bluuebunny/crossref_metadata_2025 huggingface dataset:
Giant Topological Hall Effect and Colossal Magnetoresistance in Heusler Ferromagnet near Room Temperature
Authors: Yanda Premakumar , Noohinejad Leila , Mao Ning , Peshcherenko Nikolai , Imasato Kazuki , Srivastava Abhay K. , Guan Yicheng , Giri Bimalesh , Sharma Avdhesh Kumar , Manna Kaustuv , Parkin Stuart S. P. , Zhang Yang , Shekhar Chandra , Felser Claudia
Published: November 2024

Colossal magnetoresistance (CMR) is an exotic phenomenon that allows for the efficient magnetic control of electrical resistivity and has attracted significant attention in condensed matter due to its potential for memory and spintronic applications. Heusler alloys are the subject of considerable interest in this context due to the electronic properties that result from the nontrivial band topology. Here, the observation of CMR near room temperature is reported in the shape memory Heusler alloy Ni2Mn1.4In0.6, which is attributed to the combined effects of magnetic field‐induced martensite twin variant reorientation (MFIR) and magnetic field‐induced structural phase transformation (MFIPT). This compound undergoes a structural phase transition from a cubic (austenite‐L21) ferromagnetic (FM) to a monoclinic (martensite) antiferromagnetic (AFM), which leads to an effective increase in the size of the Fermi surface and consequently in CMR. Additionally, it exhibits significant anomalous Hall conductivity in both antiferromagnetic and ferromagnetic phases. Furthermore, it demonstrates a giant topological Hall resistivity (THR) ≈6 µΩ.cm in the vicinity of martensite transition due to the enhanced spin chirality resulting from the formation of magnetic domains with Bloch‐type domain walls. The findings contribute to the understanding of the magnetotransport of Ni‐Mn‐In Heusler alloys, which are prospective candidates for room‐temperature spintronic applications.
Molecular Design of a Diketopyrrolopyrrole Conjugated Oligoelectrolyte Capable of Imaging Intracellular Vesicle Membrane Dynamics
Authors: Chan Samuel J. W. , Zhu Ji‐Yu , Yip Benjamin Rui Peng , Shyamasundar Sukanya , Bazan Guillermo C.
Published: November 2024

Conjugated oligoelectrolytes (COEs) are lipid bilayer spanning optical reporters that hold promise for delineating spatiotemporal changes in subcellular compartments. However, their ability to probe a broader range of biological processes remains restricted due to the lack of environmentally‐responsive chemical functionalities. Herein, the study reports a novel COE, namely COE‐KP, for monitoring spatiotemporal changes in the endolysosomal vesicles. COE‐KP features a central diketopyrrolopyrrole functional group in the optically active conjugated core that confers photophysical properties suitable for bioimaging, in particular responding to the presence of hydrogen bonding functionalities within the hydrophobic domain of the lipid bilayer. COE‐KP can thus discriminate cells in different growth states through two‐photon fluorescence lifetime imaging microscopy (FLIM) with excitation in the NIR‐II range. These changes in lifetime most reasonably reflect the degree of water permeability through the membrane and are not linked to notable differences in membrane tension or solvent polarity. Furthermore, using stimulated emission depletion (STED) nanoscopy, it is possible to directly visualize membrane‐bound COEs within cellular vesicles. These results illustrate further opportunities for applying COE‐based reporters for super‐resolution microscopy of organelle membranes, visualization of subcellular membrane morphologies, and imaging long‐term changes in membrane properties.
Isolation Transformer Based Very Low Frequency Antenna with Enhanced Radiation Characteristics
Authors: Wu Jingqi , Zeng Zilun , Wang Liwei , Xu Jianchun , Bi Ke
Published: November 2024

Very low frequency electromagnetic waves adeptly propagate in harsh cross‐medium environments, surmounting the rapid attenuation that impedes high‐frequency counterparts. Traditional low frequency antennas, however, encounter challenges concerning size, efficiency, and power. Here, an isolation transformer based very low frequency loop antenna with compact size and well impedance matching is proposed to enhance radiation characteristics for long‐distance communication. By utilizing the high magnetic permeability amorphous/nanocrystalline alloy Fe73.5Cu1Nb3B9Si13.5, the isolation transformer enables efficient and stable high‐current input. This design surpasses the current limitation of the conventional loop antennas, thereby improving its electromagnetic performance. Consequently, the radiation intensity of proposed antenna can be effectively increased over 30 times compared to traditional loop antennas. According to the experimental measurements, the transmission distance is over 340 m at 15 kHz using a single proposed antenna with a diameter of 2 m. Its robust performance, such as high radiation efficiency, low power consumption, and long‐distance transmission capacity, suggests significant potential for applications in underground communications and underwater information transmission.
Polymeric Multivalent Fc Binding Peptides‐Fabricated Clinical Compounding Bispecific Antibody Potentiates Dual Immunotherapy Targeting PD1 and CTLA‐4
Authors: Liu Zongyu , Chu Hongyu , Zhao Weidong , Yang Chenguang , Liu Tongjun , Shen Na , Tang Zhaohui
Published: November 2024

Dual Opdivo plus Yervoy immunotherapy, targeting the immune checkpoints PD1 and CTLA‐4, is successful in clinical use. However, it is associated with a high incidence of adverse events, and its therapeutic efficacy needs improving. In this study, polymeric multivalent Fc‐binding peptides (PLG‐Fc‐III‐4C) are employed to fabricate a bispecific antibody (PD1/CTLA‐4 BsAb) to potentiate dual immunotherapy targeting PD1 and CTLA‐4. The PD1/CTLA‐4 BsAb is prepared by mixing PLG‐Fc‐III‐4C with aPD1 and aCTLA‐4 in an aqueous solution for 3 h using the clinically optimal 3:1 proportion of aPD1 to aCTLA‐4. PD1/CTLA‐4 BsAb significantly inhibits tumors in MC38 colon cancer‐bearing mice more effectively than the combination of aPD1 and aCTLA‐4, with tumor suppression rates of 96.8% and 77.3%, respectively. It also induces a higher percentage of CD8+ T cells and increases the secretion of effector cytokines while reducing Treg levels in tumors compared to phosphate‐buffered saline, indicating significant tumor immunity regulation. Mechanistically, a 6.3‐fold increase in PD1/CTLA‐4 BsAb accumulation in tumors due to the tumor targeting ability of aPD1, and the PD1/CTLA‐4 BsAb significantly reduces the adverse colitis event in healthy mice, compared to aPD1 and aCTLA‐4. Thus, these findings provide a novel approach to enhance antitumor therapy using aPD1 and aCTLA‐4.
Cyclic Evolution of Synergized Spin and Orbital Angular Momenta
Authors: Liu Lei , Sun Xiao‐Chen , Tian Yuan , Zhang Xiujuan , Lu Ming‐Hui , Chen Yan‐Feng
Published: November 2024

Spin angular momentum (SAM) and orbital angular momentum (OAM) are fundamental physical characteristics described by polarization and spatial degrees of freedom, respectively. Polarization is a feature of vector fields while spatial phase gradient determines the OAM ubiquitous to any scalar field. Common wisdom treats these two degrees of freedom as independent principles to manipulate wave propagations. Here, their synergy is demonstrated. This is achieved by introducing two orthogonal p‐orbitals as eigenbases, whose spatial modal features are exploited to generate OAM, and the associated orbital orientations provide means to simultaneously manipulate polarizations. Through periodic modulation and directional coupling, a full cyclic evolution of synchronized and synergized SAM‐OAM is realized. Remarkably, this evolution acquires a nontrivial geometric phase, leading to its representation on a Möbius strip. Experimentally, an acoustic cavity array is designed, whose dipole resonances precisely mimic the p‐orbitals, with pressure fields featuring the spatial characteristics and velocity fields the vectorial orientations. Based on this synergy, a spin‐orbital‐Hall effect is further showcased, highlighting the intricate locking of handedness, directionality, spin density, and spatial mode profile. This study unveils a fundamental connection between SAM and OAM, promising avenues for their novel applications in trapping, coding, and communications.
Photothermal Synergistic Hydrogen Production via a Fly‐Ash‐made Interfacial Vaporific System
Authors: Xie Yin , Xu Chenyu , Liu Yan , Zhang Entao , Chen Ziying , Zhan Xiaopeng , Deng Guangyu , Gao Yuan , Zhang Yanwei
Published: November 2024

Employing UV–vis spectrum for hydrogen generation and vis‐IR spectrum to elevate reaction temperatures and induce phase transitions effectively enhances yield and purifies water, demonstrating a judicious strategy for solar energy utilization. This study presents an interfacial photothermal water splitting system that utilizes all‐inorganic, economical industrial by‐products known as fly ash cenospheres (FAC) for solar‐driven hydrogen generation. In this system, the yield reaches 254.8 µmol h−1 cm−1, representing an 89% augmentation compared to that of the three‐phase system. In situ experiments, combined with theoretical calculation, reveal the system's robust light absorption capacity, facilitating rapid gas separation, thus improves the solar‐to‐hydrogen (STH) efficiency. Furthermore, the system demonstrates strong performance in turbid water and scalability for expansive applications, achieving a hydrogen yield exceeding 50 L h−1 m−2 from various water sources. Facilitating large‐scale hydrogen production and water purification, it thereby establishing its potential as a viable solution for sustainable energy generation.
Corneal Mucin‐Targeting Liposome Nanoplatforms Enable Effective Treatment of Dry Eye Diseases by Integrated Regulation of Ferroptosis and Inflammation
Authors: Zhang Yin , Zhou Tinglian , Wang Kai , Luo Chenqi , Chen Dan , Lv Zeen , Han Haijie , Yao Ke
Published: November 2024

The incidence of dry eye disease (DED) has been increasing annually worldwide, creating an urgent need for new therapies. Due to the multifactorial mechanism underlying DED, traditional medications focused on decreasing ocular surface inflammation have been unable to address all the harmful factors and fail to achieve a complete clinical cure. Ferroptosis, a new form of programmed cell death characterized by lipid peroxidation, has become a pivotal contributor to dry eye oxidative stress‐driven pathology. Therefore, therapeutic targeting of ferroptosis may be an attractive option for dry eye management. Herein, a sialic acid‐targeting peptide‐modified liposome loaded with Cyclosporine A (CsA), a typical anti‐inflammatory drug, and Ferrostatin‐1 (Fer‐1), a selective ferroptosis inhibitor, is developed termed as CF@SNPs, for combing and sustaining DED treatment. This multifunctional liposomal encapsulation demonstrates excellent aqueous solubility; moreover, the sialic acid‐targeting peptide prolongs ocular surface retention, further enhancing therapeutic efficacy. The CF@SNPs treatment comprehensively alleviates DED symptoms, including improving corneal defects, augmenting goblet cell count, and restoring tear secretion. Specifically, CF@SNPs attenuate dry eye pathology by suppressing p53‐SLC7A11‐GSH‐dependent ferroptosis and TNF‐α‐associated inflammatory cascades, accompanied by favorable biocompatibility in vivo. These results underscore the promising potential of this superior nano‐formulation for DED pharmacotherapy.
Soil depth distribution of particulate organic carbon and nitrogen in the southeastern United States
Authors: Franzluebbers Alan J.
Published: November 2024

Particulate organic matter may be an important component feeding soil microbial activity. This study described population‐level statistics of particulate organic carbon (C) and nitrogen (N) in predominately Ultisols across 181 farms throughout North Carolina, Virginia, and Georgia. Soil profiles were sampled under conventional‐till cropland (n = 186), no‐till cropland (n = 127), grassland (n = 322), and woodland (n = 171). Particulate organic C (g C kg−1 soil) varied from 2.0 to 18.0 (5% to 95% distribution) at 0‐ to 10‐cm depth, 0.4 to 3.9 at 10‐ to 30‐cm depth, and 0.1 to 1.9 at 30‐ to 60‐cm depth. As a proportion of total N, particulate organic N was 0.26 ± 0.10, 0.12 ± 0.09, and 0.08 ± 0.08 kg kg−1 at 0‐ to 10‐, 10‐ to 30‐, and 30‐ to 60‐cm depths, respectively. Particulate organic C was most dramatically affected at 0‐ to 10‐cm depth, following the order: conventional‐till cropland < no‐till cropland < grassland < woodland. Particulate organic N followed a similar order, except there was no difference between grassland and woodland. Particulate organic matter brings vitality to soil along a trajectory toward greater organic matter.
Economic potential of industrial hemp in Oregon: An ex ante minimum‐data assessment
Authors: Antle John M. , Cho Seojin
Published: November 2024

This paper provides an ex ante evaluation of the economic potential of the emergent industrial hemp industry in Oregon, a state with conditions favorable to hemp cultivation. The analysis exploits available data to simulate the performance of hemp for fiber and oil in existing cropping systems. The study finds that profitability and adoption of hemp into existing crop production systems in Oregon could range widely, depending on key factors including hemp prices, costs of production, investments in production technology and supply chains, and policies affecting hemp production and utilization.
dP/dtmax: An underestimated prognostic factor in large animal infarction model
Authors: Garamvölgyi Rita , Kőrösi Dénes , Tátrai Ottó , Bodor Emőke , Fajtai Dániel , Farkas Kornélia , Vorobcsuk András
Published: November 2024

The present study aims to establish a reproducible large animal experimental unit using a minipig model to monitor cardiac function changes. A 90‐min closed‐chest balloon occlusion of the left anterior descending branch of the coronary artery was used to induce myocardial infarction in Pannon minipigs. To monitor the cardiac function, measurements were made by cardiac magnetic resonance imaging (cMRI), invasive pressure monitoring, and a Pulse index Continuous Cardiac Output (PiCCO) hemodynamic system at 0, 72, and 720 h during the follow‐up period. End‐diastolic and end‐systolic volumes (EDV, ESV), left ventricular ejection fraction (LVEF) obtained by cMRI evaluation, global ejection fraction and aortic dP/dtmax obtained by the invasive method, were recorded and compared. The 72‐ and 720‐h EDV data showed a significant increase (p = 0.012, <0.001) compared to baseline, and the Day 30 data showed a significant increase compared to Day 3 (p = 0.022). The ESV 72 h after the infarction showed a significant increase (p = 0.001) compared to baseline, which did not change significantly by Day 30 (p = 0.781) compared to Day 3. EDV and ESV were significantly negatively correlated with aortic dpmax, and ESV was significantly correlated with LVEF. For LVEF and dPmax, a significant (p < 0.001 and p = 0.002) worsening was demonstrated at Day 3 compared to baseline, which was no longer statistically detectable for LVEF at Day 30 (p = 0.141), while the difference for dPmax was maintained (p = 0.002). The complementary use of PiCCO hemodynamic measurements in large animal models makes the previously used methodologies more robust and reliable.
The effect of ICU diary on psychiatric symptoms after ICU discharge among adult critically ill patients: A prospective comparative study
Authors: Shibata Mami , Miyamoto Kyohei , Shima Nozomu , Nakashima Tsuyoshi , Fukushima Junichi , Yamada Shinichi , Kimoto Sohei , Inoue Shigeaki
Published: November 2024

Aim

Psychiatric problems are common in critically ill patients after discharge from an intensive care unit (ICU). The effect of intensive care unit (ICU) diaries on psychiatric symptoms after ICU discharge was investigated in this prospective study.

Methods

Enrolled were critically ill adult patients who were emergently admitted to an ICU and expected to stay for at least 2 days. These patients received ICU diaries filled out by healthcare professionals and family members. Comparison was made with a historical cohort from a previous trial conducted in the same ICU but without ICU diaries. The primary outcome was the presence of significant post‐traumatic stress disorder (PTSD) symptoms 3 months after ICU discharge. Secondary outcomes included significant symptoms of anxiety and depression.

Results

Among 61 patients with ICU diaries, questionnaires were sent to 44 patients 3 months after ICU discharge; 29 patients responded and were analyzed (ICU diary group). Seventy‐four patients from a historical cohort were used as a control group. The proportion of patients with significant PTSD symptoms was 19% in the ICU diary group and 16% in the control group (adjusted odds ratio [aOR] [95% confidence interval: 95% CI]: 0.98 [0.26–3.70]). For anxiety and depression, the proportions were 25% and 29% in the ICU diary group, and 38% and 45% in the control group (aOR [95% CI]: 0.46 [0.15–1.38] for anxiety, aOR [95% CI] 0.40 [0.14–1.16] for depression).

Conclusion

ICU diaries were not associated with a reduced incidence of PTSD symptoms 3 months after ICU discharge.
Unveiling the Clinical and Imaging Signatures of Intravascular Lymphoma of the Central Nervous System: A Multicentric Cohort Study
Authors: Berthet Elodie , Guillonnet Antoine , Houillier Caroline , Ursu Renata , Soussain Carole , Touat Mehdi , Gueguen Antoine , de Renzis Benoît , Bigaut Kevin , Ahle Guido , Durozard Pierre , Grosset‐Janin Deborah , Oberic Lucie , Bonnet Antoine , Grandjean Anne‐Pascale , Moluçon‐Chabrot Cécile , Hoang‐Xuan Khê , Chabriat Hugues , Guey Stéphanie
Published: November 2024

Objective

Intravascular lymphoma is a rare subtype of B‐cell lymphoma characterized by a clonal proliferation restricted to the lumen of small vessels. Over 50% of patients exhibit central nervous system (CNS) involvement, but diagnosis is often delayed due to the lack of distinctive features. We aimed to identify key phenotypic features for early diagnosis of intravascular lymphoma with CNS involvement through an in‐depth cohort study.

Methods

We built up a multicenter retrospective cohort of 17 patients recruited in collaboration with the French Expert Network for Oculo‐Cerebral Lymphomas (LOC network), and retrospectively analyzed data from medical records.

Results

In this cohort, 15 of 17 (88%) patients developed focal neurological episodes, often fluctuating and/or recurrent, with a sudden onset in 68% of episodes, suggesting a vascular origin. Rapid cognitive deterioration occurred in 15 of 17 (88%) patients, psychiatric manifestations in 8 of 17 (47%), and “B signs” in 14 of 17 (82%). Brain MRI showed polymorphic FLAIR hyperintensities in 14 of 16 (87%) patients, and DWI‐positive lesions in 13 of 16 (81%) of patients, which accumulated over time and had unusual characteristics for ischemic lesions (progressive growth, persistent DWI‐hyperintensity over 1 month, surrounded by a wider FLAIR hyperintensity). Early‐onset inflammatory syndrome, and elevated lactate dehydrogenase (LDH) levels were observed in over 90% of cases. Mild and inconsistent meningitis contrasted with a nearly‐constant hyperproteinorachia. An increased interleukin 10/6 ratio over 0,7 was found in 4 of 7 (57%) patients, and skin biopsy led to a pathological diagnosis in 3 of 6 (50%) patients.

Interpretation

The results of this study highlight “red flags” that could help accelerate the diagnosis of intravascular lymphoma involving the CNS. ANN NEUROL 2025;97:435–448
Intratumoral Transforming Boron Nanosensitizers for Amplified Boron Neutron Capture Therapy
Authors: Li Liping , Wang Mixue , Zhao Qian , Bai Peirong , Hao Haotian , Zhang Zizhu , Liu Tong , Yang Yongzhen , Pu Kanyi , Zhang Ruiping
Published: November 2024

Boron neutron capture therapy (BNCT) is an advanced binary tumor‐cell‐selected heavy‐particle radiotherapy used for treating invasive malignant tumors. However, its clinical applications have been impeded by the rapid metabolism and insufficient tumor‐specific accumulation of boron agents. To tackle this issue, we develop a smart boron nanosensitizer (BATBN) capable of transforming its size in response to cancer biomarker for optimal balance between penetration and retention of boron‐10 for BNCT. BATBN comprises an ultrasmall boron quantum dots (BQD) core (4 nm) conjugated with cell‐penetrating peptides, which facilitates its cellular uptake and deep tumor penetration. In the tumor microenvironment, the tumor biomarker can specifically initiate a self‐condensation reaction of BATBN, leading to the formation of larger‐sized nanoaggregates. Due to such a specific intratumoral transformation, BATBN demonstrates a 2.4‐fold increase in intratumoral boron concentration and a 5.0‐fold increase in tumor retention time compared to the BQDs. Thus, the tumor volume of the BATBNs‐treatment group is 2.7‐fold smaller than that of BQDs in preclinical tumor models after 21 days of neutron irradiation treatment. This study presents a supramolecular strategy to endow BNCT agents with the biomarker‐activated size interconversion, permitting precise and efficient BNCT for cancer treatment.
Upconversion Luminescence with Bis‐pyclen Yb(III) Chelates: Crown vs. Linear Polyether Linkers in Discrete Heteropolynuclear Architectures
Authors: Hamon Nadège , Godec Léna , Sanchez Samuel , Beyler Maryline , Charbonnière Loïc J. , Tripier Raphaël
Published: November 2024

Ligands combining two lateral bis‐pyridyl‐phosphonated‐pyclens were synthesized, using a flexible linear pegylated linker (L2) or a bulkier K22 crown‐ether (L3). A functionalized pyridyl‐phosphonated‐pyclen (L1) was also prepared as a mononuclear analogue. Coordination behavior of lanthanide cations was studied via NMR titration with Lu for L1, and UV/Vis and luminescence spectroscopy with Yb for L2/L3. Strong coordination of two Yb atoms enabled isolation and spectroscopic characterization of dinuclear complexes in H2O and D2O. Excited state lifetime analysis at 980 nm revealed strong protection of Yb cations, with no coordinated water molecule. Upon titration of the isolated dinuclear Yb complexes with Tb cations, cooperative upconversion (UC) sensitization of Tb in the visible was observed upon excitation of Yb at 980 nm in D2O. In the absence of Tb, the Yb complexes also exhibited cooperative luminescence with a weak emission band around 500 nm upon NIR Yb excitation. Efficient UC with Tb was only observed after thermal treatment, suggesting a slow kinetic of formation of the UC species. [Yb2TbL3] showed weak Tb centered UC emission, while the dinuclear complex of L2 displayed more intense UC emission up to two equivalents of Tb, forming [(Yb2L2)Tbx] (x=1–2), with the tetranuclear heterometallic complex being the most intense emitter. Log‐Log plot analysis confirmed the two‐photon nature of the UC process.
Controlling the Mechanism of Nucleation and Growth Enables Synthesis of UiO‐66 Metal–Organic Framework with Desired Macroscopic Properties
Authors: Artsiusheuski Mikalai A. , Casati Nicola P. M. , Clark Adam H. , Nachtegaal Maarten , Verel René , van Bokhoven Jeroen A. , Sushkevich Vitaly L.
Published: November 2024

By combining in situ X‐ray diffraction, Zr K‐edge X‐ray absorption spectroscopy and 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, we show that the properties of the final MOF are influenced by H2O and HCl via affecting the nucleation and crystal growth at the molecular level. The nucleation implies hydrolysis of monomeric zirconium chloride complexes into zirconium‐oxo species, and this process is promoted by H2O and inhibited by HCl, allowing to control crystal size by adjusting H2O/Zr and HCl/Zr ratios. The rate‐determining step of crystal growth is represented by the condensation of monomeric and oligomeric zirconium‐oxo species into clusters, or nodes, with the structure identical to that in secondary building units (SBU) of UiO‐66 framework. The rapid crystallization in the absence of HCl leads to formation of defective secondary building units with missing zirconium atoms, providing a pathway to control the number of defects in UiO‐66 crystals. Remarkably, we have shown that assembling of the metal nodes and linkers into the UiO‐66 structure is not the rate‐limiting step, and the degree of deprotonation of the linker has no direct effect on the crystallization kinetics or crystal size of product.
Bead‐Based DNA Synthesis and Sequencing for Integrated Data Storage Using Digital Microfluidics
Authors: Piao Yuhao , Fang Yitong , Li Bin , Man Tiantian , Chen Jie , Zhu Fulin , Wang Weiqiang , Wan Ying , Deng Shengyuan
Published: November 2024

DNA is considered as a prospective candidate for the next‐generation data storage medium, due to its high coding density, long cold‐storage lifespan, and low energy consumption. Despite these advantages, challenges remain in achieving high‐fidelity, fully integrated, and cost‐efficient DNA storage system. In this study, a homemade digital microfluidic (DMF)‐based compact DNA data storing pipeline is orchestrated to complete the entire process from the synthesis to the sequencing. The synthetic half employs phosphoramidite chemistry on 200 nm magnetic beads (MBs), where the dimethyltrityl protecting group is removed by droplet manipulation of trichloroacetic acid. The sequencing counterpart relies on pyrophosphate releasing originated from polymerase‐catalyzed primer extension, which leads to photon‐countable chemiluminescence (CL) signal in 2.5‐μL drops of trienzyme cascading reactions. Further by DNA denaturation, repeated pyrosequencing plus plurality voting can improve the nucleobase accuracy beyond 95 %. As a proof‐of‐concept trial, semantic information is saved in DNA via the Huffman coding algorithm plus the Reed‐Solomon error‐correction, and then robustly retrieved from this streamlined platform. As a result, it took a net total of approximately 6.5 h to writing and reading 8 bytes of data, that equal to a storaging speed of 49 min/byte, much quicker than the previously reported 2.8–4.2 h/byte. This bead‐based miniaturized device promises an unattended protocol for achieving high‐throughput, full‐packaged, and above all, neatly precision DNA storage.
Unveiling Surface Reconstruction as the Primary Trigger for Capacity Loss in Ultra‐High Nickel Cathodes
Authors: Qiu Lang , Zhang Mengke , Hua Weibo , Wang Yi , Deng Yuting , Li Zhuangzhi , Song Yang , Wu Zhenguo , Xiao Yao , Guo Xiaodong
Published: November 2024

Mechanical failures, such as cracks and nanopores, along with the associated surface reconstruction, have long been regarded as the primary causes of capacity decay in ultra‐high Ni layered oxides. However, the impact of these failures on performance degradation has not yet been effectively elucidate and distinguished. Herein, we develop ultra‐high Ni cathodes with tailored morphological structures by incorporating B and Mo to optimize lithiation kinetics, which can suppress lattice strain, particle cracking, and surface reconstruction during charging/discharging. And the role of chemo‐mechanical failures in capacity loss is systematically investigated. Surprisingly, contrary to the traditional view, structural and electrochemical characterizations of the cycled cathodes demonstrate that intragranular cracks, intergranular cracks, and nanopores are not the primary contributing factors of capacity loss. Instead, surface reconstruction triggers rapid capacity decay. Notably, compared to nanopores, intragranular cracks expose a significantly larger quantity of active substances, thereby promoting interfacial side reactions and accelerating surface structural reconstruction during cycling.
Polymeric Carbon Nitride Edged with Spatially Isolated Donor and Acceptor for Sunlight‐Driven H2O2 Synthesis and In‐Situ Utilization
Authors: Zhang Qiang , Gu Kaiye , Dong Chaoran , Xue Chao , Che Huinan , Zhang Kan , Ao Yanhui
Published: November 2024

On‐site H2O2 activation attracts much attention in energy conversion and environment remediation et al., yet remains challenging in its highly efficient and sustainable synthesis. Herein, we grafted a pair of spatially isolated donor (methoxyphenyl unit) and acceptor (anthraquinone unit) in polymeric carbon nitride edges, which induce directional electron‐hole transfer to the two spatially separated dual active centers. Specifically, photogenerated electrons in the anthraquinone unit facilitate the 2e− ORR, while the methoxyphenyl unit, which gathers photogenerated holes, enables rapid 4e− WOR. More impressively, the anthraquinone unit also exhibits strong proton extraction capabilities to boost the generation of *OOH intermediates and H2O2. Consequently, the synthesized donor‐polymeric carbon nitride‐acceptor (DPA) catalyst shows a remarkable H2O2 yield of 6497.1 μM h−1 g−1 in pure water, surpassing traditional DP and PA catalysts. Because of its high efficiency, the H2O2 product can efficiently degrade and mineralize various organic contaminants in a continuous‐flow self‐Fenton reactor under sunlight irradiation. Our work presents an unprecedented approach to designing photocatalysts with efficient H2O2 synthesis and practical application from a molecular engineering perspective.
Anomere Amide Ermöglichen Aminative Alken‐Aryl‐ und Alken‐Alken‐Kupplungen
Authors: Stein Colin , Tyler Jasper L. , Wiener Julius , Boser Florian , Daniliuc Constantin G. , Glorius Frank
Published: November 2024

Trotz der Bedeutung von Kreuzkupplungsreaktionen, bei denen C−N‐Bindungen gebildet werden, stellen aminative Kupplungsansätze, bei denen zwei Fragmente direkt am Heteroatom verknüpft werden, eine selten genutzte retrosynthetische Strategie für den molekularen Aufbau dar. In diesem Artikel berichten wir über das Design, die Synthese und die Implementierung eines anomeren Amid‐Reagenzes, welches in der Lage ist, aminative Alken‐Aryl‐ und Alken‐Alken‐Kupplungsreaktionen in hoher Regioselektivität zu ermöglichen. Diese Transformation entspricht einer Abfolge von katalysatorfreier 1,2‐Chloraminierung, N‐Entschützung und formalem Nitrentransfer in einem einzigen Reaktionsgefäß. Die Einfachheit sowohl des Protokolls als auch der benötigten Bausteine machte die Nutzung von Hochdurchsatzscreening (engl. HTE) attraktiv, um schnell und effizient einen großen Bereich des chemischen Raums zu erkunden und die Grenzen der Reaktivität aufzuzeigen. Zusätzlich wurde die Substratbreite auf größerem Maßstab erkundet. Darüber hinaus zeigen alternative Reaktivitätsmodi der funktionalisierten Zwischenprodukte, welche durch dieses Protokoll geliefert werden, die divergente Natur dieser aminativen Kupplungsstrategie auf.
Divergent Activity Shifts of Tin‐Based Catalysts for Electrochemical CO2 Reduction: pH‐Dependent Behavior of Single‐Atom Versus Polyatomic Structures
Authors: Wang Yuhang , Zhang Di , Sun Bin , Jia Xue , Zhang Linda , Cheng Hefeng , Fan Jun , Li Hao
Published: November 2024

Tin (Sn)‐based catalysts have been widely studied for electrochemical CO2 reduction reaction (CO2RR) to produce formic acid, but the intricate influence of the structural sensitivity in single‐atom Sn (e.g., Sn−N−C) and polyatomic Sn (e.g., SnOx and SnSx; x=1,2) on their pH‐dependent performance remains enigmatic. Herein, we integrate large‐scale data mining (with >2,300 CO2RR catalysts from available experimental literature during the past decade), ab initio computations, machine learning force field accelerated molecular dynamic simulations, and pH‐field coupled modelling to unravel their pH dependence. We reveal a fascinating contrast: the electric field response of the binding strength of *OCHO on Sn−N4−C and polyatomic Sn exhibits opposite behaviors due to their differing dipole moment changes upon *OCHO formation. Such response leads to an intriguing opposite pH‐dependent volcano evolution for Sn−N4−C and polyatomic Sn. Subsequent experimental validations of turnover frequency and current density under both neutral and alkaline conditions well aligned with our theoretical predictions. Most importantly, our analysis suggests the necessity of distinct optimization strategies for *OCHO binding energy on different types of Sn‐based catalysts.
Targeted Synthesis of Interpenetration‐Free Mesoporous Aromatic Frameworks by Manipulating Catalysts as Templates
Authors: Wang Zihao , Jiang Li , Jia Jiangtao , Zhu Guangshan
Published: November 2024

Reticular chemistry allows the design and synthesis of mesoporous networks by extending the size of the building blocks. However, interpenetration of the nets easily happens against the designed mesoporous networks, thereby falling short of achieving the intended specific surface area and pore size. Controlling the framework interpenetration has always been a challenge in the synthesis section of reticular chemistry. In this work, based on our previously reported type of highly porous aromatic frameworks (named PAF‐1), we extended the tetrahedral building blocks to target an iso‐reticular mesoporous PAF‐333. A series of Ni(0) ligands with different sizes were employed to confirm that suitable‐sized catalyst ligands could successfully inhibit skeleton interpenetration in the coupling reaction through the steric hindrance effect. The obtained mesoporous PAF‐333 possessed a pore size of approximately 3.2 nm matching well with the value from the predicted non‐interpenetrated structure. PAF‐333 showed great high‐pressure hydrogen and methane storage potential with a 13.4 wt % H2 uptake at 77 K, 100 bar and a 0.537 g g−1 CH4 uptake at 298 K, 98 bar, ranking at the top of the reported porous adsorbents in the gas storage applications.
Mineralizing Biofilm towards Sustainable Conversion of Plastic Wastes to Hydrogen
Authors: Li Baoyuan , Xu Zhijun , Wang Ruifang , Nie Rui , Tao Zhengyu , Huang Xin
Published: November 2024

The integration of inorganic materials with biological machinery to convert plastics into fuels offers a promising strategy to alleviate environmental pollution and energy crisis. Herein, we develop a type of hybrid living material via biomineralization of CdS onto Shewanella oneidensis‐based biofilm, which is capable of sustainable hydrogen production from poly(lactic acid) (PLA) wastes under daylight. We reveal that the formed biofilm microstructure provides an independent anaerobic microenvironment that simultaneously supports cellular viability, maintains hydrogenase activity, and preserves the functional stability of CdS, giving rise to the efficient plastic‐to‐hydrogen conversion efficiency as high as 3751 μmol H2 g‐1 PLA. Besides, by genetically engineering transmembrane pili conduit and incorporating conductive nanomaterials to strengthen the electron transfer across cellular interface and biofilm matrices, we show that the conversion efficiency is further enhanced to 5862 μmol H2 g‐1 PLA. Significantly, we exhibit that a long‐term sustainable plastic‐to‐hydrogen conversion of 63 d could be achieved by periodically replenishing PLA wastes. Overall, by the synergistic integration of biotic‐abiotic characteristics the developed biofilm‐based biomineralized hybrid living material is anticipated to provide a new platform toward the efficient conversion of plastic wastes into valuable fuels, and bridge the gap between environmental contamination and green energy production.
Narrative exposure therapy in a child protection context: Breaking intergenerational cycles by providing a pathway through past trauma
Authors: Carpenter Samuel , Sarkar Agnik
Published: November 2024

Trauma is a central theme in child protection. Responding to and preventing traumatic harm to children is a key function of statutory child protection agencies and systems in Australia. Parents who encounter these systems are also known to be a highly traumatised cohort, often experiencing trauma throughout their own early development and into their adult lives. Despite these being broadly accepted principles amongst practitioners, there are limited pathways for parents to undertake trauma‐processing therapy as an integrated part of current child protection practice. Narrative exposure therapy (NET) is a manualised therapy model that has been used successfully to support individuals with life‐threatening trauma to process these experiences and take agency over their lives. The successful use of this model by non‐traditional therapists such as community health workers, in brief timeframes, has made it a valuable approach in settings with a high need for therapeutic support and low resources, such as refugee accommodation. Although these themes also have synergy with the child protection setting, there is relatively little research on the use of NET in this setting. This paper is written by practitioners and for practitioners and examines the real‐world application of NET with parents involved with a non‐statutory reunification service in the South Australian child protection system, grounded in a trauma‐informed model of practice. As such, the paper considers extending the possible value of NET into an area of limited previous use. The paper highlights observational findings suggesting that NET has the potential to be an effective tool for bringing focus to the trauma experiences of the parent, so that they may process these and develop greater capacity to parent safely as well as engage more productively with the demands of the child protection system.
Exploration of the Differences in Coordination Behaviors and Spectrographic Properties of Two Novel Seven‐Nucleated Ni (II) Complexes of a Salamo‐Type Flexible‐Bisoxime Ligand
Authors: Zhang Yang , Chen Rui , Shi Hao‐Nan , Yan Yi‐Bin , Dong Wen‐Kui
Published: November 2024

A salamo‐type bis‐oxime ligand H2L was synthesized, which reacted with Ni (NO3)2·6H2O in different reaction solvents to synthesize two novel heptanuclear Ni (II) complexes: [Ni7(L)3(μ3‐OH)8(EtOH)6]·2CH2Cl2 (1) and [Ni7(L)3(μ3‐OMe)2(μ3‐OH)6(MeOH)6]·CH2Cl2 (2). X‐ray crystal diffraction results showed that each Ni (II) ion exhibits a distorted octahedral geometry. Its uniqueness lies in the fact that the Ni (II) ion in Complex 1 not only coordinates with ligand units but also coordinates with ethanol solvent molecules and water molecules participating in bridging. Complex 2 is composed of water molecules and methanol molecules connected together. Interestingly, the coordination mode is different due to the different reaction solvents. The energy gap changes of the ligand, and its complexes were then explored by DFT calculations. In addition, the influence of the weak interaction force was confirmed through the in‐depth study of electrostatic potential, IRI, freedom analysis, and Hirshfeld surfaces analyses, which is important for explaining the formation of reaction sites and supramolecular structures. UV‐visible spectrometric titration tests showed that the binding ratios of the ligand to Ni (II) ions are all 3:7, which is consistent with the crystal structure. Finally, fluorescence characterization studies showed that both complexes exhibited reduced fluorescence compared to H2L.
Quantitative Determination of Metal Center Coordination Numbers in Resin‐Based Supported Catalysts via CO2 Adsorption
Authors: Meng Qi , Fan Yun , Wang Bozhi , Ni Shuaibo , Chen Shengbin , Jin Hao , Teng Qiaoqiao
Published: November 2024

A novel method was described for quantitatively determining the metal centers' average coordination numbers in as‐prepared supported metal catalysts using polyamine‐modified resin carriers via CO2 adsorption. Using porous resin (PS) and pentaethylenehexamine (PEHA) as starting materials, a new polyamine‐modified resin carrier PS‐PEHA was obtained to anchor various metals (Cu, Pd, Co, Ni, and Zn), thereby preparing a range of supported catalysts. The structures of the metal catalysts were characterized through FT‐IR, XPS, SEM, EDS, BET, and ICP‐OES. DVS was employed to study the carrier and catalyst performance of CO2 adsorption. The average coordination numbers of the metal centers were quantitatively determined based on their differences in CO2 adsorption capacities. The coordination numbers determined were Co (3.5), Ni (3.5), Pd (4.8), Zn (3.6), and Cu (5.9).
Synthesis, Characterization, and Investigation of Advanced Biological Properties of Non‐Ionic Group Substituted Water‐Soluble BODIPYs
Authors: Sekban Lamia Sevire , Kaplan Ekrem , Özdemir Sadin , Tollu Gülşah , Hamuryudan Esin , Özçeşmeci Mukaddes
Published: November 2024

In this study, glycerol, glycosyl, and tetraethyleneglycol monomethyl ether group substituted BODIPY compounds were successfully synthesized and characterized. The antioxidant, antidiabetic, antibiofilm, microbial cell viability, antimicrobial, antimicrobial photodynamic therapy, and DNA cleavage abilities of the BODIPY derivates were also tested. The highest antioxidant activity at 100 mg/L was 87.12% for BODIPY‐1, 85.61% for BODIPY‐2, and 92.78% for BODIPY‐3. The most effective inhibition of microbial cell viability was obtained for these BODIPY molecules at 100% at 50 and 100 mg/L. It was also observed that these BODIPY molecules exhibited excellent biofilm inhibition activities. The derivates were found to exhibit higher antibiofilm abilities against Staphylococcus aureus compared to Pseudomonas aeruginosa. When the antidiabetic effects of water‐soluble BODIPY compounds were examined, the highest effect was found to be 64.40% for BODIPY‐1 at 200 mg/L.
AIE Active Polymeric Fluorescent Nanoaggregates from Glycogen for Sensitive Detection of Tetracycline
Authors: Panigrahi Abhiram , Vishwakarma Ravindra , Sarma Tridib K.
Published: November 2024

Detection and monitoring of environmental contaminants such as antibiotic residues in aquatic environments is challenging. To address this, a variety of detection methods has been developed; out of which optical sensing using fluorescence is found as one of the most robust methods. However, most of the reported sensors are made from metal ions using tedious synthetic processes, on the other hand, optical sensors using biosourced polymers are rarely reported. Herein, an anionic glycogen functionalized aggregation induced emission (AIE) active system; NCMCTPN was prepared using a simple Schiff base condensation reaction of tetraphenylethene amine (TPENH2) and carboxymethyl cellulose dialdehyde (NCMCA) and its self‐assembled polymeric nanoaggregates were explored for sensitive and selective turn‐off fluorescence detection of a broad‐spectrum tetracycline antibiotic, in an aqueous medium with a limit of detection of 127.5 ppb. The combination of factors such as inner filter effect and photoinduced electron transfer from the polymeric nanoaggregates to tetracycline through activation of a non‐radiative decay process is possibly responsible for the high sensitivity of the fluorescent nanoprobe towards the antibiotic.
Syntheses of Variants of π(σ) Aromatic Modified N‐Methyl N‐Confused Porphyrinoids with Adaptive Properties
Authors: Panua Anirban , Velmurugan Gunasekaran , Comba Peter , Rath Harapriya
Published: November 2024

Retrosynthetically designed and syntheses of three unprecedented core modified N‐confused porphyrinoids exhibiting vis‐NIR absorption with tunable aromaticity is reported. Controlled modification of types of oxidants (chloranil vs. DDQ) has led to the isolation of 18π‐aromatic porphyrinoid 7 (upon chloranil oxidation) while DDQ oxidation has led to 18 e σ‐aromatic porphyrinoids 8 and 9. All the three SN3 hybrid N‐confused porphyrinoids 7–9 have been thoroughly characterized via solution state spectroscopic measurements and in‐depth DFT studies for concluding π‐aromaticity of 7 and σ‐aromaticity of 8 and 9. While 7 could recognize the fluoride anion with high selectivity via deprotonation rather than an anion recognition based mechanism, acetate anion binding studies clearly revealed NH⋅⋅⋅AcO− H‐bonding interaction in the host‐guest complex [7‐AcO−] supporting an anion recognition based mechanism. Porphyrinoids 8 and 9 remain unsusceptible to anion recognition. The conformational preorganization and anion induced deprotonation leading to conformational reorganization have been extensively studied by solution state spectroscopic techniques and in depth DFT level theoretical calculations.
Promoting CO2 Electroreduction Over ion‐exchange Resin‐derived Ni−N−C Catalyst with Sulfur Doping
Authors: Wang Yicheng , Zhang Qiyu , Wang Chenxu , Ayeza  , Zhang Yating , Hu Chao
Published: November 2024

The utilization of renewable energy for electrocatalytic carbon dioxide reduction reaction (CO2RR) represents a pivotal technology in sustainable carbon conversion. Single‐atom catalysts (SACs) featuring transition metal‐nitrogen‐carbon (M−N−C) structures have demonstrated exceptional electrocatalytic efficacy in CO2RR by maximizing atom efficiency. Nevertheless, further investigation is warranted to optimize the catalytic performance of SACs through the selection of suitable carbon sources and supports, as well as the modulation of the microenvironment surrounding individual metal atoms. In this study, a sulfur‐doped Ni−N−C catalyst was prepared using a two‐step strategy involving metal ion adsorption and thermal decomposition, with porous ion exchange resin serving as the carbon source. Due to the uniform distribution of single atom active centers on the resin‐based carbon support and sulfur doping, this catalyst efficiently converts CO2 into CO with a Faradaic efficiency exceeding 90 % within the range of −0.69~−1.29 V (vs. RHE), reaching a maximum value of 97.7 % (−0.79 V vs. RHE). Theoretical calculations indicate that second‐shell sulfur doping effectively promotes coupled transfer of protons and electrons, leading to a significant reduction in Gibbs free energy barriers for CO2RR intermediate products.
Comparison Between Hierarchical Time Series Forecasting Approaches for the Electricity Consumption in the Brazilian Industrial Sector
Authors: Mesquita Lopes Cabreira Marlon , Leite Coelho da Silva Felipe , da Silva Cordeiro Josiane , Ureta Tolentino Jeremias Macias , Carbo‐Bustinza Natalí , Canas Rodrigues Paulo , López‐Gonzales Javier Linkolk
Published: November 2024

In Brazil, the industrial sector is the largest electricity consumer. Therefore, energy planning becomes important for industrial development. Electricity consumption data in the Brazilian industrial sector can be organized into a hierarchical structure composed of each geographic region (South, Southeast, Center‐West, Northeast, and North) and their respective states. This work aims to evaluate the predictive capacity of the bottom‐up, top‐down, and optimal combination approaches used to obtain electricity consumption forecasting in the Brazilian industrial sector. These approaches were integrated with the predictive models of exponential smoothing, Box and Jenkins, and neural networks. The results showed that the bottom‐up approach integrated with the Long Short‐Term Memory (LSTM) model provided the best predictions and outperformed the other hierarchical forecasting approaches with an average MAPE of less than 3%.
Domain Selection for Gaussian Process Data: An Application to Electrocardiogram Signals
Authors: Hernández Nicolás , Martos Gabriel
Published: November 2024

Gaussian processes and the Kullback–Leibler divergence have been deeply studied in statistics and machine learning. This paper marries these two concepts and introduce the local Kullback–Leibler divergence to learn about intervals where two Gaussian processes differ the most. We address subtleties entailed in the estimation of local divergences and the corresponding interval of local maximum divergence as well. The estimation performance and the numerical efficiency of the proposed method are showcased via a Monte Carlo simulation study. In a medical research context, we assess the potential of the devised tools in the analysis of electrocardiogram signals.