bluuebunny/crossref_metadata_2025 huggingface dataset:
Benchmarking Noise and Dephasing in Emerging Electrical Materials for Quantum Technologies
Authors: Islam Saurav , Shamim Saquib , Ghosh Arindam
Published: May 2022

As quantum technologies develop, a specific class of electrically conducting materials is rapidly gaining interest because they not only form the core quantum‐enabled elements in superconducting qubits, semiconductor nanostructures, or sensing devices, but also the peripheral circuitry. The phase coherence of the electronic wave function in these emerging materials will be crucial when incorporated in the quantum architecture. The loss of phase memory, or dephasing, occurs when a quantum system interacts with the fluctuations in the local electromagnetic environment, which manifests in “noise” in the electrical conductivity. Hence, characterizing these materials and devices therefrom, for quantum applications, requires evaluation of both dephasing and noise, although there are very few materials where these properties are investigated simultaneously. Here, the available data on magnetotransport and low‐frequency fluctuations in electrical conductivity are reviewed to benchmark the dephasing and noise. The focus is on new materials that are of direct interest to quantum technologies. The physical processes causing dephasing and noise in these systems are elaborated, the impact of both intrinsic and extrinsic parameters from materials synthesis and devices realization are evaluated, and it is hoped that a clearer pathway to design and characterize both material and devices for quantum applications is thus provided.
Recent Progress in SERS‐Based Anti‐counterfeit Labels
Authors: Huo Yifeng , Yang Zishen , Wilson Tanner , Jiang Chaoyang
Published: May 2022

Anti‐counterfeit labels protect many commercial goods, drugs, and currencies from counterfeiting activities. Recently, the designs of anti‐counterfeit labels have emerged utilizing surface‐enhanced Raman scattering (SERS) as a powerful technique, in which SERS‐active materials provide strong Raman signals of probe molecules. These signals are unique and, so far, have rarely been used in practical anti‐counterfeit labels applications. In this review, the general methodology of using Raman and SERS in designing anti‐counterfeit labels is first introduced. Then, two types of secret information in SERS labels, spectroscopic information and graphical information, are detailed and discussed with a focus on how the molecular information is encoded with SERS labels. Later, several advanced SERS labels are presented which combine existing security features such as barcode, quick response code, fluorescence, and unclonable features. Finally, the challenges in building usable SERS anti‐counterfeit labels are discussed and possible research directions are described.
Tautomeric Dual‐Site Passivation for Carbon‐Based Printable Mesoscopic Perovskite Solar Cells
Authors: Chen Yan , Ma Dun , Wang Zhiqiang , He Jingshan , Gong Xueqing , Wu Wenjun
Published: May 2022

Although ionic conjugated passivation systems, such as ionic liquids (ILs), have been used to passivate perovskite in carbon‐based printable mesoscopic perovskite solar cells (FP‐PSCs), their tautomerism process and synergistic effect of multifunctional groups have not yet caused enough attention. In this work, a series of novel ILs including 1‐allyl‐3‐methylimidazole tetrafluoroborate ([AMIm]BF4) and 1‐benzyl‐3‐methylimidazole tetrafluoroborate ([BzMIm]BF4) used as passivants for FP‐PSCs are reported. Combining Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculation, it is found that one of its tautomers (positive ion at the near end N atom of conjugated side chain) plays a key role on dual‐site simultaneous passivation. As the conjugation degree of side chain increases from allyl to benzyl, it not only effectively inhibits the non‐radiative charge recombination, but also reduces the passivation adsorption energy and increases the charge transfer rate. A high efficiency of 16.87% has been achieved with a high FF (>0.7), a Jsc of 23.88 mA cm–2 value and Voc value up to 1.0 V, by using the “tautomeric dual‐site passivation” strategy.
Cyanostilbene‐Based AIEgen Smart Film: Optical Switching by Engineering Molecular Packing Structure and Molecular Conformation Through Thermal and Photoinduced Monotropic Phase Transition
Authors: Koo Jahyeon , Jang Junhwa , Oh Mintaek , Kim Minwook , Hyeong Jaeseok , Lim Seok‐In , Cao Yan , Tran Duy Thanh , Park Sungjune , Jeong Kwang‐Un
Published: May 2022

The optical properties of newly synthesized cyanostilbene‐based AIEgen (D4CS) exhibiting a unique monotropic phase transition are modulated by engineering molecular packing structure and molecular conformation through temperature change and light irradiation. D4CS exhibits only a low‐ordered smectic liquid crystal (SmA) phase over a wide temperature range during cooling and subsequent heating processes, while D4CS crystallizes after a significantly long annealing time at room temperature. Crystallized D4CS exhibits a complex phase transition (SmCr–SmB–SmA–Iso) in the subsequent heating process. In addition, the photoisomerization behavior of D4CS from trans to cis conformer can induce a phase transition to the isotropic (Iso) state, and the reverse isomerization can occur by high‐temperature heat treatment. This unique thermal and photoinduced phase transition of D4CS is accompanied by changes in optical properties including transmittance and luminescence. Based on the optical switching behavior of D4CS, photopatternable temperature and time‐dependent optical films are demonstrated. The newly developed cyanostilbene‐based AIEgen is a smart optical material with great potential for advanced optical sensors, anti‐counterfeiting ink and smart display system.
Recent Advances and Challenges in Ultrafast Photonics Enabled by Metal Nanomaterials
Authors: Wang Gang , Liu Tingyi , Chao Jiale , Jin Hong , Liu Jiayao , Zhang Han , Lyu Wenhao , Yin Peng , Al‐Ghamdi Ahmed , Wageh Swelm , Fu Bo , Zhang Han
Published: May 2022

Nanomaterials with outstanding optical properties are widely used in ultrafast photonics. Especially, metal nanomaterials have attracted increasing attention in recent years owing to the surface plasmon resonance that further enhances their nonlinear optical response, making them suitable for generating ultrafast pulses in a wide range of wavebands. Herein, the fabrication and integration processes of typical metal nanomaterials such as gold, silver, and copper, as well as their applications in ultrafast lasers are reviewed. The synthesis methods of metal nanomaterials, which can be divided into dry and wet methods, are first introduced with their characteristics and advantages summarized. Moreover, the integration approaches that are used to incorporate metal nanomaterials into laser cavities are discussed, where sandwich structure based on polymer film and deposition method, as well as evanescent‐wave structure based on D‐shaped and tapered fiber are demonstrated. Besides, the state of the art of typical ultrafast lasers enabled by metal nanoparticles is systematically reviewed. Finally, current challenges and perspectives on the development of ultrafast photonics enabled by metal nanomaterials are proposed.
Macromolecular Viral Entry Inhibitors as Broad‐Spectrum First‐Line Antivirals with Activity against SARS‐CoV‐2
Authors: Groß Rüdiger , Dias Loiola Lívia Mesquita , Issmail Leila , Uhlig Nadja , Eberlein Valentina , Conzelmann Carina , Olari Lia‐Raluca , Rauch Lena , Lawrenz Jan , Weil Tatjana , Müller Janis A. , Cardoso Mateus Borba , Gilg Andrea , Larsson Olivia , Höglund Urban , Pålsson Sandra Axberg , Tvilum Anna Selch , Løvschall Kaja Borup , Kristensen Maria M. , Spetz Anna‐Lena , Hontonnou Fortune , Galloux Marie , Grunwald Thomas , Zelikin Alexander N. , Münch Jan
Published: May 2022

Inhibitors of viral cell entry based on poly(styrene sulfonate) and its core–shell nanoformulations based on gold nanoparticles are investigated against a panel of viruses, including clinical isolates of SARS‐CoV‐2. Macromolecular inhibitors are shown to exhibit the highly sought‐after broad‐spectrum antiviral activity, which covers most analyzed enveloped viruses and all of the variants of concern for SARS‐CoV‐2 tested. The inhibitory activity is quantified in vitro in appropriate cell culture models and for respiratory viral pathogens (respiratory syncytial virus and SARS‐CoV‐2) in mice. Results of this study comprise a significant step along the translational path of macromolecular inhibitors of virus cell entry, specifically against enveloped respiratory viruses.
Learning From Plants: Lycopene Additive Passivation toward Efficient and “Fresh” Perovskite Solar Cells with Oxygen and Ultraviolet Resistance
Authors: Zhuang Xinmeng , Zhou Donglei , Liu Shuainan , Sun Rui , Shi Zhichong , Liu Le , Wang Tianyuan , Liu Bin , Liu Dali , Song Hongwei
Published: May 2022

Currently, the photovoltaic performance of perovskite solar cells (PSCs) is closely linked to undermined defects in the perovskite, and the correct approach to ensure stability under practical conditions is still in dispute. Therefore, natural, healthy, and low‐cost additives are expected to not only reduce the trap sites but also drastically improve stability. In this work, the natural antioxidant additive lycopene extracted from tomatoes is introduced into PSCs. The results indicate that lycopene can passivate the grain boundaries, improve the crystallinity, reduce trap density, and facilitate the α phase formation of perovskite at room temperature. As a result, the power conversion efficiency (PCE) is considerably improved from 20.57% to 23.62% with vastly enhanced Jsc and Voc. Additionally, lycopene can eliminate the UV‐induced free radicals in the light aging process. The target device displays the enhanced hydrophobic, antioxidative properties, which demonstrates high O2 stability with 91.2% average PCE for 960 h, improved UV stability and long‐term stability with an average PCE of 92.4% after 3500 h. This work provides a strategy to solve the existing efficiency and stability issues in PSC devices through learning from natural plants, which paves the way for the development of environmentally friendly PSCs with high efficiency and stability, on the path toward industrialization.
Benchmarking US consumption and perceptions of beef and plant‐based proteins
Authors: Taylor Hannah , Tonsor Glynn T. , Lusk Jayson L. , Schroeder Ted C.
Published: May 2022

This article uses two complementary analyses to document consumption of beef and plant‐based proteins along with perceptions held by US consumers. Beef is chosen three times more often than plant‐based proteins and consumers hold a positive image of beef overall. Key differences are outlined between regular meat consumers and those declaring alternative diets. Combined these findings extend understanding in the dynamic situation presented by plant‐based proteins in the US market.
Heterozygous variants in PRPF8 are associated with neurodevelopmental disorders
Authors: O'Grady Lauren , Schrier Vergano Samantha A. , Hoffman Trevor L. , Sarco Dean , Cherny Sara , Bryant Emily , Schultz‐Rogers Laura , Chung Wendy K. , Sacharow Stephanie , Immken Ladonna L. , Holder Susan , Blackwell Rebecca R. , Buchanan Catherine , Yusupov Roman , Lecoquierre François , Guerrot Anne‐Marie , Rodan Lance , de Vries Bert B. A. , Kamsteeg Erik Jan , Santos Simarro Fernando , Palomares‐Bralo Maria , Brown Natasha , Pais Lynn , Ferrer Alejandro , Klee Eric W. , Babovic‐Vuksanovic Dusica , Rhodes Lindsay , Person Richard , Begtrup Amber , Keller‐Ramey Jennifer , Santiago‐Sim Teresa , Schnur Rhonda E. , Sweetser David A. , Gold Nina B.
Published: May 2022

The pre‐mRNA‐processing factor 8, encoded by PRPF8, is a scaffolding component of a spliceosome complex involved in the removal of introns from mRNA precursors. Previously, heterozygous pathogenic variants in PRPF8 have been associated with autosomal dominant retinitis pigmentosa. More recently, PRPF8 was suggested as a candidate gene for autism spectrum disorder due to the enrichment of sequence variants in this gene in individuals with neurodevelopmental disorders. We report 14 individuals with various forms of neurodevelopmental conditions, found to have heterozygous, predominantly de novo, missense, and loss‐of‐function variants in PRPF8. These individuals have clinical features that may represent a new neurodevelopmental syndrome.
Nonsyndromic arteriopathy and aortopathy and vascular Ehlers–Danlos syndrome causing COL3A1 variants
Authors: Yagi Hiroki , Takeda Norifumi , Amiya Eisuke , Akiyama Nana , Chang Hyangri , Ishiura Hiroyuki , Sato Jiro , Akazawa Hiroshi , Morita Hiroyuki , Komuro Issei
Published: May 2022

Vascular Ehlers–Danlos syndrome (vEDS) is an autosomal dominant genetic disorder characterized by soft connective tissue vulnerability due to dysfunction of Type III collagen and caused by the pathogenic variants in COL3A1 gene. In the era of next‐generation sequencing, multiple genes including COL3A1 can be simultaneously analyzed, and among patients suffering from aortopathy even without any other clinical features suggestive of vEDS, pathogenic COL3A1 variants have been increasingly identified. Here, we briefly summarize the characteristics of 12 Japanese patients from 11 families with arteriopathy and pathogenic or likely pathogenic COL3A1 variants in our hospital. Five patients did not have any extra‐arterial clinical features, however, the multigene panel testing for hereditary thoracic aortic aneurysm and dissection unexpectedly revealed that two had glycine substitutions in the triple‐helical region and three had haploinsufficient type variants in the COL3A1 gene, whose pathogenicities were all classified as pathogenic or likely pathogenic. Further genetic screening and identification of pathogenic variants in patients with nonsyndromic arteriopathy and aortopathy will enable us to develop risk‐stratification and management based on the genetic diagnosis.
Fast and Robust Quantum State Transfer via Optimal Transitionless Quantum Driving
Authors: Zhang Chun‐Ling , Lin Xiu‐Min
Published: May 2022

For the past few years, shortcuts to adiabaticity have attracted great attention since they can avoid the necessity of slow driving for adiabatic method while inheriting the partial robustness of the adiabatic dynamics. In this paper, a universal approach to implement quantum state transfer in a three‐state system via optimal transitionless quantum driving is presented. The fast path is optimized for great robustness against uncontrolled systematic error by selecting appropriate experimental parameters. The robustness of the protocol is discussed via numerical simulations. Compared with conventional transitionless quantum driving and adiabatic passage, the protocol via optimized transitionless quantum driving possesses more robustness against the systematic error. Furthermore, decoherence arising from atomic spontaneous emission and dephasing only has a slight impact on the fidelity of quantum state transfer. This work opens up a new avenue for high‐fidelity quantum state transfer in the case of the uncontrolled errors.
Copper‐Bridged Tetrakis(4‐ethynylphenyl)ethene Aggregates with Photo‐Regulated 1O2 and O2.− Generation for Selective Photocatalytic Aerobic Oxidation
Authors: Sun Huiying , Lang Zhongling , Zhao Yingnan , Zhao Xinyu , Qiu Tianyu , Hong Qiang , Wei Kaiqiang , Tan Huaqiao , Kang Zhenhui , Li Yangguang
Published: May 2022

Active species regulation is a key scientific issue that essentially determines the selectivity and activity of a photocatalyst. Herein, CuI‐bridged tetrakis(4‐ethynylphenyl)ethene aggregates (T4EPE‐Cu) with photo‐regulated 1O2 and O2.− generation were demonstrated for selective photocatalytic aerobic oxidation. In this system, transient photovoltage combined with the density functional theory calculations confirmed that Cu‐alkynyl was the main oxygen activation site. The adsorbed O2 tends to produce O2.− because of the potential well effect of Cu‐alkynyl under high‐energy light excitation. But under low‐energy light, O2 tends to produce 1O2 via resonance energy transfer with Cu‐alkynyl. For α‐terpinene oxidation, the ratios of 1O2 products to O2.− products can be controlled from 1.3 (380 nm) to 10.7 (600 nm). Furthermore, T4EPE‐Cu exhibited ultrahigh photocatalytic performance for Glaser coupling and benzylamine oxidation, with a conversion and selectivity of over 99 %.
Synthesis and Characterization of Stable Iron Pentacarbonyl Radical Cation Salts
Authors: Rall Jan M. , Schorpp Marcel , Keilwerth Martin , Mayländer Maximilian , Friedmann Christian , Daub Michael , Richert Sabine , Meyer Karsten , Krossing Ingo
Published: May 2022

The open‐shell iron pentacarbonyl cation [Fe(CO)5].+ was isolated by deelectronation, i.e., the single‐electron oxidation of the parent neutral Fe(CO)5 using [phenazineF].+ as the [Al(ORF)4]− and [F‐{Al(ORF)3}2]− salt (RF=C(CF3)3; phenazineF=perfluoro‐5,10‐bis(perfluorophenyl)‐5,10‐dihydrophenazine). [Fe(CO)5].+[Al(ORF)4]− was fully characterized (scXRD analysis, IR, NMR, EPR, 57Fe spectroscopy, CV and SQUID magnetization study) and, apart from being a compound of fundamental interest, may serve as a precursor for low‐valent iron coordination chemistry.
Metathesis between E−C(spn) and H−C(sp3) σ‐Bonds (E=Si, Ge; n=2, 3) on an Osmium‐Polyhydride
Authors: Esteruelas Miguel A. , López Ana M. , Oñate Enrique , Raga Esther
Published: May 2022

The silylation of a phosphine of OsH6(PiPr3)2 is performed via net‐metathesis between Si−C(spn) and H−C(sp3) σ‐bonds (n=2, 3). Complex OsH6(PiPr3)2 activates the Si−H bond of Et3SiH and Ph3SiH to give OsH5(SiR3)(PiPr3)2, which yield OsH4{κ1‐P,η2‐SiH‐[iPr2PCH(Me)CH2SiR2H]}(PiPr3) and R−H (R=Et, Ph), by displacement of a silyl substituent with a methyl group of a phosphine. Such displacement is a first‐order process, with activation entropy consistent with a rate determining step occurring via a highly ordered transition state. It displays selectivity, releasing the hydrocarbon resulting from the rupture of the weakest Si‐substituent bond, when the silyl ligand bears different substituents. Accordingly, reactions of OsH6(PiPr3)2 with dimethylphenylsilane, and 1,1,1,3,5,5,5‐heptamethyltrisiloxane afford OsH5(SiR2R′)(PiPr3)2, which evolve into OsH4{κ1‐P,η2‐GeH‐[iPr2PCH(Me)CH2SiR2H]}(PiPr3) (R=Me, OSiMe3) and R′−H (R′=Ph, Me). Exchange reaction is extended to Et3GeH. The latter reacts with OsH6(PiPr3)2 to give OsH5(GeEt3)(PiPr3)2, which loses ethane to form OsH4{κ1‐P,η2‐GeH‐[iPr2PCH(Me)CH2GeEt2H]}(PiPr3).
Iridium‐Catalyzed Asymmetric Hydrogenation of 2,3‐Diarylallyl Amines with a Threonine‐Derived P‐Stereogenic Ligand for the Synthesis of Tetrahydroquinolines and Tetrahydroisoquinolines
Authors: Rojo Pep , Molinari Medea , Cabré Albert , García‐Mateos Clara , Riera Antoni , Verdaguer Xavier
Published: May 2022

Chiral compounds containing nitrogen heteroatoms are fundamental substances for the chemical, pharmaceutical and agrochemical industries. However, the preparation of some of these interesting scaffolds is still underdeveloped. Herein we present the synthesis of a family of P‐stereogenic phosphinooxazoline iridium catalysts from L‐threonine methyl ester and their use in the asymmetric hydrogenation of N‐Boc‐2,3‐diarylallyl amines, achieving very high enantioselectivity. Furthermore, the synthetic utility of the 2,3‐diarylpropyl amines obtained is demonstrated by their transformation to 3‐aryl‐tetrahydroquinolines and 4‐benzyl‐tetrahydroisoquinolines, which have not yet been obtained in an enantioselective manner by direct reduction of the corresponding aromatic heterocycles. This strategy allows the preparation of these types of alkaloids with the highest enantioselectivity reported up to date.
Molecular Motion and Nonradiative Decay: Towards Efficient Photothermal and Photoacoustic Systems
Authors: Xu Changhuo , Ye Ruquan , Shen Hanchen , Lam Jacky W. Y. , Zhao Zheng , Zhong Tang Ben
Published: May 2022

Nonradiative decay invariably competes with radiative decay during the deexcitation process of matter. In the community of luminescence research, nonradiative decay has been deemed less attractive than radiative decay. However, all things in their being are good for something and so is nonradiative decay. As the molecular motion‐facilitated nonradiative decay (MMFND) effect is inevitable in photophysical processes, it provides a new avenue to convert the harvested light energy into exploitable forms by harnessing molecular motion. In many cases, active molecular motion enables thermal deactivation from excited states. In this Minireview, recent advances in photothermal and photoacoustic systems with MMFND character are summarized. We believe that this presentation of the rational engineering of molecular motion for efficient photothermal generation will deepen the understanding of the relationship between molecular motion and nonradiative decay and navigate people to rethink the positive aspects of nonradiative decay for the establishment of new light‐controllable techniques.
Organocatalytic Enantioselective Synthesis of Bicyclo[2.2.2]octenones via Oxaziridinium Catalysed ortho‐Hydroxylative Phenol Dearomatization**
Authors: D'Arcy Tom D. , Elsegood Mark R. J. , Buckley Benjamin R.
Published: May 2022

Hydroxylative dearomatization reactions of phenols (HPD) offer an efficient way to assemble complex, biologically relevant scaffolds. Despite this, enantioselective hydroxylative phenol dearomatizations for the construction of bicyclo[2.2.2]octenones are classically limited to stoichiometric chiral reagents, and a practical, enantioselective catalytic method has remained elusive. Herein, we describe a highly enantioselective, organocatalytic tandem o‐HPD‐[4+2] reaction. Our methodology utilizes a chiral oxaziridinium organocatalyst, that is available in both enantiomeric forms, to afford dearomatized products in high enantioselectivity over a range of phenol substitution patterns. This approach was applied to the highly enantioselective synthesis of (+)‐biscarvacrol (99 : 1 e.r.) and (−)‐bis(2,6‐xylenol) (94 : 6 e.r.). The practicality of our conditions was demonstrated at gram‐scale, using an amine precatalyst, accessible in a single synthetic step.
Ligand Fluorination to Mitigate the Raman Relaxation of DyIII Single‐Molecule Magnets: A Combined Terahertz, Far‐IR and Vibronic Barrier Model Study
Authors: Ma Yan , Zhai Yuan‐Qi , Luo Qian‐Cheng , Ding You‐Song , Zheng Yan‐Zhen
Published: May 2022

The fast Raman relaxation process via a virtual energy level has become a puzzle for how to chemically engineer single‐molecule magnets (SMMs) with better performance. Here, we use the trifluoromethyl group to systematically substitute the methyl groups in the axial position of the parent bis‐butoxide pentapyridyl dysprosium(III) SMM. The resulting complexes—[Dy(OLA)2py5][BPh4] (LA=CH(CF3)2− 1, CH2CF3− 2, CMe2CF3− 3)—show progressively enhanced TBhys (@100 Oe s−1) from 17 K (for 3), 20 K (for 2) to 23 K (for 1). By experimentally identifying the varied under barrier relaxation energy in the 5–500 cm−1 regime, we are able to identify that the C−F bond related vibration energy of the axial ligand ranging from 200 to 350 cm−1 is the key variant for this improvement. Thus, this finding not only reveals a correlation between the structure and the Raman process but also provides a paradigm for how to apply the vibronic barrier model to analyze multi‐phonon relaxation processes in lanthanide SMMs.
A Chain‐Growth Mechanism for Conjugated Polymer Synthesis Facilitated by Dinuclear Complexes with Redox‐Active Ligands
Authors: King Andrew J. , Zhukhovitskiy Aleksandr V.
Published: May 2022

Conjugated polymers are widely used in energy conversion and sensor applications, but their synthesis relies on imprecise step‐growth or narrow‐scope chain‐growth methods, typically based on transition metal (TM)‐catalyzed cross‐coupling. Here we report that a dinickel complex with a redox‐active naphthyridine diimine ligand accesses new chain‐growth mechanistic manifolds for both donor and acceptor conjugated polymers, represented by poly(3‐hexylthiophene), poly(2,3‐bis(2‐ethylhexyl)thienopyrazine), and poly(2‐(2‐octyldodecyl)benzotriazole). For the latter, our method is particularly effective: we achieve high degrees of polymerization (DP) (>100) with moderate dispersities (Đ) of ≈1.4. Mechanistic analysis supports a radical/radical anion chain‐growth mechanism with organometallic intermediates instead of TM‐catalyzed cross‐couplings. Hence, our work develops new mechanisms for conjugated polymer synthesis and furnishes insights about the elementary reactivity of dinuclear complexes.
COVID Couple Therapy: Telehealth and Somatic Action Techniques
Authors: Lord Susan A.
Published: May 2022

In March of 2020, during the global COVID‐19 pandemic, therapists quickly transitioned to telehealth platforms to provide their services. Teletherapy, while subject to some constraints, presents unique opportunities to work creatively with couples, particularly during these uncertain times. This paper offers a case study of work with a couple using systemic, developmental attachment, dialogical, and somatic trauma theories. Action techniques, including doubling, ideal futures creation, and a foam roller trust exercise are employed to facilitate change processes as couples face the chaos and unknowns of the pandemic and the difficulties that have become triggered between them. These exercises help to open perspective, increase awareness, and lower resistance to change. Couples are able to physically enact and metabolise alternative realities while discharging excess energies in familiar surroundings.
Synthesis and application of temperature‐sensitive polymer as a novel plugging agent for water‐based drilling fluids
Authors: Bai Xiaodong , Yong Xuemei , Luo Yumei , Deng Licheng , Li Ke , Zhou Yi
Published: May 2022

In the process of drilling with water‐based drilling fluid, polymer plugging agent is very important to solve the problem of wellbore instability in the formation with micropores and microfractures. In this study, N‐isopropyl acrylamide and 2‐acrylamide‐2‐methylpropanesulfonic acid were grafted onto the surface of SiO2 modified by vinyl trimethoxysilane by reverse suspension polymerization reaction, and a heat‐sensitive polymer plugging agent was synthesized. The structure analysis showed that the synthetic material was the target product, with a particle size of 49.665 μm, high‐temperature resistance and sensitive temperature response behavior. According to laboratory evaluation experiments, it can be seen that the addition of the polymer increased the electrostatic stability of bentonite particles and had a chemical inhibition effect. Under the action of temperature and pressure, the synthesized temperature sensitive plugging agent formed a dense hydrophobic membrane on the surface of mud cake, which physically sealed the microcracks and pores, and reduced the filtration loss, so as to greatly improve the stability of shale. The experimental results showed that the synthesized temperature sensitive plugging agent has excellent high‐temperature resistance and plugging performance.
Preceding winter Okhotsk Sea ice as a precursor to the following winter extreme precipitation in South China
Authors: Ji Kai , Zhang Zhongshi , Ding Ruiqiang , Li Jianping , Tian Yurun , Gao Yongqi , Zheng Jiayu
Published: May 2022

The winter extreme precipitation over South China (SC) experiences a large year‐to‐year variability, causing uncertainty in its prediction. Here, we find that the boreal winter sea ice concentration (SIC) in the Okhotsk Sea can serve as a precursor to the following winter's extreme precipitation frequency (EPF) over SC, which has important implications for its prediction. Further analysis reveals that the Okhotsk Sea SIC anomalies help to reinforce North Pacific Oscillation‐like atmospheric variability over the North Pacific, which induces the development of El Niño‐Southern Oscillation (ENSO)‐like SST anomalies in the equatorial eastern Pacific. The ENSO may act as a “power amplifier” to boost the impact of the Okhotsk Sea winter SIC anomalies on the following winter EPF over SC via a positive atmosphere–ocean feedback process. Our findings suggest that the Okhotsk Sea SIC may act as a potential precursor for the winter EPF over SC leading by about 1 year, and further improve our understanding of extratropical‐tropical interactions and aid predictability of winter extreme precipitation over SC.
Multi‐information source Bayesian optimization of culture media for cellular agriculture
Authors: Cosenza Zachary , Astudillo Raul , Frazier Peter I. , Baar Keith , Block David E.
Published: May 2022

Culture media used in industrial bioprocessing and the emerging field of cellular agriculture is difficult to optimize due to the lack of rigorous mathematical models of cell growth and culture conditions, as well as the complexity of the design space. Rapid growth assays are inaccurate yet convenient, while robust measures of cell number can be time‐consuming to the point of limiting experimentation. In this study, we optimized a cell culture media with 14 components using a multi‐information source Bayesian optimization algorithm that locates optimal media conditions based on an iterative refinement of an uncertainty‐weighted desirability function. As a model system, we utilized murine C2C12 cells, using AlamarBlue, LIVE stain, and trypan blue exclusion cell counting assays to determine cell number. Using this experimental optimization algorithm, we were able to design media with 181% more cells than a common commercial variant with a similar economic cost, while doing so in 38% fewer experiments than an efficient design‐of‐experiments method. The optimal medium generalized well to long‐term growth up to four passages of C2C12 cells, indicating the multi‐information source assay improved measurement robustness relative to rapid growth assays alone.
Recombinant Snail Sialic Acid Aldolase is Promiscuous towards Aliphatic Aldehydes
Authors: Hu Zi‐Xuan , Cheng Cheng , Li Yu‐Qian , Qi Xiao‐Han , Wang Ting , Liu Li , Voglmeir Josef
Published: May 2022

Aldolases are enzymes that reversibly catalyze the cleavage of carbon‐carbon bonds. Here we describe a recombinant sialic acid aldolase originating from the freshwater snail Biomphalaria glabrata (sNPL), and compare its substrate spectrum with a sialic acid aldolase originating from chicken (chNPL). In contrast to vertebrate animals which can synthesize, degrade, and incorporate sialic acids on glycoconjugate ubiquitously, snails (as all mollusks) cannot synthesize sialic acids endogenously, and therefore the biological function and substrate scope of sNPL ought to differ significantly from vertebrate sialic aldolases such as chNPL. sNPL was active towards a series of sialic acid derivatives but was in contrast to chNPL unable to catalyze the cleavage of N‐acetylneuraminic acid into N‐acetylmannosamine and pyruvate. Interestingly, chNPL and sNPL showed contrasting C4(R)/(S) diastereoselectivity towards the substrates d‐mannose and d‐galactose in the presence of pyruvate. In addition, sNPL was able to synthesize a series of 4‐hydroxy‐2‐oxoates using the corresponding aliphatic aldehyde substrates in the presence of pyruvate, which could be not achieved by chNPL.
Mechanistic Investigations on Hydrogenation, Isomerization and Hydrosilylation Reactions Mediated by a Germyl‐Rhodium System
Authors: Bajo Sonia , Theulier Cyril A. , Campos Jesús
Published: May 2022

We recently disclosed a dehydrogenative double C−H bond activation reaction in the unusual pincer‐type rhodium‐germyl complex [(ArMes)2ClGeRh] (ArMes=C6H3‐2,6‐(C6H2‐2,4,6‐Me3)2). Herein we investigate the catalytic applications of this Rh/Ge system in several transformations, namely trans‐semihydrogenation of internal alkynes, trans‐isomerization of olefins and hydrosilylation of alkynes. We have compared the activity and selectivity of this catalyst against other common rhodium precursors, as well as related sterically hindered rhodium complexes, being the one with the germyl fragment superior in terms of selectivity towards E‐isomers. To increase this selectivity, a tandem catalytic protocol that incorporates the use of a heterogeneous catalyst for the trans‐semihydrogenation of internal alkynes has been devised. Kinetic mechanistic investigations provide important information regarding the individual catalytic cycles that comprise the overall trans‐semihydrogenation of internal alkynes.
Sulfur and Azobenzenes, a Profitable Liaison: Straightforward Synthesis of Photoswitchable Thioglycosides with Tunable Properties
Authors: Berry Jonathan , Lindhorst Thisbe K. , Despras Guillaume
Published: May 2022

Azobenzene photoswitches are valuable tools for controlling properties of molecular systems with light. We have been investigating azobenzene glycoconjugates to probe carbohydrate‐protein interactions and to design glycoazobenzene macrocycles with chiroptical and physicochemical properties modulated by light irradiation. To date, direct conjugation of glycosides to azobenzenes was performed by reactions providing target compounds in limited yields. We therefore sought a more effective and reliable coupling method. In this paper, we report on a straightforward thioarylation of azobenzene derivatives with glycosyl thiols as well as other thiols, thereby increasing the scope of azobenzene conjugation. Even challenging unsymmetrical conjugates can be achieved in good yields via sequential or one‐pot procedures. Importantly, red‐shifted azoswitches, which are addressed with visible light, were easily functionalized. Additionally, by oxidation of the sulfide bridge to the respective sulfones, both the photochromic and the thermal relaxation properties of the core azobenzene can be tuned. Utilizing this option, we realized orthogonal three‐state photoswitching in mixtures containing two distinct azobenzene thioglycosides.
Experimental and Theoretical Study of NiII‐ and PdII‐Promoted Double Geminal C(sp3)−H Bond Activation Providing Facile Access to NHC Pincer Complexes: Isolated Intermediates and Mechanism
Authors: He Fengkai , Gourlaouen Christophe , Pang Huan , Braunstein Pierre
Published: May 2022

We report the first examples of metal‐promoted double geminal activation of C(sp3)−H bonds of the N−CH2−N moiety in an imidazole‐type heterocycle, leading to nickel and palladium N‐heterocyclic carbene complexes under mild conditions. Reaction of the new electron‐rich diphosphine 1,3‐bis((di‐tert‐butylphosphaneyl)methyl)‐2,3‐dihydro‐1H‐benzo[d]imidazole (1) with [PdCl2(cod)] occurred in a stepwise fashion, first by single C−H bond activation yielding the alkyl pincer complex [PdCl(PC
HP)] (3) with two trans phosphane donors and a covalent Pd−C
bond. Activation of the C−H bond of the resulting α‐methine C
H−M group occurred subsequently when 3 was treated with HCl to yield the NHC pincer complex [PdCl(PCNHCP)]Cl (2). Treatment of 1 with [NiBr2(dme)] also afforded a NHC pincer complex, [NiBr(PCNHCP)]Br (6), but the reactions leading to the double geminal C−H bond activation of the N−CH2−N group were too fast to allow identification or isolation of an intermediate analogous to 3. The determination of six crystal structures, the isolation of reaction intermediates and DFT calculations provided the basis for suggesting the mechanism of the stepwise transformation of a N−CH2−N moiety in the N−CNHC−N unit of NHC pincer complexes and explain the key differences observed between the Pd and Ni chemistries.
Tuning Deazaflavins Towards Highly Potent Reducing Photocatalysts Guided by Mechanistic Understanding – Enhancement of the Key Step by the Internal Heavy Atom Effect
Authors: Pavlovska Tetiana , Král Lesný David , Svobodová Eva , Hoskovcová Irena , Archipowa Nataliya , Kutta Roger Jan , Cibulka Radek
Published: May 2022

Deazaflavins are well suited for reductive chemistry acting via a consecutive photo‐induced electron transfer, in which their triplet state and semiquinone – the latter is formed from the former after electron transfer from a sacrificial electron donor – are key intermediates. Guided by mechanistic investigations aiming to increase intersystem crossing by the internal heavy atom effect and optimising the concentration conditions to avoid unproductive excited singlet reactions, we synthesised 5‐aryldeazaflavins with Br or Cl substituents on different structural positions via a three‐component reaction. Bromination of the deazaisoalloxazine core leads to almost 100 % triplet yield but causes photo‐instability and enhances unproductive side reactions. Bromine on the 5‐phenyl group in ortho position does not affect the photostability, increases the triplet yield, and allows its efficient usage in the photocatalytic dehalogenation of bromo‐ and chloroarenes with electron‐donating methoxy and alkyl groups even under aerobic conditions. Reductive powers comparable to lithium are achieved.
The Aryl Sulfide Synthesis via Sulfide Transfer
Authors: Liang Xinyu , Wen Kaikai , Shi Qinqin , Zhang Bei‐Bei , Pei Shurui , Lin Qijie , Ma Bowei , Wang Song , Zhang Meng , Li Xiang , Wang Zhi‐Xiang , Huang Hui
Published: May 2022

Aryl sulfides are in great demands in drugs and materials sciences. To avoid using nucleophilic and noxious thiols, many efforts have been focused on exploring novel sulfide resources. Herein, a reductive Pd‐catalyzed, Ni‐mediated method to synthesize aryl sulfides via a sulfide transfer reaction is developed. The utility and scope of this reaction is exemplified by various aryl electrophiles and aryl sulfides. Mechanistic studies reveal two competing catalytic cycles of sulfide transfer and aryl transfer in this reaction, where the former one is favored over the later one because of the large energy barrier difference during the transmetalation. Moreover, two important chemicals are late‐stage functionalized by this method, exhibiting the potential applications in drugs and materials science.
Direct Perfluoroalkylation of C−H Bonds in (Hetero)arenes
Authors: Baguia Hajar , Evano Gwilherm
Published: May 2022

Perfluoroalkylated (hetero)arenes represent an extremely important family of molecules commonly utilized in many areas such as medicinal chemistry, agrochemistry and material sciences. Due to their unique properties, they have attracted significant interest from synthetic chemists and various methods have been developed for their synthesis. Among them, the direct perfluoroalkylation of C(sp2)−H bonds in (hetero)arenes is one of the most attractive and straightforward ones, provided that it proceeds with high levels of regioselectivity. In this review article, a comprehensive overview of advances in this field is presented, with a special focus on the reaction mechanisms involved in these transformations and their regioselectivity. All methods available have been classified according to the nature of the perfluoroalkyl chain introduced, trifluoromethylation reactions being overviewed in a separate section, and to the nature of the reagents/catalysts required.
Formal Umpolung Addition of Phosphites to 2‐Azaaryl Ketones under Chiral Brønsted Base Catalysis: Enantioselective Protonation Utilizing [1,2]‐Phospha‐Brook Rearrangement
Authors: Kondoh Azusa , Hirozane Takayuki , Terada Masahiro
Published: May 2022

The formal enantioselective umpolung addition of dialkyl phosphites to 2‐azaaryl ketones was developed under Brønsted base catalysis. The reaction involves the enantioselective protonation of the transient α‐oxygenated (2‐azaaryl)methyl anion generated through the 1,2‐addition of the anion of dialkyl phosphite to the 2‐azaaryl ketone and the subsequent [1,2]‐phospha‐Brook rearrangement. A chiral bis(guanidino)iminophosphorane organosuperbase efficiently catalyzed the reaction to provide enantio‐enriched phosphates in high yields with good to high enantioselectivities. This is a rare example of the catalytic enantioselective protonation of transient carbanions other than enolates, constructing a trisubstituted stereogenic center α to 2‐azaarenes.
Organic and Inorganic Nitrogen forms as Affected by Phosphorus Additions in a Maize–Mustard Cropping System
Authors: Zhang Yang , Zhang Xiaojia , Zhou Chuan , Lei Ping , Sootahar Mahendar Kumar , Ni Jiupai
Published: May 2022

Phosphorus (P) availability affects the accumulation and enrichment of soil nitrogen (N) forms. However, the effect of P addition on the distribution and turnover of soil N forms in the mustard–maize rotation system is unclear. A field experiment is conducted to investigate the effect of P addition on the turnover of soil N forms in a mustard–maize rotation system. The results show that after maize harvesting, the levels of ammonium N in soil with P addition are smaller compared to those without P addition. The organic N forms in soil with P addition are greater compared without P addition after mustard harvest. Moreover, the hydrolysable ammonium N and unknown hydrolysable N in soil with P addition are smaller than those without P addition after maize harvest. Structured equation model results show the intensities of hydrolysable amino acid N, hydrolysable amino sugar N, and unknown hydrolysable N transformed into ammonium N in soil with P addition are greater than those without P addition, and the intensities of these organic N forms transformed into nitrate N are weaker. The results indicate that P addition affect the accumulation and enrichment of soil N by altering the turnover of soil N forms.
An ECG denoising method combining variational modal decomposition and wavelet soft threshold
Authors: Hu Xiaoxu , Yu Qingwen , Yu Hongpeng
Published: May 2022

Cardio‐cerebrovascular disease is one of the malignant diseases with the highest morbidity and mortality in the world. Medical research shows that the factors that induce heart blood cerebrovascular disease are diverse, and electrocardiogram (ECG) has important reference significance for the diagnosis and pathological research of cardiovascular and cerebrovascular diseases. This paper proposes a method of denoising ECG signals by combining variational mode decomposition with wavelet soft‐threshold. First perform variational modal decomposition on the ECG signal to obtain several modal components, and then the decomposed modals components are denoised by wavelet threshold, and finally the signal reconstruction of the denoised modal components is carried out through Matlab simulation experiment analysis. Compared with the soft‐threshold denoising method of ensemble empirical mode decomposition (EEMD), the soft‐threshold denoising method of complete ensemble empirical mode decomposition with adaptive noise (CEEMDAN), the variational modal decomposition wavelet threshold denoising algorithm combined with ECG signal denoising has better denoising effect. This method is used to denoise the ECG signal from the MIT‐BIH database of the Massachusetts Institute of Technology. Under the condition of ensuring the smoothness of the ECG signal image, the signal‐to‐noise ratio value is 27.1121 and the mean square error value is 0.0535, which has achieved good results.
Mitochondrial GCN5L1 regulates glutaminase acetylation and hepatocellular carcinoma
Authors: Zhang Taotao , Cui Yunlong , Wu Yanjin , Meng Jiahui , Han Linmeng , Zhang Jiaqi , Zhang Chunyu , Yang Chenxi , Chen Lu , Bai Xue , Zhang Kai , Wu Kaiyuan , Sack Michael N. , Wang Lingdi , Zhu Lu
Published: May 2022

Background

Glutaminolysis is a critical metabolic process that promotes cancer cell proliferation, including hepatocellular carcinoma (HCC). Delineating the molecular control of glutaminolysis could identify novel targets to ameliorate this oncogenic metabolic pathway. Here, we evaluated the role of general control of amino acid synthesis 5 like 1 (GCN5L1), a regulator of mitochondrial protein acetylation, in modulating the acetylation and activity of glutaminase to regulate HCC development.

Methods

Cell proliferation was determined by MTT, 2D and soft agar clone formation assays and orthotopic tumour assays in nude mice. GLS1/2 acetylation and activities were measured in cells and tumours to analyse the correlation with GCN5L1 expression and mTORC1 activation.

Results

Hepatic GCN5L1 ablation in mice markedly increased diethylnitrosamine (DEN)‐induced HCC, and conversely, the transduction of mitochondrial‐restricted GCN5L1 protected wild‐type mice against HCC progression in response to DEN and carbon tetrachloride (CCl4) exposure. GCN5L1–depleted HepG2 hepatocytes enhanced tumour growth in athymic nude mice. Mechanistically, GCN5L1 depletion promoted cell proliferation through mTORC1 activation. Interestingly, liver–enriched glutaminase 2 (GLS2) appears to play a greater role than ubiquitous and canonical tumour–enriched glutaminase 1 (GLS1) in promoting murine HCC. Concurrently, GCN5L1 promotes acetylation and inactivation of both isoforms and increases enzyme oligomerisation. In human HCC tumours compared to adjacent tissue, there were variable levels of mTORC1 activation, GCN5L1 levels and glutaminase activity. Interestingly, the levels of GCN5L1 inversely correlated with mTORC1 activity and glutaminase activity in these tumours.

Conclusions

Our study identified that glutaminase activity, rather than GLS1 or GLS2 expression, is the key factor in HCC development that activates mTORC1 and promotes HCC. In the Kaplan–Meier analysis of liver cancer, we found that HCC patients with high GCN5L1 expression survived longer than those with low GCN5L1 expression. Collectively, GCN5L1 functions as a tumour regulator by modulating glutaminase acetylation and activity in the development of HCC.
Optimizing the stochastic deployment of small base stations in an interleave division multiple access‐based heterogeneous cellular networks
Authors: Noma‐Osaghae Etinosa , Misra Sanjay , Koyuncu Murat
Published: May 2022

The use of small base stations (SBSs) to improve the throughput of cellular networks gave rise to the advent of heterogeneous cellular networks (HCNs). Still, the interleave division multiple access (IDMA) performance in sleep mode active HCNs has not been studied in the existing literature. This research examines the 24‐h throughput, spectral efficiency (SE), and energy efficiency (EE) of an IDMA‐based HCN and compares the result with orthogonal frequency division multiple access (OFDMA). An energy‐spectral‐efficiency (ESE) model of a two‐tier HCN was developed. A weighted sum modified particle swarm optimization (PSO) algorithm simultaneously maximized the SE and EE of the IDMA‐based HCN. The result obtained showed that the IDMA performs at least 68% better than the OFDMA on the throughput metric. The result also showed that the particle swarm optimization algorithm produced the Pareto optimal front at moderate traffic levels for all varied network parameters of SINR threshold, SBS density, and sleep mode technique. The IDMA‐based HCN can improve the throughput, SE, and EE via sleep mode techniques. Still, the combination of network parameters that simultaneously maximize the SE and EE is interference limited. In sleep mode, the performance of the HCN is better if the SBSs can adapt to spatial and temporal variations in network traffic.