reaction (ECO2RR), whose improvements in product selectivity still require considerable efforts. Here, we present an efficient strategy for controlling the ECO2RR product by modifying the surface of nano‐Cu2O, i.e., by controlling the exposed facets via a reductant‐controlled method to achieve the highest C2H4 selectivity (Faradic efficiency=74.1 %) for Cu2O‐based catalysts in neutral electrolytes, and introducing a well‐suited metal–organic framework (MOF) coating on the surface of nano‐Cu2O to obtain syngas completely with an appropriate H2:CO ratio. Detailed mechanism and key intermediate have been illustrated by DFT calculations. Our systematic strategy is expected to control the ECO2RR product, improve the selectivity, and provide a reliable method for CO2 management and the green production of important carbon resources.
Fold‐in Synthesis of a Pentabenzopentaaza[10]circulene
Authors: Matsuo Yusuke , Kise Koki , Morimoto Yuki , Osuka Atsuhiro , Tanaka Takayuki
Published: January 2022

A pentabenzopentaaza[10]circulene has been synthesized as the largest fully conjugated hetero[n]circulene via a fold‐in oxidative fusion reaction of an ortho‐phenylene‐bridged cyclic pyrrole pentamer. This circulene takes a saddle‐distorted structure with bond lengths of the central ten‐membered‐ring in the range of 1.455–1.493 Å. Relatively broad absorption and fluorescence spectra were observed, which reflects its flexible structure, in accordance with the low‐temperature NMR spectra and theoretical calculations. The energy barrier for saddle‐to‐saddle interconversion was estimated to be quite small (≈3 kcal mol−1).
Polyyne [3]Rotaxanes: Synthesis via Dicobalt Carbonyl Complexes and Enhanced Stability
Authors: Patrick Connor W. , Woods Joseph F. , Gawel Przemyslaw , Otteson Claire E. , Thompson Amber L. , Claridge Tim D. W. , Jasti Ramesh , Anderson Harry L.
Published: January 2022

New strategies for synthesizing polyyne polyrotaxanes are being developed as an approach to stable carbyne “insulated molecular wires”. Here we report an active metal template route to polyyne [3]rotaxanes, using dicobalt carbonyl masked alkyne equivalents. We synthesized two [3]rotaxanes, both with the same C28 polyyne dumbbell component, one with a phenanthroline‐based macrocycle and one using a 2,6‐pyridyl cycloparaphenylene nanohoop. The thermal stabilities of the two rotaxanes were compared with that of the naked polyyne dumbbell in decalin at 80 °C, and the nanohoop rotaxane was found to be 4.5 times more stable.
Concentrated Electrolyte for High‐Performance Ca‐Ion Battery Based on Organic Anode and Graphite Cathode
Authors: Li Jin , Han Chengjun , Ou Xuewu , Tang Yongbing
Published: January 2022

Due to the large abundance, low redox potential, and multivalent properties of calcium (Ca), Ca‐ion batteries (CIBs) show promising prospects for energy storage applications. However, current research on CIBs faces the challenges of unsatisfactory cycling stability and capacity, mainly restricted by the lack of suitable electrolytes and electrode materials. Herein, we firstly developed a 3.5 m concentrated electrolyte with a calcium bis(fluorosulfonyl)imide (Ca(FSI)2) salt dissolved in carbonate solvents. This electrolyte significantly improved the intercalation capacity for anions in the graphite cathode and contributed to the reversible insertion of Ca2+ in the organic anode. By combining this concentrated electrolyte with the low‐cost and environmentally friendly graphite cathode and organic anode, the assembled Ca‐based dual‐ion battery (Ca‐DIB) exhibits 75.4 mAh g−1 specific discharge capacity at 100 mA g−1 and 84.7 % capacity retention over 350 cycles, among the best results known for CIBs.
A bis(thiosemicarbazonato)‐zinc complex, an electrocatalyst for hydrogen evolution and oxidation via ligand‐assisted metal‐centered reactivity
Authors: Du Juan , Yang Hao , Wang Chun‐Li , Zhan Shu‐Zhong
Published: January 2022

Based on that hydrogen energy is widely used in fuel cells, the design and research of new catalysts for both hydrogen evolution reactions (HERs) and hydrogen oxidation reactions (HORs) are becoming increasingly important. A new catalyst for both hydrogen evolution and oxidation, based on a zinc complex, [Zn‐ATSE]2, is designed and provided by the reaction of Zn (CH3CO2)2 with diacetyl‐2‐(4‐N‐ethyl‐3‐thiosemicarbazone)‐3‐(4‐N‐amino‐3‐thiosemicarbazone) (H2ATSE) in our group. Electrochemical investigations show that [Zn‐ATSE]2 can electro‐catalyze hydrogen evolution from acetic acid with a turnover frequency (TOF) of 64 mol H2 mol catalyst−1 h−1 under an overpotential of 914.6 mV. Moreover, [Zn‐ATSE]2 also can electro‐catalyze hydrogen oxidation with a TOF of 13.52 s−1. The results can be attributed to the hydrazine group of [Zn‐ATSE]2 that can form a ligand‐based radical species. Possible electrocatalytic cycles for H2 production and oxidation by [Zn‐ATSE]2 are afforded. We hope these findings can afford a new method for the design of electrocatalysts for both H2 evolution and H2 oxidation.
Ferrocene conjugates linked by 1,2,3‐triazole and their Zn(II) and Cu(II) complexes: Synthesis, characterization and biological activity
Authors: Jakopec Silvio , Pantalon Juraj Natalija , Brozovic Anamaria , Jadreško Dijana , Perić Berislav , Kirin Srećko I. , Raić‐Malić Silvana
Published: January 2022

Ferrocene derivatives with mono‐ (8a–c) and bis‐1,2,3‐triazolyl (9 and 10a–13c) chelating groups were synthesized by regioselective copper(I)‐catalysed 1,3‐dipolar cycloaddition of terminal alkynes with ferrocene azides. Metal complexes of the ligands were prepared with Cu(II) and Zn(II) salts. Crystal structures of ligands 9 and 11a were determined, as well as the structures of complexes [Cu(8a)2](CF3SO3)2 (8aCu) and [Cu(8c)2(CH3OH)2](BF4)2 (8cCu). In addition to NMR and UV–Vis spectroscopy, the metal complexes were characterized by cyclic voltammetry. The cytotoxic effect of ferrocene conjugates and their Zn(II) and Cu(II) complexes was explored, and cell cycle analysis was performed. The complex [Cu(8c)2](CF3SO3)2 showed the most prominent and selective cytotoxicity on cervical carcinoma (HeLa), ovarian cancer (MES‐OV), non‐small cell lung cancer (A549) and breast carcinoma (MDA‐MB‐231) cells. This complex increased cell population in the S and G2/M phase of the cell cycle, which was accompanied by an increase of the cells present in the sub‐G0/G1 fraction.
Synthesis, characterization, and biological evaluation of some novel Schiff bases as potential metabolic enzyme inhibitors
Authors: Çakmak Reşit , Başaran Eyüp , Şentürk Murat
Published: January 2022

In this study, a series of novel Schiff base derivatives containing a pyrazolone ring (2a–e) were designed, successfully synthesized for the first time, and characterized by elemental analysis and some spectroscopic methods. These compounds were tested for their inhibitory activities on acetylcholinesterase (AChE), butyrylcholinesterase (BChE), and the human carbonic anhydrase isoenzymes I and II (hCA I and II). All synthesized molecules indicated significant inhibition effects with IC50 values ranging from 14.15 to 107.62 nM against these enzymes. Compound 2d showed the most potent inhibitory activity among the tested molecules toward AChE and BChE (IC50 = 15.07 and 14.15 nM) compared to the standard drug neostigmine. We determined that the IC50 values of the tested molecules ranged between 16.86 and 57.96 nM for hCA I and 15.24–46.21 nM for hCA II. As a consequence, we may say that some of the Schiff base derivatives may be used as potential drug candidates in later studies.
The question of dissection in medical training: Not just “if,” but “when”? A student perspective
Authors: Webb Alexandra L. , Smyth Lillian , Hafiz Mustafa , Valter Krisztina
Published: January 2022

While debate about the use of—and alternatives to—human cadaveric dissection in medical training is robust, little attention has been paid to questions about timing. This study explores the perspectives of medical students and recent graduates with regard to two key questions: when in the degree program do students prefer dissection opportunities and what are the students getting out of participating in dissection? Self‐report survey data from students in preclinical years (n = 105), clinical years (n = 57), and graduates (n = 13) were analyzed. Most (89%) preferred dissection during the preclinical years, with no effect by training year (χ2 = 1.98, p = 0.16), previous anatomy (χ2 = 3.64, p = 0.31), or dissection (χ2 = 3.84, p = 0.26) experience. Three key findings emerged. First, the majority of students prefer to dissect in the preclinical years because they view dissection as important for developing foundation knowledge and delivering an opportunity for consolidation prior to transitioning to primarily clinical studies. In addition, students recognize that it is a time‐consuming activity requiring specialized facilities. Second, three main understandings of the purpose of dissection were reported: depth of learning, learning experience, and real‐world equivalence. Third, these student perspectives of the purpose of dissection are associated with timing preferences for dissection opportunities. The results identify the preclinical phase as the optimal time to strategically integrate dissection into medical training in order to maximize the benefits of this unique learning opportunity for students and minimize its impact upon curricular time.
Real‐time predictive control‐based anti‐pitching method for high‐speed multihull with appendages constraints
Authors: Li Guosheng , Zhang Jun , Liu Zhilin , Hu Haojun , Zheng Linhe
Published: January 2022

In order to mitigate the excessive amplitudes of pitch and heave motions, a real‐time predictive control method is proposed for the high‐speed multihull with strict input constraints of anti‐pitching appendages. The vertical control model of the high‐speed multihull has been established with T‐foil and flap served as anti‐pitching appendages, and the motion couplings between heave and pitch have been analyzed. The wave disturbance considered as a kind of colored noise can be whitened so as to obtain the control signal, and then adaptive extended Kalman filtering method can be used to get the online estimates of the heave velocity and pitch angular velocity. The proposed predictive control‐based anti‐pitching method mainly contains two reformed aspects of the predictive control. One is to take into account the error between the actual and predicted system values, such that the prediction model with linear error correction can be obtained resulting in the enhanced robustness. The other is to employ the Laguerre function to convert the control sequence of moving horizon optimization into the fewer‐dimensional Laguerre parameters, and then the computational burden of online optimization can be significantly reduced indicating the improved real‐time performance. The closed‐loop system stability has also been theoretically analyzed. The simulation and experiment have been carried out to verify the effectiveness of the proposed algorithm in this paper.
Adaptive frequency‐limited ‐model order reduction
Authors: Zulfiqar Umair , Sreeram Victor , Du Xin
Published: January 2022

In this paper, we present an adaptive framework for constructing a pseudo‐optimal reduced model for the frequency‐limited‐optimal model order reduction problem. We show that the frequency‐limited pseudo‐optimal reduced‐order model has an inherent property of monotonic decay in error if the interpolation points and tangential directions are selected appropriately. We also show that this property can be used to make an automatic selection of the order of the reduced model for an allowable tolerance in error. The proposed algorithm adaptively increases the order of the reduced model such that the frequency‐limited‐norm error decays monotonically irrespective of the choice of interpolation points and tangential directions. The stability of the reduced‐order model is also guaranteed. Additionally, it also generates the approximations of the frequency‐limited system Gramians that monotonically approach the original solution. Further, we show that the low‐rank alternating direction implicit iteration method for solving large‐scale frequency‐limited Lyapunov equations implicitly performs frequency‐limited pseudo‐optimal model order reduction. We consider two numerical examples to validate the theory presented in the paper.
Nonlinear cascade control of an electro‐hydraulic actuator with large payload variation
Authors: Wang Yunfei , Zhao Jiyun , Ding Haigang , Zhang He
Published: January 2022

Electro‐hydraulic actuators have been widely used in industrial production, but the unknown variable payload seriously affects its position control accuracy. Therefore, a radial basis function neural network disturbance observer is designed to estimate the lumped disturbance force through strong online learning ability in the absence of force sensor. Besides, a nonlinear cascade controller with double loop structure is proposed in this paper. A global fast terminal sliding mode control method is firstly applied in the outer loop position system, which can eliminate chattering and improve convergence speed comparing to traditional sliding mode control. The inner loop force system adopts a backstepping control method to calculate the actual input of the whole system. Theoretical analysis indicates that the proposed controller is stable even if existing time‐variant disturbance. Moreover, three comparative controllers are designed and tested in both simulations and experiments. Comparative results show that the developed method has absolute average errors of 1.14 and 0.49 mm in different position tracking, which means more satisfactory tracking performance compared to the contrast controllers.
Role of membrane structure on the filtrate flux during monoclonal antibody filtration through virus retentive membranes
Authors: Billups Matthew , Minervini Mirko , Holstein Melissa , Feroz Hasin , Ranjan Swarnim , Hung Jessica , Bao Haiying , Li Zheng Jian , Ghose Sanchayita , Zydney Andrew L.
Published: January 2022

Virus removal filtration is a critical step in the manufacture of monoclonal antibody products, providing a robust size‐based removal of both enveloped and non‐enveloped viruses. Many monoclonal antibodies show very large reductions in filtrate flux during virus filtration, with the mechanisms governing this behavior and its dependence on the properties of the virus filter and antibody remaining largely unknown. Experiments were performed using the highly asymmetric Viresolve® Pro and the relatively homogeneous Pegasus™ SV4 virus filters using a highly purified monoclonal antibody. The filtrate flux for a 4 g/L antibody solution through the Viresolve® Pro decreased by about 10‐fold when the filter was oriented with the skin side down but by more than 1000‐fold when the asymmetric filter orientation was reversed and used with the skin side up. The very large flux decline observed with the skin side up could be eliminated by placing a large pore size prefilter directly on top of the virus filter; this improvement in filtrate flux was not seen when the prefilter was used inline or as a batch prefiltration step. The increase in flux due to the prefilter was not related to the removal of large protein aggregates or to an alteration in the extent of concentration polarization. Instead, the prefilter appears to transiently disrupt reversible associations of the antibodies caused by strong intermolecular attractions. These results provide important insights into the role of membrane morphology and antibody properties on the filtrate flux during virus filtration.
Leaf and Flower Extracts of Six Michelia L.: Polyphenolic Composition, Antioxidant, Antibacterial Activities and in Vitro Inhibition of α‐Amylase and α‐Glucosidase
Authors: Liao Tianzhu , Cao Jiwu , Yang Zhenyu , Cheng Jing , Lu Jun
Published: January 2022

Methanolic extracts of the leaf and flower of Michelia L., an evergreen aromatic genus widely used in landscaping, industry and medicine of various countries, were analyzed. The UPLC‐ESI‐MS/MS analysis led to the identification of 28 polyphenols from six Michelia species that widely distributed and cultivated in southern China, among which quinic acid and chlorogenic acid were the main components. The flower extract of Michelia maudiae had the most abundant polyphenols content, as well as high contents of total phenolic (117.31±7.26 mg GAE/g DW) and total flavonoid (251.60±15.56 mg CE/g DW). Meanwhile, it also showed outstanding performance in three antioxidant indexes of DPPH, ABTS and FRAP. The leaf extracts of Michelia chapensis and Michelia floribunda exhibited excellent inhibition against four pathogenic bacteria. Moreover, certain inhibitory activities were displayed by Michelia macclurei extracts against α‐amylase and α‐glucosidase. This study explored the biological activities of six Michelia species, and provided reference for variety selection with the aim of designing novel phyto‐pharmaceuticals.
Chronic total occlusion percutaneous coronary intervention in prior coronary artery bypass graft surgery patients: Caveat Emptor!
Authors: Simsek Bahadir , Brilakis Emmanouil S.
Published: January 2022

Key Points

Stable angina patients with prior coronary artery bypass graft surgery (CABG) who underwent chronic total occlusion percutaneous coronary intervention (CTO PCI) in England and Wales between 2007 and 2014 had more complex clinical and angiographic characteristics, lower success, similar incidence of periprocedural complications, and higher mortality at follow‐up compared with patients who had not had prior CABG.

After adjustment, CTO PCI in prior CABG patients was associated with 66% lower success rates, but similar risk of periprocedural complications and mortality at follow‐up.

CTO PCI in prior CABG patients can be very challenging, is subject to unique complications and risks, and should be undertaken with caution by experienced operators.
One‐Pot Synthesis and Antiproliferative Activity of Highly Functionalized Pyrazole Derivatives
Authors: Lusardi Matteo , Rotolo Chiara , Ponassi Marco , Iervasi Erika , Rosano Camillo , Spallarossa Andrea
Published: January 2022

A series of highly functionalized pyrazole derivatives has been prepared by a one‐pot, versatile and regioselective procedure. Pyrazoles 1–29 were tested in cell‐based assay to assess their antiproliferative activity against a panel of tumour cells. Additionally, the cytotoxicity of prepared compounds was evaluated against normal human fibroblasts. The antiproliferative activity of the synthesized molecules emerged to be affected by the nature of the substituents of the pyrazole scaffold and derivatives 21–23 proved to inhibit the growth of melanoma and cervical cancer cells. Compound 23 was identified as the most active derivative and docking simulations predicted its ability to interact with estrogen receptors.
Relative Bioavailability and Food Effect of GSK3640254 Tablet and Capsule Formulations in Healthy Participants
Authors: Johnson Mark , Pene Dumitrescu Teodora , Joshi Samit R. , Mathew Ashwin , Bainbridge Veronica , Zhan Joyce , Lataillade Max
Published: January 2022

GSK3640254 is a next‐generation maturation inhibitor with demonstrated potency across HIV‐1 subtypes and a high barrier to emergent resistance. This phase I, 2‐part, randomized, open‐label study (ClinicalTrials.gov identifier, NCT04263142) in healthy participants assessed the relative bioavailability of a single dose of GSK3640254 200 mg in tablet and capsule formulations (part 1) and the effect of food on the pharmacokinetic profile of the tablet formulation (part 2). Overall, 39 participants were randomized to treatment (part 1, n = 18; part 2, n = 21). All participants in part 1 completed the study; 2 participants in part 2 withdrew before study completion (adverse event, n = 1; physician decision, n = 1). In part 1, plasma exposures of the GSK3640254 tablet formulation were not meaningfully different from those of the capsule formulation when administered in the presence of a moderate‐fat meal. In part 2, GSK3640254 plasma exposures increased by ≈3‐ to 4‐fold under high‐ and moderate‐fat conditions, respectively, compared with fasted conditions. No major safety or tolerability findings were observed. The highest incidence of adverse events (24%) was reported under high‐fat conditions. Taken together, these data support the use of the tablet formulation coadministered with food in the clinical development of GSK3640254 for treatment of HIV‐1.
When a pest is not a pest: Birds indirectly increase defoliation but have no effect on yield of soybean crops
Authors: Garfinkel Megan B. , Fuka Mark E. , Minor Emily , Whelan Christopher J.
Published: January 2022

Natural habitats near agricultural systems can be sources of both ecosystem services and disservices on farms. Ecosystem disservices, those aspects of an ecosystem that have negative impacts on humans, may disproportionately affect conservation decisions made by farmers. Birds, in particular, can have complex effects on crops, ranging from positive to neutral to negative. Therefore, it is important to quantify them in a meaningful way. Birds may be more abundant on farms near natural areas and may provide ecosystem services by consuming insect pests. However, when birds consume beneficial predatory arthropods rather than pest species (intraguild predation), they can provide a disservice to the farmer if the intraguild predation decreases crop yield. We studied bird intraguild predation in Illinois (USA) at six soybean fields adjacent to grasslands that provided source habitat for bird populations. We placed cages over soybean crops, which excluded birds but allowed access to arthropods, and measured differences in leaf damage and crop yield of plants in control and exclosure plots. We also conducted point counts at each site to quantify the bird communities. We found that plants within the bird exclosures had lower levels of leaf damage by pests than those in control plots, but there was no resulting effect on crop yield. We also found that sites with higher bird abundance had higher levels of leaf damage by pests, but bird species richness was not a significant predictor of leaf damage. These results suggest that although birds may have released pests through intraguild predation, there was no net disservice when considering crop yield, the variable most important to stakeholders.
Socio‐economic status and 1 year mortality among patients hospitalized for heart failure in China
Authors: Ge Yilan , Zhang Lihua , Gao Yan , Wang Bin , Zheng Xin ,   for the China PEACE Collaborative Group
Published: January 2022

Aims

This study explored the association between socio‐economic status (SES) and mortality among patients hospitalized for heart failure (HF) in China.

Methods and results

We used data from the China Patient‐centred Evaluative Assessment of Cardiac Events‐Prospective Heart Failure Study (China PEACE 5p‐HF Study), which enrolled patients hospitalized primarily for HF from 52 hospitals between 2016 and 2018. SES was measured using the income, employment status, educational attainment, and partner status. Individual socio‐economic risk factor (SERF) scores were assigned based on the number of coexisting SERFs, including low income, unemployed status, low education, and unpartnered status. We assessed the effects of SES on 1 year all‐cause mortality using Cox models. We used the Harrell c statistic to investigate whether SES added incremental prognostic information for mortality prediction. A total of 4725 patients were included in the analysis. The median (interquartile range) age was 67 (57–76) years; 37.6% were women. In risk‐adjusted analyses, patients with low/middle income [low income: hazard ratio (HR) 1.61, 95% confidence interval (CI) 1.21–2.14; middle income: HR 1.32, 95% CI 1.00–1.74], unemployment status (HR 1.43, 95% CI 1.10–1.86), low education (HR 1.25, 95% CI 1.03–1.53), and unpartnered status (HR 1.22, 95% CI 1.03–1.46) had a higher risk of death than patients with high income, who were employed, who had a high education level, and who had a partner, respectively. Compared with the patients without SERFs, those with 1, 2, 3, and 4 SERFs had 1.52‐, 2.01‐, 2.45‐, and 3.20‐fold increased risk of death, respectively. The addition of SES to fully adjusted model improved the mortality prediction, with increments in c statistic of 0.01 (P < 0.01).

Conclusions

In a national Chinese cohort of patients hospitalized for HF, low income, unemployment status, low education, and unpartnered status were all associated with a higher risk of death 1 year following discharge. In addition, incorporating SES into a clinical‐based model could better identify patients at risk for death. Tailored clinical interventions are needed to mitigate the excess risk experienced by those socio‐economic deprived HF patients.