bluuebunny/crossref_metadata_2025 huggingface dataset:
Understanding the Structure and Properties of Sesqui‐Chalcogenides (i.e., V2VI3 or Pn2Ch3 (Pn = Pnictogen, Ch = Chalcogen) Compounds) from a Bonding Perspective
Authors: Cheng Yudong , Cojocaru‐Mirédin Oana , Keutgen Jens , Yu Yuan , Küpers Michael , Schumacher Mathias , Golub Pavlo , Raty Jean‐Yves , Dronskowski Richard , Wuttig Matthias
Published: September 2019

A number of sesqui‐chalcogenides show remarkable properties, which make them attractive for applications as thermoelectrics, topological insulators, and phase‐change materials. To see if these properties can be related to a special bonding mechanism, seven sesqui‐chalcogenides (Bi2Te3, Bi2Se3, Bi2S3, Sb2Te3, Sb2Se3, Sb2S3, and β‐As2Te3) and GaSe are investigated. Atom probe tomography studies reveal that four of the seven sesqui‐chalcogenides (Bi2Te3, Bi2Se3, Sb2Te3, and β‐As2Te3) show an unconventional bond‐breaking mechanism. The same four compounds evidence a remarkable property portfolio in density functional theory calculations including large Born effective charges, high optical dielectric constants, low Debye temperatures and an almost metal‐like electrical conductivity. These results are indicative for unconventional bonding leading to physical properties distinctively different from those caused by covalent, metallic, or ionic bonding. The experiments reveal that this bonding mechanism prevails in four sesqui‐chalcogenides, characterized by rather short interlayer distances at the van der Waals like gaps, suggestive of significant interlayer coupling. These conclusions are further supported by a subsequent quantum‐chemistry‐based bonding analysis employing charge partitioning, which reveals that the four sesqui‐chalcogenides with unconventional properties are characterized by modest levels of charge transfer and sharing of about one electron between adjacent atoms. Finally, the 3D maps for different properties reveal discernible property trends and enable material design.
1 cm2 Organic Photovoltaic Cells for Indoor Application with over 20% Efficiency
Authors: Cui Yong , Yao Huifeng , Zhang Tao , Hong Ling , Gao Bowei , Xian Kaihu , Qin Jinzhao , Hou Jianhui
Published: September 2019

Organic photovoltaic (OPV) technologies have the advantages of fabricating larger‐area and light‐weight solar panels on flexible substrates by low‐cost roll‐to‐toll production. Recently, OPV cells have achieved many significant advances with power conversion efficiency (PCE) increasing rapidly. However, large‐scale solar farms using OPV modules still face great challenges, such as device stability. Herein, the applications of OPV cells in indoor light environments are studied. Via optimizing the active layers to have a good match with the indoor light source, 1 cm2 OPV cells are fabricated and a top PCE of 22% under 1000 lux light‐emitting diode (2700 K) illumination is demonstrated. In this work, the light intensities are measured carefully. Incorporated with the external quantum efficiency and photon flux spectrum, the integral current densities of the cells are calculated to confirm the reliability of the photovoltaic measurement. In addition, the devices show much better stability under continuous indoor light illumination. The results suggest that designing wide‐bandgap active materials to meet the requirements for the indoor OPV cells has a great potential in achieving higher photovoltaic performance.
Hierarchically Organized Ultrathin NiO Nanofibers/Highly Defective‐rGO Heteronanocomposite: An Advanced Electrode Material for Asymmetric Supercapacitors
Authors: Paliwal Mahesh Kumar , Meher Sumanta Kumar
Published: September 2019

Herein, defective‐rGO (D‐rGO) is endorsed as a unique conducting matrix for defect‐induced interfacial growth of ultrathin dangling‐NiO nanofibers. The physicochemical analyses corroborate added defect density on the graphene surface, defect‐induced growth of NiO, and excellent hydrophilicity of NiO/D‐rGO heteronanocomposite. Thorough electrochemical analyses of NiO/D‐rGO heteronanocomposite show high specific capacitance of 1992 F g−1, ultralow equivalent series resistance (ESR) of 1.7 Ω, and ≈92.5% retention of charge storage after 5000 galvanostatic charge–discharge (GCD) cycles. The advanced NiO/D‐rGO ‖ Bi2O3 asymmetric supercapacitor (ASC) device delivers high areal/mass specific capacitance and exhibits outstanding rate capacitance under extreme current density conditions. The ASC device retains a significant 89.5% of areal capacitance after 5000 GCD cycles under high rate conditions. The ASC device also delivers a high energy density of ≈43.7 Wh kg−1 at a power density of ≈4799 W kg−1 and retains ≈46% of the energy density at a very high power density of ≈18 518 W kg−1. The excellent performance of the ASC device is ascribed to defect‐induced improved bonding between D‐rGO and NiO, microstructural stability of NiO/D‐rGO, D‐rGO prompted conductivity, and “ion‐buffering‐reservoir” ‐alike behavior of the fiber assembly. The present approach is significant in developing new‐age supercapacitors for high rate applications.
Hybrid Supercapacitors Based on Interwoven CoO‐NiO‐ZnO Nanowires and Porous Graphene Hydrogel Electrodes with Safe Aqueous Electrolyte for High Supercapacitance
Authors: Sun Mingze , Wang Jingmin , Xu Mingsheng , Fang Zhenbin , Jiang Lei , Han Qiang , Liu Jichang , Yan Manqing , Wang Qiyang , Bi Hong
Published: September 2019

Metal oxides–based supercapacitors have attracted much attention due to their easy fabrication and ultra‐high theoretical specific capacitance. Here, a novel ternary metal oxide (CoO‐NiO‐ZnO, CNZO) in situ grown on Ni foam (CNZO@Ni foam) is prepared by one‐pot hydrothermal synthesis and a subsequent annealing method. Compared with the corresponding binary and single metal oxides of CoO‐ZnO, NiO‐ZnO, CoO‐NiO, CoO, NiO, and ZnO, this ternary metal oxide shows an ultra‐high specific capacitance (areal capacitance) of 2115.5 F g−1 (4.23 F cm−2) at a current density of 1 A g−1 (2 mA cm−2). Further, a hybrid supercapacitor (HSC) is assembled by the CNZO@Ni foam//porous graphene hydrogel (PGH), which exhibits a wide potential window of 1.6 V, and a high energy density 53.67 Wh kg−1 at a power density of 800 W kg−1. Moreover, it also shows good cycling stability of 87.9% after 5000 charge/discharge cycles. This work provides an efficient and facile way to fabricate HSCs based on ternary metal oxide nano‐networks and PGH with an aqueous electrolyte for safe and high‐energy‐density supercapacitors.
Confined Catalysis: Progress and Prospects in Energy Conversion
Authors: Shifa Tofik Ahmed , Vomiero Alberto
Published: September 2019

Space confined catalysis has emerged as viable strategy for achieving potent and efficient catalysts in various important reactions. It offers a means of creating unique nanoscale chemical environments partitioned from the surrounding bulk space. This gives rise to the phenomena of nanoconfinement, where the energetics and kinetics of catalytic reactions can be modulated upon confining the catalysts in a particular site. Various scaffolds have been reported so far for confinement. Among these, void spaces under the cover of 2D materials, van der Waals (vdW) gaps of layered 2D materials, nanotubes, and porous surfaces have recently won copious attention. In this review, the concept of space confinement with respect to its effect on the electronic and structural properties of a catalyst is discussed. Emphasis is devoted to the catalysis of water splitting and CO2 reduction reactions. The progress in the design and applications of space confined catalysts is then traced. Finally, a discussion of emerging issues yet to be explored for this strategy to achieve a high efficiency, and future directions with the potential to become a new hotspots are presented.
Honeycomb Structure Inspired Triboelectric Nanogenerator for Highly Effective Vibration Energy Harvesting and Self‐Powered Engine Condition Monitoring
Authors: Xiao Xiu , Zhang Xiangqian , Wang Siyuan , Ouyang Han , Chen Pengfei , Song Liguo , Yuan Haichao , Ji Yulong , Wang Peihong , Li Zhou , Xu Minyi , Wang Zhong Lin
Published: September 2019

Vibration in mechanical equipment can serve as a sustainable energy source to power sensors and devices if it can be effectively collected. In this work, a honeycomb structure inspired triboelectric nanogenerator (HSI‐TENG) consisting of two copper electrode layers with sponge bases and one honeycomb frame filled with polytetrafluoroethylene (PTFE) balls is proposed to harvest vibration energy. The application of a compact honeycomb structure increases the maximum power density of HSI‐TENG by 43.2% compared to the square grid structure and provides superior advantages in large‐scale manufacturing. More importantly, the nonspring‐assisted HSI‐TENG can generate electricity once the PTFE balls obtain sufficient kinetic energy to separate from the bottom electrode layer regardless of the vibration frequency and direction. This is fundamentally different from the spring‐assisted harvesters that can only work around their natural frequencies. The vibration model and working criteria of the HSI‐TENG are established. Furthermore, the HSI‐TENG is successfully used to serve as a self‐powered sensor to monitor engine conditions by analyzing the electrical output of the HSI‐TENG installed on a diesel engine. Therefore, the nonspring‐assisted HSI‐TENG provides a novel strategy for highly effective vibration energy harvesting and self‐powered machinery monitoring.
Construction and optimization of a base editor based on the MS2 system
Authors: Zhang Shuzhen , Feng Songjie , Jiang Wen , Huang Xingxu , Chen Jieping
Published: September 2019

Background

Catalytic defect Cas9‐cytosine deaminase fusion is widely used in base editing. The Multiple copy numbers of the MS2 binding site (MBS) can recruit multiple MS2 coat proteins (MCPs), which are usually applied to amplify signals. Our study aimed to apply the MS2 signal amplification system to the base editing system in order to achieve simultaneous mutations of multiple bases at the target genome site.

Methods

Multiple copy numbers of the MS2 were ligated to the 3′‐end of sgRNA, and MCP was fused to the 5′‐end of cytosine deaminases. The MS2 was recognized by MCP to recruit cytosine deaminase for base substitutions (C‐T) at the target site. Different Cas9 variants, different cytosine deaminases and different copy numbers of MS2 were tested in this system, and the different versions of base editors were compared by editing efficiency and window.

Results

In this study, dCas9, nCas9 (D10A) and nCas9 (H840A) were used. Among these 3 Cas9 variants, dCas9 exhibited higher base mutation efficiency. Two cytosine deaminases were then applied and the efficiency of rAPOBEC1 deaminase was found to be higher than AID. We also increased the copy numbers of MS2 linked to sgRNA from 2 to 12. Disappointingly, the sgRNA‐12x MS2 did not improve the editing efficiency or increase the editing window.

Conclusion

An optimal version of base editor based on the MS2 system, MS2‐BE‐rAPOBEC1 (sgRNA‐2x MS2, MCP‐rAPOBEC1 and dCas9), was obtained. This tool can simultaneously mutate multiple bases at the target site, providing a new approach for the study of genome functions.
Rhodium(I)/Zn(OTf)2‐Catalyzed Asymmetric Ring Opening/Cyclopropanation of Oxabenzonorbornadienes with Phosphorus Ylides
Authors: Chen Tao , Gan Lifei , Wang Ran , Deng Yuhua , Peng Fangzhi , Lautens Mark , Shao Zhihui
Published: September 2019

The strong binding ability of P‐ylides with transition metals limits the utilization of stabilized P‐ylide as nucleophiles in asymmetric organometallic catalysis. Herein we describe the first rhodium‐catalyzed asymmetric ring‐opening reaction of P‐ylides utilizing oxabicyclic alkenes as the electrophilic partner. Various P‐ylides including ester‐, ketone‐ and amide‐style P‐ylides are all applicable. This asymmetric reaction occurs through the cleavage of two bridgehead C−O bonds and the formation of two C−C bonds, and oxabenzonorbornadienes are used as 1,4‐biselectrophiles, thus providing access to benzonorcaradienes in good yields with high enantioselectivity and perfect diastereoselectivity. The present protocol also constitutes the first highly enantioselective direct catalytic asymmetric cyclopropanation of stabilized P‐ylide nucleophiles.
Palladium Catalysis for Aerobic Oxidation Systems Using Robust Metal–Organic Framework
Authors: Li Jiawei , Liao Jianhua , Ren Yanwei , Liu Chi , Yue Chenglong , Lu Jiaming , Jiang Huanfeng
Published: September 2019

Described here is a new and viable approach to achieve Pd catalysis for aerobic oxidation systems (AOSs) by circumventing problems associated with both the oxidation and the catalysis through an all‐in‐one strategy, employing a robust metal–organic framework (MOF). The rational assembly of a PdII catalyst, phenanthroline ligand, and CuII species (electron‐transfer mediator) into a MOF facilitates the fast regeneration of the PdII active species, through an enhanced electron transfer from in situ generated Pd0 to CuII, and then CuI to O2, trapped in the framework, thus leading to a 10 times higher turnover number than that of the homogeneous counterpart for Pd‐catalyzed desulfitative oxidative coupling reactions. Moreover, the MOF catalyst can be reused five times without losing activity. This work provides the first exploration of using a MOF as a promising platform for the development of Pd catalysis for AOSs with high efficiency, low catalyst loading, and reusability.
Chiral‐Organotin‐Catalyzed Kinetic Resolution of Vicinal Amino Alcohols
Authors: Yang Hui , Zheng Wen‐Hua
Published: September 2019

A highly efficient kinetic resolution of racemic amino alcohols has been achieved for the first time with a chiral tin catalyst. A chiral organotin compound with 3,4,5‐trifluorophenyl groups at the 3,3′‐positions of the binaphthyl framework enabled this transformation with excellent yield and high enantioselectivity. The process tolerates aryl‐ and alkyl‐substituted amino alcohols and a variety of other substrates, affording the corresponding products in high enantioselectivity and with s factors up to >500.
Anionic Dopant Delocalization through p‐Band Modulation to Endow Metal Oxides with Enhanced Visible‐Light Photoactivity
Authors: Song Xianyin , He Dong , Li Wenqing , Ke Zunjian , Liu Jiangchao , Tang Chongyang , Cheng Li , Jiang Changzhong , Wang Ziyu , Xiao Xiangheng
Published: September 2019

An N‐doped TiO2 model reveals a conceptually different mechanism for activating the N dopant based on delocalized orbital hybridization through O vacancy incorporation. Synchrotron‐based X‐ray absorption spectroscopy, time‐resolved fluorescence, and DFT studies revealed that O vacancy incorporation can effectively stimulate the delocalization of N impurity states through p‐band orbital modulation, which leads to a significant enhancement in photocarrier lifetime. Consequently, this effect also results in a remarkable increase in the incident photon‐to‐electron conversion efficiency in the range of 400–550 nm compared to that of conventional N‐incorporated TiO2 (15 % versus 1 % at 450 nm). This work reveals the fundamental necessity of orbital modulation in the band engineering of metal oxides for driving solar water splitting and beyond.
Synthesis, characterization, molecular docking studies and in vitro screening of new metal complexes with Schiff base as antimicrobial and antiproliferative agents
Authors: Pahonțu Elena , Proks Maria , Shova Sergiu , Lupașcu Gina , Ilieș Diana‐Carolina , Bărbuceanu Ștefania‐Felicia , Socea Laura‐Ileana , Badea Mihaela , Păunescu Virgil , Istrati Dorin , Gulea Aurelian , Drăgănescu Doina , Pîrvu Cristina Elena Dinu
Published: September 2019

A series of Cu(II), Co(II), Pd(II), Pt(II), Zn(II), Cd(II) and Fe(III) complexes were designed and synthesized using Schiff base 1‐phenyl‐2,3‐dimethyl‐4‐(N‐3‐formyl‐6‐methylchromone)‐3‐pyrazolin‐5‐one (HL). The new metal complexes were investigated using various physicochemical techniques including elemental and thermal analyses, molar electric conductivity and magnetic susceptibility measurements, as well as spectroscopic methods. Also, the crystal structures of ligand HL and the Pd(II) complex were determined using single‐crystal X‐ray diffraction analysis. For all compounds, the antimicrobial activity was studied against a series of standard strains: Staphylococcus aureus, Bacillus cereus, Enterococcus faecalis, Escherichia coli, Acinetobacter baumannii, Candida albicans, Candida krusei and Cryptococcus neoformans. The in vitro antiproliferative activity of the ligand and complexes was evaluated against ten cancer cell lines: MSC, A375, B16 4A5, HT‐29, MCF‐7, HEp‐2, BxPC‐3, RD, MDCK and L20B. At 10 μM concentration a significant cytotoxic effect of the Co(II), Pd(II) and Cd(II) complexes was observed against B16 4A5 murine melanoma cells. The Zn(II) complex is active against HEp‐2, RD and MDCK cancer cell lines, where IC50 values vary between 1.0 and 77.6 and for BxPC‐3 the activity index versus doxorubicin is 3.7 times higher.
Improved photocatalytic performance of anatase TiO2 synthesized through ethanol supercritical drying technique
Authors: Zhang Xian , Liu Chang , Wang Min , Sun Xiao , Sun Xiao Yu , Qian Ni Xian , Rao Rui , Ma Yong Qing
Published: September 2019

Anatase titania (TiO2) nanoparticles were synthesized via a self‐developed ethanol vapor‐thermal method at 240°C (T240) and 250°C (T250), i.e. at temperatures lower and higher, respectively, than the supercritical temperature (243.5°C, 7.0 MPa) of ethanol. Compared to T240, T250 exhibited a higher ratio of exposed (001) facets, oxygen vacancies, and concomitant TiOx. The specific surface area of T250 was 119.0 m2 g−1, smaller than that of T240 (144.2 m2 g−1). During the degradation of methylene blue, T250 exhibited a high apparent rate constant (Kapp) of 14.5 × 10−2 min−1, which was 6.3 times larger than that for T240. Furthermore, compared to T240, T250 exhibited better performance toward degradation of phenol. Results of electron spin resonance spectroscopy and photoluminescence indicated that the photogenerated electron–hole pairs possessed higher separation efficiency for T250 than for T240. In summary, the excellent photocatalytic performance of T250 originates from the higher ratios of exposed (001) facets, oxygen vacancies or TiOx, C═O groups adsorbed at the surface of particles, and higher separation efficiency of photogenerated electron–hole pairs. By employing this self‐developed vapor‐thermal method, a variety of catalysts and their composites can be synthesized, which may exhibit novel morphological characteristics and properties as well as excellent photocatalytic performance.
Finely dispersed palladium on silk‐fibroin as an efficient and ligand‐free catalyst for Heck cross‐coupling reaction
Authors: Mirzaei Hakimeh , Eshghi Hossein , Seyedi Seyed Mohammad
Published: September 2019

A palladium–fibroin complex (Pd/Fib.) was prepared by the addition of sonicated fibroin fiber in water to palladium acetate solution. Pd (OAc)2 was absorbed by fibroin and reduced with NaBH4 at room temperature to the Pd(0) nanoparticles. Powder‐X‐ray diffraction, scanning electron microscopy–energy‐dispersive X‐ray spectroscopy, Fourier transform‐infrared, CHN elemental analysis and inductively coupled plasma‐atomic emission spectroscopy were carried out to characterize the Pd/Fib. catalyst. Catalytic activity of this finely dispersed palladium was examined in the Heck coupling reaction. The catalytic coupling of aryl halides (‐Cl, ‐Br, ‐I) and olefins led to the formation of the corresponding coupled products in moderate to high yields under air atmosphere. A variety of substrates, including electron‐rich and electron‐poor aryl halides, were converted smoothly to the targeted products in simple procedure. Heterogeneous supported Pd catalyst can be recycled and reused several times.
Enhanced Oxygen Reduction and Methanol Oxidation Electrocatalysis over Bifunctional PtPdIr Mesoporous Hollow Nanospheres
Authors: Deng Kai , Xu You , Dai Zechuan , Yu Hongjie , Yin Shuli , Wang Ziqiang , Li Xiaonian , Wang Liang , Wang Hongjing
Published: September 2019

Designing and constructing nano‐architectures with abundant reactive atoms exposed on the surface and widely open pore interiors is an effective strategy for highly efficient utilization of Pt‐based catalysts. Herein, we report a facile method to synthesize tri‐metallic PtPdIr mesoporous hollow nanospheres (PtPdIr MHNSs) by selective chemical removal of sacrificial metallic cores from pre‐constructed Pd@PtIr mesoporous nanospheres (Pd@PtIr MNSs). The unique nano‐architectures, with mesoporous shells interconnected into the interior hollow cavities and the synergistic electronic effect from tri‐metallic PtPdIr composition, enable the as‐synthesized PtPdIr MHNSs to be efficient bifunctional electrocatalysts for catalyzing both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR).
Thermische Stabilität von UHPC
Authors: Scheffler Benjamin , Wetzel Alexander , Sälzer Philipp , Middendorf Bernhard
Published: September 2019

In den letzten Jahren ist der Einsatz von Hochleistungsbetonen zunehmend gestiegen. Für die Anwendung von Ultra‐Hochleistungsbetonen (UHPC) gelten neben den Anforderungen an die Tragfähigkeit und Dauerhaftigkeit ebenso brandschutztechnische Anforderungen. Kennwerte zum thermischen sowie mechanischen Verhalten von UHPC unter Brandeinwirkung bestehen bereits. Aufgrund des hochdichten, nahezu kapillarporenfreien Mikrogefüges des UHPC führen Temperaturbelastungen > 250 °C zu einer Schädigung des Gefüges bis hin zu einem nicht vorhersehbaren Versagen durch explosionsartige Abplatzungen. Im Brandfall liegt die Temperatureinwirkung um ein Vielfaches höher und zudem sind zyklische Beanspruchungen nicht relevant. In Abgrenzung dazu wird ein Beton für den Einsatz als Konstruktionsbaustoff in Industriebereichen, wie z. B. dem Kraftwerks‐ und Schornsteinbau sowie in speziellen Applikationen im Maschinenbau, benötigt, der einer dauerhaften und zyklischen thermischen Belastung bis 500 °C standhält. Die hier aufgeführten Ergebnisse umfassen das Materialverhalten von bestehenden sowie optimierten UHPC‐Formulierungen bei unterschiedlichen thermischen Belastungsprofilen. Die Eigenschaften des Festbetons wurden vor und nach der thermischen Beanspruchung charakterisiert. Da die Basis‐Formulierung des UHPC nur bis zu einer bestimmten Temperaturstufe thermisch stabil war, wurde dieser durch Zugabe von Celluloseregeneratfasern optimiert, um explosive Abplatzungen zu vermeiden und diesen thermisch zu stabilisieren.
Mesenchymal stromal cell secretome as a therapeutic strategy for traumatic brain injury
Authors: Muhammad Suleiman A.
Published: September 2019

Traumatic brain injury (TBI) is a global health problem that is a common cause of disability and mortality. Despite the availability of many treatment options, none is capable of restoring functional and structural recovery of the damaged brain. Both the results of preclinical and clinical studies suggest the use of mesenchymal stromal cells (MSCs) as a therapeutic strategy for structural and functional recovery in TBI. However, recent evidence shows that the neuroprotective potential of MSCs is due to multiple secretions of bioactive molecules that modulate tissue microenvironment for tissue repair and regeneration. The results of preclinical studies indicate the therapeutic benefits of MSC secretome in TBI. Soluble bioactive molecules and extracellular vesicles are the various factors secreted by MSCs that can induce neurogenesis, angiogenesis, neovascularization, and anti‐inflammatory activities. This review highlights the neuroprotective effect of MSC secretome for the treatment of TBI. In addition, the possible challenges of secretome as biotherapeutics are identified and how some of the issues raised could be overcome for effective clinical application are also discussed.
Tannin‐Adsorbents for Water Decontamination and for the Recovery of Critical Metals: Current State and Future Perspectives
Authors: Santos Sílvia C. R. , Bacelo Hugo A. M. , Boaventura Rui A. R. , Botelho Cidália M. S.
Published: September 2019

Biosorption is known as an effective way to clean‐up water from organic and inorganic contaminants and has also emerged as a promising technology to recover critical substances. Tannins are renewable materials, coming from multiple vegetable sources. A variety of biosorbents have been developed from tannins, including tannin resins, rigid foams, composites with mesoporous silica, cellulose, collagen, and magnetic adsorbents. These materials have shown an excellent ability to uptake heavy‐metal cations (Cd(II), Cu(II), Pb(II), Ni(II), Cr(III)), owning to the chelating ability provided by the plentiful adjacent hydroxyl groups. In addition, tannin‐adsorbents have shown exceptional ability to remove Cr(VI), and to uptake Au(III) and Pd(II) from strong acidic solutions, which has evident application in the recovery of precious metals from e‐wastes leaching. The fact that tannin‐adsorbents can reduce the oxidation state of these adsorbates to Cr(III) and to elemental species of Au and Pd is interesting. Adsorption of dyes, surfactants, pharmaceuticals and antimony is also feasible, but the removal of certain metalloid species, such as arsenic and phosphate, seems to be limited even after applying chemical modifications. This article presents a systematic review on the preparation of tannin‐adsorbents and their application in water decontamination and in the recovery of critical metals.
A cis‐eQTL genetic variant in PLK4 confers high risk of hepatocellular carcinoma
Authors: Meng Lijuan , Zhou Yan , Ju Sihan , Han Jing , Song Ci , Kong Jing , Wu Yifei , Lu Shuai , Xu Jiani , Yuan Wenwen , Zhang Erbao , Wang Cheng , Hu Zhibin , Gu Yayun , Luo Rongcheng , Wang Xuehao
Published: September 2019

Purpose

The overexpression and knockdown of PLK4 were both reported to generate aneuploidy. Thus, we aimed to investigate whether genetic variants in PLK4 contribute to the development of hepatocellular carcinoma (HCC).

Methods

We evaluated associations of common variants in PLK4 and its promoter for the risk of HCC in our association study (1300 cases and 1344 controls). The genotype‐tissue expression (GTEx) and The cancer genome atlas (TCGA) databases were used to quantify the expression of PLK4. Cell proliferation and migration affected by PLK4 in HCC were assessed in vitro. Drug susceptibility testing (DST) model was used to assess the sensibility of PLK4‐activated HCC to CFI‐400945, a small molecule inhibitor of PLK4.

Results

Herein, we found a significant association between rs3811741, located in the PLK4 intron, and liver cancer risk (OR = 1.26, P = 9.81 × 10−5). Although PLK4 expressed at lower levels in somatic tissues compared to the testis, the risk allele A of rs3811741 was associated with increased PLK4 expression in liver cancer tissues. Additionally, PLK4 high expression was remarkably associated with shortened survival of HCC (HR = 1.97, P = .001). Furthermore, overexpression of PLK4 promoted, while knockdown of PLK4 suppressed cancer cell proliferation, migration, and invasion. DST model demonstrated that CFI‐400945 can effectively suppress rampant proliferation of HCC with highly expressed PLK4.

Conclusion

Taken together, our study demonstrated that PLK4 is a susceptibility gene and plays an oncogenic role in HCC. Furthermore, we identified that PLK4 sensitives HCC to CFI‐400945, which may be an ideal therapy target for HCC.
CRM197 reverses paclitaxel resistance by inhibiting the NAC‐1/Gadd45 pathway in paclitaxel‐resistant ovarian cancer cells
Authors: Tang Xiao‐han , Li Hui , Zheng Xiu‐shuang , Lu Mei‐song , An Yuan , Zhang Xiao‐lei
Published: September 2019

Heparin‐binding epidermal growth factor‐like growth factor (HB‐EGF) is a new promising target for the treatment of ovarian cancer. Our previous study showed that cross‐reacting material 197 (CRM197), a specific HB‐EGF inhibitor, significantly reverses resistance against paclitaxel in paclitaxel‐resistant ovarian cancer cells. However, the mechanism of the effect of CRM197 on the reversion of paclitaxel resistance was unclear. In this study, in vitro and in vivo data suggested that CRM197 treatment sensitized paclitaxel‐resistant ovarian cancer cells to paclitaxel, at least in part, via nucleus accumbens‐1 (NAC‐1) and its downstream pathway, DNA damage‐inducible 45‐γ interacting protein (Gadd45gip1)/growth arrest and DNA damage‐inducible 45 (Gadd45), in A2780/Taxol and SKOV3/Taxol cells. The results also showed that CRM197 activated the proapoptotic JNK/p38MAPK pathway to enhance caspase‐3 activity and apoptosis by downregulation of the NAC‐1/Gadd45gip1/Gadd45 pathway, leading to reversion of paclitaxel resistance in A2780/Taxol and SKOV3/Taxol cells. This study provides the first mechanism through which CRM197 significantly reverses resistance against paclitaxel by modulating the NAC‐1/Gadd45gip1/Gadd45 pathway in paclitaxel‐resistant ovarian cancer cells, and the mechanism of HB‐EGF inhibition as a novel therapeutic strategy for patients with paclitaxel‐resistant ovarian cancer.
Efficacy and safety of different fractions in stereotactic body radiotherapy for spinal metastases: A systematic review
Authors: Gong Yining , Xu Lingyi , Zhuang Hongqing , Jiang Liang , Wei Feng , Liu Zhongjun , Li Yan , Yu Miao , Ni Kaiwen , Liu Xiaoguang
Published: September 2019

Background

In the treatment of spinal metastases, stereotactic body radiotherapy (SBRT) delivers precise, high‐dose radiation to the target region while sparing the spinal cord. A range of doses and fractions had been reported; however, the optimal prescribed scheme remains unclear.

Methods

Two reviewers performed independent literature searches of the PubMed, EMBASE, Cochrane Database, and Web of Science databases. Articles were divided into one to five fractions groups. The Methodological Index for Non‐randomized Studies (MINORS) was used to assess the quality of studies. Local control (LC) and overall survival (OS) were presented for the included studies and a pooled value was calculated by the weighted average.

Results

The 38 included studies comprised 3,754 patients with 4,731 lesions. The average 1‐year LCs for the one to five fractions were 92.7%, 84.6%, 86.8%, 82.6%, and 80.6%, respectively. The average 1‐year OS for the one to five fractions were 53.0%, 70.4%, 60.1%, 48%, and 80%, respectively. The 24 Gy/single fraction scheme had a higher 1‐year LC (98.1%) than those of 24 Gy/two fractions (85.4%), 27 Gy/three fractions (84.9%), and 24 Gy/three fractions (89.0%). The incidence of vertebral compression fracture was 10.3%, with 10.7% in the single‐fraction group and 10.1% in the multi‐fraction group. The incidence of radiation‐induced myelopathy was 0.19%; three and two patients were treated with single‐fraction and multi‐fraction SBRT, respectively. The incidence of radiculopathy was 0.30% and all but one patient were treated with multi‐fraction SBRT.

Conclusions

SBRT provided satisfactory efficacy and acceptable safety for spinal metastases. Single‐fraction SBRT demonstrated a higher local control rate than those of the other factions, especially the 24 Gy dose. The risk of vertebral compression fracture (VCF) was slightly higher in single‐fraction SBRT and more patients developed radiculopathy after multi‐fraction SBRT.
Modulation of Pharmacologically Relevant Properties of Piperidine Derivatives by Functional Groups in an Equatorial or Axial β‐Position to the Amino Group
Authors: Schnider Patrick , Dolente Cosimo , Stalder Henri , Martin Rainer E. , Reinmüller Viktoria , Marty Roman , Wyss Gramberg Caroline , Wagner Björn , Fischer Holger , Alker André M. , Müller Klaus
Published: September 2019

Thirteen epimeric pairs of 5‐substituted N‐piperonyl‐3‐phenylpiperidine derivatives were synthesized in order to explore the stereospecific modulation of basicity, lipophilicity, aqueous solubility, and membrane permeation by functional groups in equatorial or axial positions beta to the amine unit. While this comprehensive data set provides enhanced insight into multiple factors that affect basicity and lipophilicity, it fills an important knowledge gap, providing a frame of reference for the property‐based design of bioactive compounds. Impacts on amine basicity are very pronounced for the β‐equatorial functional groups and parallel basicity‐lowering effects known for acyclic amine derivatives. For β‐axial functional groups, the basicity‐lowering effects are generally decreased, with the nitrile group as the only exception. Basicity and lipophilicity modulations observed for β‐axial functional groups are quite diverse and rationalized in terms of intramolecular hydrogen bonding, dipolar interactions, and special solvation effects. Aqueous solubility and (artificial) membrane permeability are discussed with reference to lipophilicity.
miR‐938 promotes cell proliferation by regulating RBM5 in lung adenocarcinoma cells
Authors: Qian Taotao , Shi Shunbin , Xie Lincen , Zhu Yong
Published: September 2019

A growing body of research suggests that microRNAs (miRNAs) may play a key part in the progression of various cancers, including lung adenocarcinoma (LUAD). However, the expression and mechanism of miR‐938 (microRNA‐938) in LUAD have not been defined. Compared with adjacent tissues, the level of miR‐938 was up‐regulated in LUAD tissues. miR‐938 expression was significantly associated with tumor size. In vitro assays indicated that miR‐938 expression was also increased in the LUAD cell lines. Overexpression of miR‐938 promoted LUAD cell proliferation, whereas down‐regulation of miR‐938 had the opposite effect. We identified RNA‐binding protein 5 (RBM5) as a potential target gene of miR‐938 in LUAD. Expression of RBM5 was down‐regulated in LUAD tumor tissues and negatively correlated with expression of miR‐938. Up‐regulation of RBM5 reversed cell proliferation by inhibition of miR‐938 expression in LUAD cells. These results showed that miR‐938 may act as an oncogenic miRNA by targeting RBM5 in LUAD, indicating that miR‐938 could be used as a potential therapeutic target for LUAD patients.
Carboxylation of Toluene with CO2‐derived Dimethyl Carbonate over Amorphous Ti−Zr Mixed‐metal Oxide Catalysts
Authors: Liu Hailong , Li Zelong , Wang Jijie , Lu Shengmei , Wang Mengmeng , Liu Yan , Li Can
Published: September 2019

Carboxylation of arenes utilizing CO2 into value‐added chemicals has received much attention but remains a challenge. Herein, we report a Ti−Zr oxide catalyst which shows high activity in the carboxylation of toluene with CO2‐derived dimethyl carbonate (DMC) into methyl methylbenzoates, while the individual TiO2 and ZrO2 component show poor catalytic performance. It was found that the excellent performance is related to the amorphous state of the Ti−Zr mixed‐metal oxide which possesses high acidity and moderate basicity together with high specific surface area.
Removal of Bisphenol A Using Magnetically Responsive Spruce Chip Biochar
Authors: Baldikova Eva , Pospiskova Kristyna , Safarik Ivo
Published: September 2019

Bisphenol A was efficiently adsorbed on biochar magnetically modified with microwave‐synthesized magnetic iron oxide particles. The adsorption followed the Langmuir isotherm model, and the maximum adsorption capacity was 77.4 mg per gram of magnetic biochar at 282.15 K. Kinetics of sorption process followed the pseudo‐second‐order kinetic model, and thermodynamic studies described an exothermic and spontaneous adsorption process. The prepared material exhibited high adsorption of bisphenol A and a rapid magnetic response to an external magnetic field.
Isoreticular Expansion of Metal–Organic Frameworks via Pillaring of Metal Templated Tunable Building Layers: Hydrogen Storage and Selective CO2 Capture
Authors: Maity Kartik , Nath Karabi , Sinnwell Michael A. , Motkuri Radha Kishan , Thallapally Praveen K. , Biradha Kumar
Published: September 2019

The deliberate construction of isoreticular eea‐metal–organic frameworks (MOFs) (Cu‐eea‐1, Cu‐eea‐2 and Cu‐eea‐3) and rtl‐MOFs (Co‐rtl‐1 and Co‐rtl‐2) has been accomplished based on the ligand‐to‐axial pillaring of supermolecular building layers. The use of different metal ions resulted in two types of supermolecular building layers (SBLs): Kagome (kgm) and square lattices (sql) which further interconnect to form anticipated 3D‐MOFs. The isoreticular expansion of (3,6)‐connected Cu‐MOFs has been achieved with desired eea‐topology based on kgm building layers. In addition, two (3,6)‐connected Co‐rtl‐MOFs were also successfully constructed based on sql building layers. The Cu‐eea‐MOFs were shown to act as hydrogen storage materials with appreciable amount of hydrogen uptake abilities. Moreover Cu‐eea‐MOFs have also exhibited remarkable CO2 capture ability at ambient condition compared to nitrogen and methane, due to the presence of amide functionalities.
A Self‐Healing Metal–Organic Hydrogel for an All‐Solid Flexible Supercapacitor
Authors: Karan Chandan Kumar , Mallick Sourav , Raj C. Retna , Bhattacharjee Manish
Published: September 2019

A zinc containing metal–organic gel (Zn‐MOG) with embedded free ions, which exhibits self‐healing properties, has been synthesized for application in supercapacitors. The activated carbon‐based flexible supercapacitor device with the MOG electrolyte has a broad potential window of 2.1 V, with high retention of specific capacitance compared to the traditional polyvinyl alcohol (PVA)‐based gel. The Zn‐MOG does not require an additional electrolyte. The sodium and sulphate ions embedded in the MOG are sufficient enough for the charge storage.
Potential Precursors for Terminal Methylidene Rare‐Earth‐Metal Complexes Supported by a Superbulky Tris(pyrazolyl)borato Ligand
Authors: Birkelbach Verena M. , Thim Renita , Stuhl Christoph , Maichle‐Mössmer Cäcilia , Anwander Reiner
Published: September 2019

A series of solvent‐free heteroleptic terminal rare‐earth‐metal alkyl complexes stabilized by a superbulky tris(pyrazolyl)borato ligand with the general formula [TptBu,MeLnMeR] have been synthesized and fully characterized. Treatment of the heterobimetallic mixed methyl/tetramethylaluminate compounds [TptBu,MeLnMe(AlMe4)] (Ln=Y, Lu) with two equivalents of the mild halogenido transfer reagents SiMe3X (X=Cl, I) gave [TptBu,MeLnX2] in high yields. The addition of only one equivalent of SiMe3Cl to [TptBu,MeLuMe(AlMe4)] selectively afforded the desired mixed methyl/chloride complex [TptBu,MeLuMeCl]. Further reactivity studies of [TptBu,MeLuMeCl] with LiR or KR (R=CH2Ph, CH2SiMe3) through salt metathesis led to the monomeric mixed‐alkyl derivatives [TptBu,MeLuMe(CH2SiMe3)] and [TptBu,MeLuMe(CH2Ph)], respectively, in good yields. The SiMe4 elimination protocols were also applicable when using SiMe3X featuring more weakly coordinating moieties (here X=OTf, NTf2). X‐ray structure analyses of this diverse set of new [TptBu,MeLnMeR/X] compounds were performed to reveal any electronic and steric effects of the varying monoanionic ligands R and X, including exact cone‐angle calculations of the tridentate tris(pyrazolyl)borato ligand. Deeper insights into the reactivity of these potential precursors for terminal alkylidene rare‐earth‐metal complexes were gained through NMR spectroscopic studies.
Does the addition of chemotherapy to neoadjuvant radiotherapy impact survival in high‐risk extremity/trunk soft‐tissue sarcoma?
Authors: Chowdhary Mudit , Chowdhary Akansha , Sen Neilayan , Zaorsky Nicholas G. , Patel Kirtesh R. , Wang Dian
Published: September 2019

Background

The role of chemotherapy in extremity/trunk soft‐tissue sarcoma (ET‐STS) is controversial, even for patients at high risk for distant recurrence and death (those with high‐grade tumors ≥5 cm in size). This study examines the impact of integrating chemotherapy with neoadjuvant radiotherapy (RT) on overall survival (OS) for patients with high‐risk ET‐STS.

Methods

The National Cancer Data Base was queried for adult patients with high‐risk ET‐STS who received neoadjuvant RT and limb salvage surgery between 2006 and 2014. Patients were stratified into RT and chemoradiotherapy (CRT) cohorts. OS for the RT and CRT cohorts was analyzed with the Kaplan‐Meier method, log‐rank tests, and Cox proportional hazards models. Propensity score matching (PSM) analysis was used to account for a potential treatment selection bias between the cohorts.

Results

A total of 884 patients were identified: 639 (72.3%) in the RT cohort and 245 (27.7%) in the CRT cohort. The unadjusted 5‐year Kaplan‐Meier OS rate was significantly higher in the CRT cohort: 72.0% versus 56.1% (P < .001). Neoadjuvant chemotherapy was associated with improved OS in univariate and multivariable analyses (hazard ratio [HR], 0.57; 95% confidence interval [CI], 0.41‐0.78; P < .001). PSM identified 2 evenly matched cohorts of 212 patients each. The 5‐year matched Kaplan‐Meier OS rates were 69.8% and 55.4% for the CRT and RT cohorts, respectively (P = .002). The addition of neoadjuvant chemotherapy remained prognostic for OS on PSM (HR, 0.56; 95% CI, 0.39‐0.83; P = .003).

Conclusions

The addition of chemotherapy to neoadjuvant RT was associated with improved OS for patients with high‐risk ET‐STS. In the absence of randomized data evaluating CRT versus RT, these findings warrant further investigation.
Enhanced Performance and Stability of TiO2‐Nanoparticles‐Based Perovskite Solar Cells Employing a Cheap Polymeric Surface Modifier
Authors: Zhuang Qixin , You Guofeng , Wang Lijun , Lin Xinyu , Zou Ding , Zhen Hongyu , Ling Qidan
Published: September 2019

Interface engineering of TiO2 nanoparticles (NPs)‐based perovskite solar cells (PVSCs) is often necessary to facilitate the extraction and transport of charge carriers. In this work, poly[{9,9‐bis[3′‐(N,N‐dimethyl)propyl]‐2,7‐fluorene}‐alt‐2,7‐(9,9‐dioctylfluorene)] (PFN) and polystyrene (PS) are demonstrated to be effective surface modifiers of the TiO2 NPs electron‐transporting layer in n‐i‐p PVSCs. The low‐cost insulating polymer PS performs better than the PFN conjugated polymer owing to its high film quality, low surface energy and insulating characteristics. A peak power conversion efficiency (PCE) of 15.09 % with an open‐circuit voltage (VOC) of 1.05 V and a PCE of 17.13 % with an ultrahigh VOC of 1.18 V is achieved with TiO2 NPs/PS‐based PVSCs using poly[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylenevinylene] (MEH‐PPV) and spiro‐OMeTAD, respectively, as the hole‐transporting material.
Automatic Bone Marrow Cellularity Estimation in H&E Stained Whole Slide Images
Authors: Nielsen Frederik Skou , Pedersen Mads Jozwiak , Olsen Mathias Vassard , Larsen Morten Skaarup , Røge Rasmus , Jørgensen Alex Skovsbo
Published: September 2019

Bone marrow cellularity is an important measure in diagnostic hematopathology. Currently, the gold standard for bone marrow cellularity estimation is manual inspection of hematoxylin and eosin stained whole slide images (H&E WSI) by hematopathologists. However, these assessments are subjective and subject to interobserver and intraobserver variability. This may be reduced by using a computer‐assisted estimate of bone marrow cellularity. The aim of this study was to develop a fully automated algorithm to estimate bone marrow cellularity in H&E WSI stains using bone marrow segmentation. Data consisted of eight bone marrow H&E WSIs extracted from eight subjects. An algorithm was developed to estimate the bone marrow cellularity consisting of biopsy segmentation, tissue classification, and bone marrow segmentation. Segmentations of the red and yellow bone marrow (YBM) were used to estimate the bone marrow cellularity within the WSI H&E stains. The DICE coefficient between automatic tissue segmentations and ground truth segmentations conducted by an experienced hematopathologist were used for validation. Furthermore, the agreement between the automatic and two manual cellularity estimates was assessed using Bland–Altman plots and intraclass correlation coefficients (ICC). The validation of the bone marrow segmentation demonstrated an average DICE of 0.901 and 0.920 for the red and YBM, respectively. A mean cellularity estimate difference of −0.552 and − 7.816 was obtained between the automatic cellularity estimates and two manual cellularity estimates, respectively. An ICC of 0.980 (95%CI: 0.925–0.995, P‐value: 5.51 × 10−7) was obtained between the automatic and manual cellularity estimates based on manual annotations. The study demonstrated that it was possible to obtain bone marrow cellularity estimates with a good agreement with bone marrow cellularity estimates obtained from an experienced hematopathologist. © 2019 International Society for Advancement of Cytometry
MolCom system with downlink/uplink biocyber interface for Internet of Bio‐NanoThings
Authors: Abd El‐atty Saied M. , Bidar Reda , El‐Rabaie El‐Sayed M.
Published: September 2019

Inspired by wireless communication systems, we propose a feasible downlink/uplink biocyber interface for the expected targeted drug delivery system based on Internet of Biological NanoThing (IoBNT) paradigm. The downlink/uplink biocyber interface of IoBNT comprises Fluorescence Resonance Energy Transfer (FRET) and Molecular Communication (MolCom) technology. On the downlink (from Internet to targeted nanonetwork), the biocyber interface transduces electromagnetic (EM) signal to biochemical signals, and thus with the help of mobile MolCom system based on FRET nanocommunication, the drug information delivers to the diseased cell within the targeted intrabody nanonetwork. On the uplink, the MolCom system consists of embedded sensor/actuator nanonetwork to detect the biochemical changes in the targeted cell, and hence biocyber interface transduces the biochemical signal to EM signal. As a result, the paradigm of IoBNT responses by proper functions to these changes according to the decision of medical health care. The performance analysis of the proposed IoBNT system is numerically investigated through MolCom system‐based FRET, while the performance evaluation is evaluated by employing spreading epidemic scheme in terms of successful probability of drug delivery, channel capacity, average drug‐delivery time, and throughput. The simulation results show that the proposed IoBNT is a promising paradigm for smart drug delivery system, and its performance is mainly based on the nanostructure and the characteristic of molecular nanomachines in the targeted nanonetwork.
Task‐specific adaptations of postural sway in sitting infants
Authors: Arnold Amanda J. , Liddy Joshua J. , Harris Rachel C. , Claxton Laura J.
Published: September 2019

When engaging in manual or visual tasks while sitting, infants modify their postural sway based on concurrent task demands. It remains unclear whether these modulations are sensitive to differences in concurrent task demands (holding a toy vs. looking at a toy being held by someone else), and whether the properties of the support surface impact these adaptations. We investigated infants’ ability to modify postural sway when holding a toy or visually attending to a toy someone else was holding while sitting on different support surfaces. Twenty‐six independently sitting infants sat on solid and compliant surfaces placed on a force plate while looking at or holding a toy. Measures of postural sway were calculated from the center of pressure data. Visually attending to a toy was associated with less sway and lower sway velocity than when holding a toy. Surprisingly, surface compliance did not affect sway and there were no interaction effects. Whereas sway modulations may facilitate infants’ performance on both manual and visual concurrent tasks, the visual task placed more constraints on the postural system leading to greater adaptations in postural sway. These findings provide insights into how infants are allocating attention and coordinating perceptual‐motor information in developing sitting skills.