bluuebunny/crossref_metadata_2025 huggingface dataset:
Meningkatkan Hasil Belajar Biologi Siswa Kelas XII IPA MA Hasanah Tahun Pelajaran 2018-2019 Melalui Model Pembelajaran Kooperatif tipe Student Teams Achievement Divisions (STAD)
Authors: Rezeki Sri
Published: March 2022

Hasil belajar yang baik merupakan tujuan dari suatu proses pembelajaran. Berbagai usaha dilakukan untuk meningkatkan hasil belajar siswa diantaranya pemilihan model pembelajaran yang tepat. Salah satu model pembelajaran yang dapat coba diterapkan untuk menghasilkan hasil belajar yang baik tersebut adalah model pembelajaran kooperatif  tipe student teams achievement division (STAD). Penelitian  ini bertujuan untuk melihat pengaruh model kooperatif tipe STAD  dalam meningkatkan hasil belajar mata pelajaran biologi di kelas  XII IPA MA Hasanah Pekanbaru tahun pelajaran 2018/2019. Penelitian ini adalah penelitian tindakan kelas yang dilakukan dalam 2 siklus, dimana masing- masing siklus terdiri dari fase perencanaan, tindakan, observasi dan refleksi. Dilaksanakan pada bulan September hingga November 2018.  Dari pelaksanaan penelitian didapat hasil bahwa terjadi peningkatan hasil belajar siswadari siklus 1 sebanyak 12 orang atau sebesar 71 % tuntas  meningkat menjadi 17 orang tuntas atau sebesar 100 % pada siklus 2.  Sementara Untuk daya serap siswa sebesar 79 % pada siklus 1 meningkat menjadi 86% pada siklus 2. Dari Penelitian ini dapat disimpulkan bahwa model pembelajaran kooperatif tipe STAD dapat digunakan sebagai alternatif model pembelajaran untuk meningkatkan hasil belajar peserta didik.
Bingkai dari Limbah Anorganik sebagai Media Pembelajaran IPA Dalam Mengembangkan Kreatif
Authors: Radeswandri Radeswandri , Cahaya Pitri Ramadan  , Rian Vebrianto
Published: March 2022

Penelitian ini bertujuan untuk melihat bentuk implementasi dari Pengembangan Media dan Sumber Belajar IPA (sains) yang berupa pemanfaatan limbah rumah tangga (sampah anorganik) berupa Bingkai cantik. Media belajar menjadi strategi yang jitu dalam pengelolaan sampah anorganik atau sampah plastik. Jenis penelitian ini merupakan penelitian pengembangan. Hasil penelitian didapatkan bahwa media pembelajaran yang dikembangkan valid dan memenuhi kriteria kelayakan. Implementasi media pembelajaran yang dikembangkan di kelas dapat meningkatkan keaktifan peserta didik sehingga dapat mengembangkan kretivitas peserta didik. Diharapkan penelitian ini dapat memberikan kontribusi pengetahuan terhadap peserta didik dan semua masyarakat akan pentingnya pengelolaan sampah anorganik, dan dapat memanfaatkan sampah anorganik sebagai Media Pembelajaran khususnya IPA
Pengaruh Media Animasi Berbasis Macromedia Flash terhadap Kemampuan Siswa Dalam Pembelajaran Fisika Hukum Archimedes di SMP/MTs
Authors: Suar Siti Hadizah  , Aulia Jannnatul , Rahmawati
Published: March 2022

The media plays a very important role in which learning process later it will affect the understanding of concepts and results learn from students. This research aims to describe the feasibility of influence-based animation media macromedia flash on student learning abilities, based on empirical feasibility namely student response. In collecting data, the method used is to use a questionnaire and then the results are analyzed. The results of the study show that macromedia flash-based animation media against students' abilities in learning physics Archimedes Law suitable for use in learning.
Self Efficacy Matematika Melalui Problem Based Instruction (PBI) Dalam Pendekatan Aptitude Treatment Interaction (ATI): Studi Eksperimen di SMP Negeri 1 Kuindra
Authors: Eko Suhendra Aris , Risnawati
Published: March 2022

The objective of this research was to tried the above effect towards mathematic self-efficacy of students taught using Problem Based on Instruction model on Aptitude Treatment Interaction with the students taught using Aptitude Treatment Interaction approach. The formulation of this research was whether problem based on instruction influenced towards self-efficacy of students and how it’s effect to it?. This research was designed as Intact-Group Comparison which was part of Pre-Experimental Designs where one group was divided into two groups; both were experiment group and control group. The writer in this research took role in the process of teaching. The subject of t this research was eight year students at state junior high school 1 KUINDRA district of Indragiri Hilir. While the object was self-efficacy of students. The data in this research was collected using documentation, observation test and questionnaires. The meetings in this research was conducted six times, five times of them were conducted using PBI model on ATI Approach and one another meeting by filing up the questionnaires and measured using likert scale and by using test-t and the effect on problem based on instruction calculated using Kp. Based on data analysis, the writer concluded that the effect of PBI model on ATI approach influenced towards students’s high ability it was around 41,44%, students’s ability of middle was 40,55% and student’s ability of low was 37,27%.
Decompression followed by enucleation in the treatment of orthokeratinized odontogenic cyst
Authors: Boas Jéssica Lopes Vilas , Lucamba Agnelo Josué , Cesconetto Lorenzzo de Angeli , Araujo André Vitor Alves , Oliveira Vinícius Dantas de , Provenzano Nilton
Published: March 2022

The orthokeratinized odontogenic cyst, currently classified as a separate entity from the odontogenic keratocyst, is a rare developmental cyst that affects the gnatic bones. It predo- minantly affects young male patients. Its clinical behavior is benign with a predominance of involvement by the posterior region of the mandible. Treatment involves enucleation, with or without prior decompression. The present case reports a 17-year-old male patient with bilateral lesion manifestation, the left osteolytic process being of large proportions. The patient was subjected to decompression prior to enucleation, and this conservative treatment is essential for successful treatment. The patient was followed up for 1 year with no signs of recurrence.
ПРЕСЕЉАВАЊЕ СТАНОВНИШТВА КАО БЕЗБОЖНО ДЕЛО
Authors: Радић Радивој Ђ.
Published: March 2022

У оквиру своје колонизационе политике, а у складу са по- требама државе, византијски цареви су пресељавали становништво из једног у други део Византије. Наравно, за житеље Царства који су били приморани да одлазе из малоазијских у европске провинције, или обра- тно, то је морала бити тешка и непопуларна мера. О таквој врсти принуде василевса Нићифора I у првој деценији IX века писао је Теофан Исповед- ник, састављач једне од најпознатијих византијских хроника. Он је мере пресељавања становништва означио као један од „десет злочина“ које је приписао цару. Међутим, у позадини оваквих оцена је Tеофанова непри- кривена нетрпељивост према Нићифору I у великој мери проистекла из цареве религијске политике, а у тесној вези и са тада актуелним питањем иконоборства. Ипак, без обзира на чињеницу да су се налазиле у служби веома оштре критике цара Нићифора I, у Теофановим речима можемо да уочимо и једну општељудску бригу и племенито старање за хиљаде име- ном непознатих Византинаца.
Remote cerebellar hemorrhage after a neurosurgical procedure: A report of three cases
Authors: Lee Wonseok , Kim Taehoon , Kim Hyeseon , Kim Jeong Eun , Baek Kyeong Hee , Koh Eun Jung , Kim Kyung-Hwan , Ha Eun Jin
Published: March 2022

Remote cerebellar hemorrhage (RCH) is a rare complication of neurosurgical procedures and is characterized by a typical bleeding pattern defined as the “zebra sign.” Only few cases of RCH have been reported in the English literature, and its pathophysiology remains unclear. In this report, we present the cases of three patients with RCH after three different procedures: burr-hole trephination and chronic subdural hematoma evacuation of bilateral cerebral convexity with subsequent subdural drain insertion, lumbar drainage for cerebrospinal fluid divergence for thoracic endovascular aortic repair, and combined bypass surgery for moyamoya disease.
Testosterone pulses paired with a location induce a place preference to the nest of a monogamous mouse under field conditions
Authors: Petric Radmila , Kalcounis-Rueppell Matina , Marler Catherine A
Published: March 2022

Changing social environments such as the birth of young or aggressive encounters present a need to adjust behavior. Previous research examined how long-term changes in steroid hormones mediate these adjustments. We tested the novel concept that the rewarding effects of transient testosterone pulses (T-pulses) in males after social encounters alter their spatial distribution on a territory. In free-living monogamous California mice (Peromyscus californicus), males administered three T-injections at the nest spent more time at the nest than males treated with placebo injections. This mimics T-induced place preferences in the laboratory. Female mates of T-treated males spent less time at the nest but the pair produced more vocalizations and call types than controls. Traditionally, transient T-changes were thought to have transient behavioral effects. Our work demonstrates that in the wild, when T-pulses occur in a salient context such as a territory, the behavioral effects last days after T-levels return to baseline.
Eco-evolutionary dynamics modulate plant responses to global change depending on plant diversity and species identity
Authors: Dietrich Peter , Schumacher Jens , Eisenhauer Nico , Roscher Christiane
Published: March 2022

Global change has dramatic impacts on grassland diversity. However, little is known about how fast species can adapt to diversity loss and how this affects their responses to global change. Here, we performed a common garden experiment testing whether plant responses to global change are influenced by their selection history and the conditioning history of soil at different plant diversity levels. Using seeds of four grass species and soil samples from a 14-year-old biodiversity experiment, we grew the offspring of the plants either in their own soil or in soil of a different community, and exposed them either to drought, increased nitrogen input, or a combination of both. Under nitrogen addition, offspring of plants selected at high diversity produced more biomass than those selected at low diversity, while drought neutralized differences in biomass production. Moreover, under the influence of global change drivers, soil history, and to a lesser extent plant history, had species-specific effects on trait expression. Our results show that plant diversity modulates plant-soil interactions and growth strategies of plants, which in turn affects plant eco-evolutionary pathways. How this change affects species' response to global change and whether this can cause a feedback loop should be investigated in more detail in future studies.
Steroid hormone signaling activates thermal nociception during Drosophila peripheral nervous system development
Authors: Jaszczak Jacob S , DeVault Laura , Jan Lily Yeh , Jan Yuh Nung
Published: March 2022

Sensory neurons enable animals to detect environmental changes and avoid harm. An intriguing open question concerns how the various attributes of sensory neurons arise in development. Drosophila melanogaster larvae undergo a behavioral transition by robustly activating a thermal nociceptive escape behavior during the second half of larval development (third instar). The Class IV dendritic arborization (C4da) neurons are multimodal sensors which tile the body wall of Drosophila larvae and detect nociceptive temperature, light, and mechanical force. In contrast to the increase in nociceptive behavior in the third instar, we find that ultraviolet light-induced Ca2+ activity in C4da neurons decreases during the same period of larval development. Loss of ecdysone receptor has previously been shown to reduce nociception in third instar larvae. We find that ligand-dependent activation of ecdysone signaling is sufficient to promote nociceptive responses in second instar larvae and suppress expression of subdued (encoding a TMEM16 channel). Reduction of subdued expression in second instar C4da neurons not only increases thermal nociception but also decreases the response to ultraviolet light. Thus, steroid hormone signaling suppresses subdued expression to facilitate the sensory switch of C4da neurons. This regulation of a developmental sensory switch through steroid hormone regulation of channel expression raises the possibility that ion channel homeostasis is a key target for tuning the development of sensory modalities.
Heart rate variability, mood and performance: a pilot study on the interrelation of these variables in amateur road cyclists
Authors: Alfonso Carla , Capdevila Lluis
Published: March 2022

Objective

The present study seeks to explore the relationship between measures of cycling training on a given day and the heart rate variability (HRV) and mood states obtained the following morning. The association between HRV and mood state is also studied, as is the relationship between internal and external measures of training.

Methods

During a 6-week period, five recreational road cyclists collected 123 recordings of morning HRV and morning mood, and 66 recordings of training power and rate of perceived exertion (RPE). Training power was used as an external measure of performance and RPE as an internal measure of performance. The HRV parameters used in the study were the mean of RR intervals (mean RR) and the standard deviation of all RR intervals (SDNN) as time domain analysis, and the normalized high frequency band (HFnu), normalized low frequency band (LFnu) and the ratio between low and high frequency bands, as frequency domain analysis. Mood was measured using a 10-point cognitive scale.

Results

It was found that the higher the training power on a given day, the lower the HFnu and the higher LF/HF were on the following morning. At the same time, results showed an inverse relationship between training and mood, so the tougher a training session, the lower the mood the following day. A relationship between morning HRV and mood was also found, so that the higher mean RR and HFnu, the more positive the mood (r = 0.497 and r = 0.420 respectively; p < 0.001). Finally, RPE correlated positively with external power load variables (IF: r = 0.545; p < 0.001).

Conclusion

Altogether, the results indicate a relationship between training of cyclists on a given day and their morning HRV and mood state on the following day. Mood and HRV also seem positively related. It is argued that developing a monitoring system that considers external and internal training loads, together with morning mood, could help understand the state of the individual, enabling feedback to athletes to facilitate the adaptation to training and to prevent problems associated with overtraining. However, more research is needed to further understand the association between the different variables considered.
Phamrmacoligical Therapies for COVID-19: A Comprehensive Review from 2022 Updated Nih, IDSA and ICMR Guidelines
Authors: Wani Ab Ahad , Ashraf Kar Tahir , Ab Malik latief , Islam Jawhar Ul , Shafi Aamir , Mubashir Wani , Ahmad Aleena , Azra Khan , Ahmad Dawood , Altaf Nayarah , Ahmad Shahid
Published: March 2022

Coronavirus disease 2019 (COVID-19) has had catestrophic results on the world’s economy and demographics leading to more than 4 million fatalities.This has been the most devastating world crisis after the 1918 pandemic which was caused by influenza. The main concerns regarding the disease have been lack of specific antiviral therapies. Results from recent trials have given some hope and promising results for the treatment of COVID-19 especially Molnupiravir, Monoclonal antibodies and  Janus kinase inhibitors. This review article gives a comprehensive update on various pharmacological therapies in the light of recently published standard treatment guidelines based on large clinical trials for the treatment of COVID-19.
Interaction kinetics reveal distinct properties of conformational ensembles of three‐repeat and four‐repeat tau proteins
Authors: Hornakova Lenka , Sinsky Jakub , Janubova Maria , Mederlyova Anna , Paulenka Ivanovova Natalia , Piestansky Juraj , Kovac Andrej , Galba Jaroslav , Skrabana Rostislav , Cehlar Ondrej
Published: March 2022

Tau protein is an intrinsically disordered protein. Its physiological state is best described as a conformational ensemble (CE) of metastable structures interconverting on the local and molecular scale. The monoclonal antibody DC39C recognizes a linear C‐terminal tau epitope, and as the tau interaction partner, its binding parameters report about tau CE. Association kinetics of DC39C binding, together with crosslinking mass spectrometry, show differences in the accessibility of the C terminus in CEs of tau isoforms. Furthermore, removal of the C terminus accelerated the aggregation kinetics of three‐repeat tau proteins. Our results suggest a novel mechanism of splicing‐driven regulation of the tau C‐terminal domain with consequences on the specific roles of tau isoforms in microtubule assembly and pathological aggregation.
The seizure‐inducing plastic explosive RDX inhibits the α1β2γ2 GABAA receptor
Authors: Pressly Brandon , Lee Ruth D. , Singh Vikrant , Pessah Isaac N. , Wulff Heike
Published: March 2022

Objective

Royal demolition explosive (RDX) can induce seizures in wildlife and humans following release into the environment or after voluntary consumption. During the Vietnam War, RDX intoxication was the most common cause of generalized seizures in US service personnel, and in some sections of the armed forces, eating of RDX has continued as “a dare” to this day. After its mechanism of action was long unknown, RDX was recently shown to be a GABAA receptor antagonist. We here determined the GABAA receptor subtype‐selectivity of RDX and mapped its functional binding site.

Methods

We used whole‐cell patch‐clamp to determine the potency of RDX on 10 recombinantly expressed GABAA receptors and mapped the RDX binding site using a combination of Rosetta molecular modeling and site‐directed mutagenesis.

Results

RDX was found to reversibly inhibit the α1β2γ2 GABAA receptor with an IC50 of 23 μmol/L (95% CI 15.1–33.3 μmol/L), whereas α4 and α6 containing GABAA receptor combinations were 4–10‐fold less sensitive. RDX is binding to the noncompetitive antagonist (NCA) site in the pore. In a molecular model based on the cryo‐EM structure of the resting state of the α1β2γ2 receptor, RDX forms two hydrogen bonds with the threonines at the T6’ ring and makes hydrophobic interactions with the valine and alanine in 2′ position of the α1 or β2 subunits.

Interpretation

Our findings characterize the mechanism of action of RDX at the atomistic level and suggest that RDX‐induced seizures should be susceptible to treatment with GABAA modulating drugs such as benzodiazepines, barbiturates, propofol, or neurosteroids.
Ultrahigh Energy Density in Continuously Gradient‐Structured All‐Organic Dielectric Polymer Films
Authors: Jiang Yanda , Wang Jian , Yan Shengliao , Shen Zhonghui , Dong Lijie , Zhang Shujun , Zhang Xin , Nan Ce‐Wen
Published: March 2022

High‐performance dielectric capacitors are critical for advanced electronics and electrical power systems. Polymeric dielectrics have been widely investigated for using in dielectric capacitors because of their high dielectric constants, flexibility, low density, and easy processability. However, it is still challenging to achieve simultaneous improvements in both energy density and efficiency in these dielectric polymers. Here, we report ferroelectric polyvinylidene‐fluoride‐based all‐organic dielectric polymer films with continuous compositional gradient structure are reported by modulating the spatial distribution of polymethyl‐methacrylate components, prepared via a facile and scalable additive manufacturing method. The continuous out‐of‐plane composition gradient in the all‐organic dielectric polymer films allows to tune electrical and mechanical behaviors, and thus induces a notably enhanced breakdown strength by modulating the electromechanical breakdown process related to the coupling of local electric field and stress. An ultrahigh discharge energy density of 38.8 J cm−3 along with a high discharge efficiency of >80% is achieved at the electric field of 800 kV mm−1 in the gradient polymer films, which is the highest energy density reported thus far in polymer‐based dielectrics including their nanocomposites and the highest energy efficiency achieved along with an energy density of >30 J cm−3.
Double‐Lattice Packing of Pentagonal Gold Bipyramids in Supercrystals with Triclinic Symmetry
Authors: Lyu Jieli , Chaâbani Wajdi , Modin Evgeny , Chuvilin Andrey , Bizien Thomas , Smallenburg Frank , Impéror‐Clerc Marianne , Constantin Doru , Hamon Cyrille
Published: March 2022

Pentagonal packing is a long‐standing issue and a rich mathematical topic, brought to the fore by recent progress in nanoparticle design. Gold pentagonal bipyramids combine fivefold symmetry and anisotropy and their section varies along the length. In this work, colloidal supercrystals of pentagonal gold bipyramids are obtained in a compact arrangement that generalizes the optimal packing of regular pentagons in the plane. Multimodal investigations reveal a two‐particle unit cell with triclinic symmetry, a lower symmetry than that of the building blocks. Monte Carlo computer simulations show that this lattice achieves the densest possible packing. Going beyond pentagons, further simulations show an odd–even effect of the number of sides on the packing: odd‐sided bipyramids are non‐centrosymmetric and require the double‐lattice arrangement to recover inversion symmetry. The supercrystals display a facet‐dependent optical response that is promising for sensing, metamaterials applications, and for fundamental studies of self‐assembly processes.
Negative Phototransistors with Ultrahigh Sensitivity and Weak‐Light Detection Based on 1D/2D Molecular Crystal p–n Heterojunctions and their Application in Light Encoders
Authors: Zhu Xiaoting , Yan Yujie , Sun Lingjie , Ren Yiwen , Zhang Yihan , Liu Yang , Zhang Xiaotao , Li Rongjin , Chen Huipeng , Wu Jishan , Yang Fangxu , Hu Wenping
Published: March 2022

Anomalous negative phototransistors in which the channel current decreases under light illumination hold potential to generate novel and multifunctional optoelectronic applications. Although a variety of design strategies have been developed to construct such devices, NPTs still suffer from far lower device performance compared to well‐developed positive phototransistors (PPTs). In this work, a novel 1D/2D molecular crystal p–n heterojunction, in which p‐type 1D molecular crystal (1DMC) arrays are embedded into n‐type 2D molecular crystals (2DMCs), is developed to produce ultrasensitive NPTs. The p‐type 1DMC arrays act as light‐absorbing layers to induce p‐doping of n‐type 2DMCs through charge transfer under illumination, resulting in ineffective gate control and significant negative photoresponses. As a result, the NPTs show remarkable performances in photoresponsivity (P) (1.9 × 108) and detectivity (D*) (1.7 × 1017 Jones), greatly outperforming previously reported NPTs, which are one of the highest values among all organic phototransistors. Moreover, the device exhibits intriguing characteristics undiscovered in PPTs, including precise control of the threshold voltage by controlling light signals and ultrasensitive detection of weak light. As a proof‐of‐concept, the NTPs are demonstrated as light encoders that can encrypt electrical signals by light. These findings represent a milestone for negative phototransistors, and pave the way for the development of future novel optoelectronic applications.
A Novel Methodology of Using Nonsolvent in Achieving Ultraclean Transferred Monolayer MoS2
Authors: Bhuyan C. Abinash , Madapu Kishore K. , Prabakar K. , Das Arindam , Polaki S. R. , Sinha Shyam K. , Dhara Sandip
Published: March 2022

The transfer of monolayer molybdenum disulfide (1L‐MoS2) onto any target substrates is inevitable for the next generation of optoelectronic devices such as flexible electronics. However, the existing post‐transfer treatments are ineffective for the complete removal of poly(methyl methacrylate) (PMMA) polymer, which is usually used as carrier polymer in the wet‐transfer method. The presence of PMMA residues seriously degrades the intrinsic properties of any 2D materials. Several new cleaning methods such as annealing, ozone cleaning, and acetone treatment adopted in this report are found to be ineffective for the complete removal of PMMA residues on the transferred 1L‐MoS2 film. A new chemical route is developed and demonstrated with a PMMA nonsolvent, ethanol, and ultraclean transferred 1L‐MoS2 is obtained after 96 h hot ethanol treatment. An interfacial diffusion model is proposed for the mechanism of PMMA removal from the 1L‐MoS2 surface. To observe the effect of cleaning process on electrical properties, 1L‐MoS2 field‐effect transistor (FET) devices are fabricated. An enhancement of 80%–85% in the electron mobility is achieved for ultraclean 1L‐MoS2. One order improvement in the FET parameters such as ON/OFF ratio and the subthreshold slope is also observed. It is believed that this novel method can also be applicable for other 2D materials.
Multifunctional Molecule‐Modified SnO2–Perovskite Interface for Efficient Planar Perovskite Solar Cells
Authors: Xin Xu , Yang Jiabao , Pu Xingyu , Li Yuke , Wang Tong , Chen Hui , Cao Qi , Zhang Yixin , Tojiboyev Ilhom , Salari Hadi , Ye Fei , Li Xuanhua
Published: March 2022

The electron transport layer (ETL) is one of the determinants for the performance improvement of perovskite solar cells (PSCs). Here, a multifunctional molecule named 4‐fluoro‐phenylalanine (4‐F‐Phe) to modify the surface of tin oxide (SnO2) ETL is introduced as a novel interfacial layer for high‐efficiency PSCs. The modified SnO2 ETLs exhibit an elevated Fermi level, increasing the carrier extraction and suppressing the interfacial recombination. In addition, the various functional groups of the 4‐F‐Phe realize strong interfacial interactions with both the bottom SnO2 ETLs and the top perovskite, which reduces trap state density significantly to promote the interfacial charge transport. As a result, power conversion efficiency (PCE) for the 4‐F‐Phe optimized device reaches 21.91%. Most importantly, the 4‐F‐Phe optimized device without encapsulation maintains 91% of its initial PCE after 2000 h at 25 °C with a humidity of 50 ± 5%, and 90% of the initial PCE after 1000 h at 80 °C in N2. In addition, the encapsulated devices maintain 94% of their initial efficiency under continuous 1 sun illumination for 1000 h when tracking the maximum power point at 45 °C. This work provides a new strategy of modifying ETL to simultaneously improve the efficiency and stability of PSCs.
Synergistic Pd/Cu Catalyzed Allylation of Cyclic Ketimine Esters with Vinylethylene Carbonates: Enantioselective Construction of Trisubstituted Allylic 2H‐Pyrrole Derivatives
Authors: Ke Miaolin , Yu Yuyan , Zhang Ke , Zuo Sheng , Liu Zhigang , Xiao Xiao , Chen Fener
Published: March 2022

An asymmetric allylation of cyclic ketimine esters with vinylethylene carbonates was accomplished through a Pd/Cu dual catalysis system under a mild condition, providing a range of trisubstituted allylic 2H‐pyrrole analogues bearing a chiral quaternary stereogenic center in high yields (up to 92% yield) and with excellent regioselectivities and enantioselectivities (up to 96% ee). A gram‐scale operation was also conducted in high efficiency without erosion of enantioselectivity and stereoselectivity.

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Metal‐Free Photochemical C−Se Cross‐Coupling of Aryl Halides with Diselenides
Authors: Wang Ruizhe , Wang Xinyu , Mao Shuai , Zhao Yahao , Yuan Bo , Yang Xue‐Yan , Li Jianjun , Chen Zhengkai
Published: March 2022

A light‐mediated C−Se bond coupling reaction of aryl halides with diselenides under mild photocatalyst‐free conditions for preparing aryl selenoethers has been achieved. The transformation is charactered by readily available materials, mild conditions, broad substrate scope and high efficiency. A reasonable mechanism has been proposed based on the preliminary mechanistic investigation. The protocol is also suitable for forging C−S bond and C−Te bond by the use of disulfides and ditellurides.

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Remote Giese Radical Addition by Photocatalytic Ring Opening of Activated Cycloalkanols
Authors: Salaverri Noelia , Carli Benedetta , Gratal Patricia B. , Marzo Leyre , Alemán José
Published: March 2022

The application of proton coupled electron transfer (PCET) processes in organic synthesis has opened the door to new radical intermediates for synthesis such as alkyl radicals in remote positions to a ketone. Herein, we present the addition of these remote alkyl radicals to electron deficient double bonds under photoorganocatalyzed and very mild conditions. The method is not only applicable to diactivated double bonds, but monoactivated ones are also accessible using more stabilized alkyl radicals, and alkyl chains of any length can be introduced. The final products can be easily converted into more complex structures via a one‐pot process, and the activating functional groups were transformed in the more versatile methyl esters. Mechanistic investigations support a mechanistic proposal based on a PCET process.

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Revealing the Sole Impact of Acceptor's Molecular Conformation to Energy Loss and Device Performance of Organic Solar Cells through Positional Isomers
Authors: Cai Guilong , Chen Zeng , Li Mengyang , Li Yuhao , Xue Peiyao , Cao Qingbin , Chi Weijie , Liu Heng , Xia Xinxin , An Qiaoshi , Tang Zheng , Zhu Haiming , Zhan Xiaowei , Lu Xinhui
Published: March 2022

Two new fused‐ring electron acceptor (FREA) isomers with nonlinear and linear molecular conformation, m‐BAIDIC and p‐BAIDIC, are designed and synthesized. Despite the similar light absorption range and energy levels, the two isomers exhibit distinct electron reorganization energies and molecular packing motifs, which are directly related to the molecular conformation. Compared with the nonlinear acceptor, the linear p‐BAIDIC shows more ordered molecular packing and higher crystallinity. Furthermore, p‐BAIDIC‐based devices exhibit reduced nonradiative energy loss and improved charge transport mobilities. It is beneficial to enhance the open‐circuit voltage (VOC) and short‐current current density (JSC) of the devices. Therefore, the linear FREA, p‐BAIDIC yields a relatively higher efficiency of 7.71% in the binary device with PM6, in comparison with the nonlinear m‐BAIDIC. When p‐BAIDIC is incorporated into the binary PM6/BO‐4Cl system to form a ternary system, synergistic enhancements in VOC, JSC, fill factor (FF), and ultimately a high efficiency of 17.6% are achieved.
Single‐Cell RNA‐seq Reveals a Developmental Hierarchy Super‐Imposed Over Subclonal Evolution in the Cellular Ecosystem of Prostate Cancer
Authors: Ge Guangzhe , Han Yang , Zhang Jianye , Li Xinxin , Liu Xiaodan , Gong Yanqing , Lei Zhentao , Wang Jie , Zhu Weijie , Xu Yangyang , Peng Yiji , Deng Jianhua , Zhang Bao , Li Xuesong , Zhou Liqun , He Huiying , Ci Weimin
Published: March 2022

Prostate cancer (PCa) is a complex disease. An ongoing accumulation of mutations results in increased genetic diversity, with the tumor acquiring distinct subclones. However, non‐genetic intra‐tumoral heterogeneity, the cellular differentiation state and the interplay between subclonal evolution and transcriptional heterogeneity are poorly understood. Here, the authors perform single‐cell RNA sequencing from 14 untreated PCa patients. They create an extensive cell atlas of the PCa patients and mapped developmental states onto tumor subclonal evolution. They identify distinct subclones across PCa patients and then stratify tumor cells into four transcriptional subtypes, EMT‐like (subtype 0), luminal A‐like (subtype 1), luminal B/C‐like (subtype 2), and basal‐like (subtype 3). These subtypes are hierarchically organized into stem cell‐like and differentiated status. Strikingly, multiple subclones within a single primary tumor present with distinct combinations of preferential subtypes. In addition, subclones show different communication strengths with other cell types within the tumor ecosystem, which may modulate the distinct transcriptional subtypes of the subclones. Notably, by integrating TCGA data, they discover that both tumor cell transcriptional heterogeneity and cellular ecosystem diversity correlate with features of a poor prognosis. Collectively, their study provides the analysis of subclonal and transcriptional heterogeneity and its implication for patient prognosis.
Material‐Assisted Strategies for Osteochondral Defect Repair
Authors: Lesage Constance , Lafont Marianne , Guihard Pierre , Weiss Pierre , Guicheux Jérôme , Delplace Vianney
Published: March 2022

The osteochondral (OC) unit plays a pivotal role in joint lubrication and in the transmission of constraints to bones during movement. The OC unit does not spontaneously heal; therefore, OC defects are considered to be one of the major risk factors for developing long‐term degenerative joint diseases such as osteoarthritis. Yet, there is currently no curative treatment for OC defects, and OC regeneration remains an unmet medical challenge. In this context, a plethora of tissue engineering strategies have been envisioned over the last two decades, such as combining cells, biological molecules, and/or biomaterials, yet with little evidence of successful clinical transfer to date. This striking observation must be put into perspective with the difficulty in comparing studies to identify overall key elements for success. This systematic review aims to provide a deeper insight into the field of material‐assisted strategies for OC regeneration, with particular considerations for the therapeutic potential of the different approaches (with or without cells or biological molecules), and current OC regeneration evaluation methods. After a brief description of the biological complexity of the OC unit, the recent literature is thoroughly analyzed, and the major pitfalls, emerging key elements, and new paths to success are identified and discussed.
3D‐Laminated Graphene with Combined Laser Irradiation and Resin Infiltration toward Designable Macrostructure and Multifunction
Authors: Gao Yan , Zhai Yujiang , Wang Guantao , Liu Fu , Duan Haibin , Ding Xilun , Luo Sida
Published: March 2022

Macroscopic 3D graphene has become a significant topic for satisfying the continuously upgraded smart structures and devices. Compared with liquid assembling and catalytic templating methods, laser‐induced graphene (LIG) is showing facile and scalable advantages but still faces limited sizes and geometries by using template induction or on‐site lay‐up strategies. In this work, a new LIG protocol is developed for facile stacking and shaping 3D LIG macrostructures by laminating layers of LIG papers (LIGPs) with combined resin infiltration and hot pressing. Specifically, the constructed 3D LIGP composites (LIGP‐C) are compatible with large area, high thickness, and customizable flat or curved shapes. Additionally, systematic research is explored for investigating critical processing parameters on tuning its multifunctional properties. As the laminated layers are stacked from 1 to 10, it is discovered that piezoresistivity (i.e., gauge factor) of LIGP‐C dramatically reflects an ≈3900% improvement from 0.39 to 15.7 while mechanical and electrical properties maintain simultaneously at the highest levels, attributed to the formation of densely packed fusion layers. Along with excellent durability for resisting multiple harsh environments, a sensor‐array system with 5 × 5 LIGP‐C elements is finally demonstrated on fiber‐reinforced polymeric composites for accurate strain mapping.
Through‐Space Conjugated Electron Transport Materials for Improving Efficiency and Lifetime of Organic Light‐Emitting Diodes
Authors: Shen Pingchuan , Liu Hao , Zhuang Zeyan , Zeng Jiajie , Zhao Zujin , Tang Ben Zhong
Published: March 2022

Thermally stable electron transport (ET) materials with high electron mobility and high triplet state energy level are highly desired for the fabrication of efficient and stable organic light‐emitting diodes (OLEDs). Herein, a new design strategy of constructing through‐space conjugated folded configuration is proposed to explore robust ET materials, opposite to the widely used planar configuration. By bonding two quinolines to the 9,10‐positions of phenanthrene, two novel folded molecules with high thermal and morphological stabilities and high triplet state energy levels (>2.7 eV) are created. These folded molecules possess excellent ET ability with electron mobilities of three orders of magnitude higher than those of linear and planar counterparts. Theoretical calculation and crystallography analysis demonstrate the through‐space conjugated folded configuration has not only reduced reorganization energy but also enlarged charge transfer integral at various dimensions, bringing about efficient multi‐dimensional ET, independent of molecular orientation. By adopting the folded molecule as ET layers, OLEDs with no matter delayed fluorescence or phosphorescence emitters can achieve high external quantum efficiencies and long operational lifetimes simultaneously. This work paves a new avenue towards robust ET materials to improve efficiency and stability of OLEDs.
Direkte Affinitätsreinigung lang wirksamer PASylierter Proteine mit therapeutischem Anwendungspotential unter Nutzung von L‐Prolinamid zur milden Elution
Authors: Schilz Jonas , Clement Charlotte , Greiner Franziska , Skerra Arne
Published: March 2022

Sowohl unzureichende Plasma‐Halbwertszeit (Zirkulation für nur wenige Stunden oder kürzer) als auch ein aufwendiger Reinigungsprozeß können Flaschenhals sein für die biologische Wirkstoffentwicklung. Wir berichten über eine neuartige Strategie zur effizienten und schonenden Afinitätsreinigung pharmakologisch relevanter Proteine, die durch PASylierung hinsichtlich verlängerter Aktivität in vivo modifiziert wurden. Zuvor hatten wir Antikörper mit Spezifität für Pro/Ala‐reiche Sequenzen (PAS) beschrieben, die ein Spektrum an Bindungseigenschaften abdecken. Unser Ansatz hier beruht auf einer Chromatographiematrix, die mit einem niedrigaffinen PAS‐spezifischen Fab‐Fragment zum Zweck der spezifischen Adsorption des PASylierten Proteins aus einer makromolekularen Mischung funktionalisiert ist. Aufgrund vollständiger Abwesenheit hydrophober/aromatischer oder ionischer Gruppen in dem PAS‐Sequenzepitop wird die Bindung allein durch Van‐der‐Waals‐Kontakte und charakteristische Wasserstoffbrückenbindungen vermittelt. Überraschenderweise kann die selektive kompetitive Elution durch Anwendung des hochlöslichen und biologisch inaktiven Iminosäurederivats L‐Prolinamid erreicht werden. Basierend auf der spezifischen, aber hochdynamischen biomolekularen Wechselwirkung gestattet unser Verfahren die direkte Einschrittreinigung PASylierter Proteine aus einem Zellextrakt oder Kulturüberstand, wobei grobe Elutionsbedingungen, wie sie häufig für die konventionelle Affinitätschromatographie erforderlich sind, vermieden werden.
Änderungen der elektronischen Struktur einer Amino‐Photosäure entlang des Förster Zyklus
Authors: Eckert Sebastian , Winghart Marc‐Oliver , Kleine Carlo , Banerjee Ambar , Ekimova Maria , Ludwig Jan , Harich Jessica , Fondell Mattis , Mitzner Rolf , Pines Ehud , Huse Nils , Wernet Philippe , Odelius Michael , Nibbering Erik T. J.
Published: March 2022

Photosäuren sind Moleküle, die einen starken Anstieg ihrer Acidität im ersten elektronisch angeregten Zustand aufweisen. Diese Eigenschaft ermöglicht Echtzeitstudien des Protonentransfers in Säure‐Base‐Reaktionen, des Protonentransports in Energiespeichern und biomolekularen Sensorproteinsystemen. Erklärungsansätze für die Ursachen der Photoacidität reichen von Variationen der freien Solvatationsenergie bis hin zu Veränderungen der elektronischen Struktur während der vier Phasen des Förster‐Zyklus. Wir berichten hier Veränderungen der elektronischen Struktur der Protonen‐Donor Gruppe in einer protonierten aromatischen Amino‐Photosäure in Lösung bei Photoanregung und anschließender Protonentransferdynamik mit Hilfe von Pikosekunden‐Stickstoff‐K‐Kanten‐Spektroskopie. Anhand der Orbitalspezifität von Rumpf‐Valenz‐Übergängen an der funktionellen Aminogruppe weisen wir deutlich ausgeprägte Veränderungen der elektronischen Struktur, des Dipolmoments und der Energiezustände auf der Seite der konjugierten Photobase nach. Diese Ergebnisse bilden die Grundlage für eine zukünftige detaillierte Charakterisierung des Phänomens der Photoacidität im Lichte der elektronischen Struktur.
In Situ Spectroscopic Characterization and Theoretical Calculations Identify Partially Reduced ZnO1−x/Cu Interfaces for Methanol Synthesis from CO2
Authors: Liu Xinyu , Luo Jie , Wang Hengwei , Huang Li , Wang Shasha , Li Shang , Sun Zhihu , Sun Fanfei , Jiang Zheng , Wei Shiqiang , Li Wei‐Xue , Lu Junling
Published: March 2022

The active site of the industrial Cu/ZnO/Al2O3 catalyst used in CO2 hydrogenation to methanol has been debated for decades. Grand challenges remain in the characterization of structure, composition, and chemical state, both microscopically and spectroscopically, and complete theoretical calculations are limited when it comes to describing the intrinsic activity of the catalyst over the diverse range of structures that emerge under realistic conditions. Here a series of inverse model catalysts of ZnO on copper hydroxide were prepared where the size of ZnO was precisely tuned from atomically dispersed species to nanoparticles using atomic layer deposition. ZnO decoration boosted methanol formation to a rate of 877 gMeOH kgcat−1 h−1 with ≈80 % selectivity at 493 K. High pressure in situ X‐ray absorption spectroscopy demonstrated that the atomically dispersed ZnO species are prone to aggregate at oxygen‐deficient ZnO ensembles instead of forming CuZn metal alloys. By modeling various potential active structures, density functional theory calculations and microkinetic simulations revealed that ZnO/Cu interfaces with oxygen vacancies, rather than stoichiometric interfaces, Cu and CuZn alloys were essential to catalytic activation.
Nitrate‐to‐Ammonia Conversion at an InSn‐Enriched Liquid‐Metal Electrode
Authors: Crawford Jessica , Yin Hanqing , Du Aijun , O'Mullane Anthony P.
Published: March 2022

The renewable energy driven electrochemical conversion of nitrates to ammonia is emerging as a viable route for the creation of this hydrogen carrier. However, the creation of highly efficient electrocatalysts that show prolonged stability is an ongoing challenge. Here we show that room temperature liquid metal Galinstan can be used as an efficient and stable electrocatalyst for nitrate conversion to ammonia achieving rates of up to 2335 μg h−1 cm−2 with a Faradaic efficiency of 100 %. Density functional theory (DFT) calculations and experimental observation indicated the activity is due to InSn alloy enrichment within the liquid metal that occurs during the electrocatalytic reaction. This high selectivity for NH3 is also due to additional suppression of the competing hydrogen evolution reaction at the identified In3Sn active site. This work adds to the increasing applicability of liquid metals based on Ga for clean energy technologies.
Euglenatides, Potent Antiproliferative Cyclic Peptides Isolated from the Freshwater Photosynthetic Microalga Euglena gracilis
Authors: Aldholmi Mohammed , Ahmad Rizwan , Carretero‐Molina Daniel , Pérez‐Victoria Ignacio , Martín Jesús , Reyes Fernando , Genilloud Olga , Gourbeyre Léa , Gefflaut Thierry , Carlsson Hanne , Maklakov Alexei , O'Neill Ellis , Field Robert A. , Wilkinson Barrie , O'Connell Maria , Ganesan A.
Published: March 2022

By limiting the nitrogen source to glutamic acid, we isolated cyclic peptides from Euglena gracilis containing asparagine and non‐proteinogenic amino acids. Structure elucidation was accomplished through spectroscopic methods, mass spectrometry and chemical degradation. The euglenatides potently inhibit pathogenic fungi and cancer cell lines e.g., euglenatide B exhibiting IC50 values of 4.3 μM in Aspergillus fumigatus and 0.29 μM in MCF‐7 breast cancer cells. In an unprecedented convergence of non‐ribosomal peptide synthetase and polyketide synthase assembly‐line biosynthesis between unicellular species and the metazoan kingdom, euglenatides bear resemblance to nemamides from Caenorhabditis elegans and inhibited both producing organisms E. gracilis and C. elegans. By molecular network analysis, we detected over forty euglenatide‐like metabolites in E. gracilis, E. sanguinea and E. mutabilis, suggesting an important biological role for these natural products.
Preparation and application of dielectric polymers with high permittivity and low energy loss: A mini review
Authors: Qiu Jie , Gu Qun , Sha Ye , Huang Yang , Zhang Meng , Luo Zhenyang
Published: March 2022

This article reviews the preparation strategies of dielectric polymers with high permittivity and low energy loss, as well as their applications in the field of energy storage and intelligent sensors. We discuss the dependence of dielectric properties of polymer composites on different types of dielectric polarizations, including interfacial polarization, orientational polarization, ionic polarization, and electronic polarization, as well as the improvement of dielectric properties by synergetic effects of multiple polarizations. Due to the difficulties of achieving both high dielectric polarization (hence high permittivity) and low dielectric loss, we focus on the energy loss mechanism of different polarization types and issues in the preparation process. We also discuss current applications and future prospects of dielectric polymers in the field.
Rapid Generation of Tetrahydropyridines and Tetrahydroquinolines by Dearomative Cyanation/Grignard Addition
Authors: Zheng Shixin , Wang Dong , Huang Mindong , Yu Peng
Published: March 2022

A rapid, practical and scalable method for the reductant and tansition‐metal‐free synthesis of a variety of novel 2,4‐disubstituted tetrahydropyridines and tetrahydroquinolines is disclosed. The method is based upon dearomative functionalization of pyridines or quinolines to generate amino nitrile intermediates as masked iminium ions, which then react rapidly with various Grignard reagents in complete stereocontrol.
Light‐Controlled Ionic/Molecular Transport through Solid‐State Nanopores and Nanochannels
Authors: Lu Jiahao , Jiang Yanan , Yu Ping , Jiang Wei , Mao Lanqun
Published: March 2022

Biological nanochannels perfectly operate in organisms and exquisitely control mass transmembrane transport for complex life process. Inspired by biological nanochannels, plenty of intelligent artificial solid‐state nanopores and nanochannels are constructed based on various materials and methods with the development of nanotechnology. Specially, the light‐controlled nanopores/nanochannels have attracted much attention due to the unique advantages in terms of that ion and molecular transport can be regulated remotely, spatially and temporally. According to the structure and function of biological ion channels, light‐controlled solid‐state nanopores/nanochannels can be divided into light‐regulated ion channels with ion gating and ion rectification functions, and light‐driven ion pumps with active ion transport property. In this review, we present a systematic overview of light‐controlled ion channels and ion pumps according to the photo‐responsive components in the system. Then, the related applications of solid‐state nanopores/nanochannels for molecular sensing, water purification and energy conversion are discussed. Finally, a brief conclusion and short outlook are offered for future development of the nanopore/nanochannel field.