bluuebunny/crossref_metadata_2025_split huggingface dataset:
Near‐Infrared‐II Plasmonic Trienzyme‐Integrated Metal–Organic Frameworks with High‐Efficiency Enzyme Cascades for Synergistic Trimodal Oncotherapy
Authors: Zhou Guangzhi , Li Ming 
Published: April 2022

AbstractNatural enzyme‐based catalytic cascades hold great promise for cancer therapy, but their clinical utility is greatly hindered by the loss of their functions during in vivo delivery. Herein, a plasmonic trienzyme‐integrated metal–organic framework (plasEnMOF) nanoplatform with high‐efficiency enzyme cascades is reported for synergistic starvation, chemodynamic, and plasmonic hyperthermia trimodal therapy of hypoxic tumors. These plasEnMOFs are created with encapsulation of near‐infrared‐II (NIR‐II) plasmonic Au nanorods and natural enzymes—catalase (CAT), glucose oxidase (GOx), and horseradish peroxidase (HRP) within zeolitic imidazolate framework‐8 (ZIF‐8) MOFs. As a trienzyme cascade system, the plasEnMOFs effectively deplete intratumoral glucose and generate toxic reactive oxygen species (ROS) for starvation therapy and chemodynamic therapy (CDT) combined with the plasmonic hyperthermia therapy (PHT). The enhanced glucose consumption and ROS generation by the NIR‐II plasmonic photothermal effect are also demonstrated. The improved chemo‐ and thermotolerance of the encapsulated natural enzymes within the protective ZIF‐8 MOFs are evidenced. With the integrated enzyme cascades and NIR‐II photothermal effects, these plasEnMOFs are demonstrated with exceptional therapeutic effects on 4T1 xenograft tumors through the combined starvation/CDT/PHT therapy. This work highlights the superiority of natural enzyme cascade systems integrated in plasmonic MOFs for high‐efficiency enzymatic cancer therapy.
Synthesis and Catalysis of NHC Coordinated Cyclometalated Palladium(II) Complexes with Bridging Hydroxide Ligands
Authors: Nakajima Isami , Shimizu Minori , Okuda Yuta , Akiyama Ryo , Tadano Ryu , Nagaoka Masahiro , Uemura Naohiro , Yoshida Yasushi , Mino Takashi , Shinozaki Hiraku , Yamamoto Tetsuya 
Published: April 2022

Abstract1,2‐Addition reactions using organoboron compounds are one of the useful syntheses of various functionalized alcohols, but they generally require a large quantity of bases. In this study, we attempted to solve this problem by synthesizing unsymmetrical 1,3‐diarylimidazoline‐type N‐heterocyclic carbene (NHC)‐coordinated C^C* cyclometalated palladium(II) complexes with bridging hydroxide ligands (CYPOHs) in two steps and one pot from the corresponding Cl bridged dimer and using them as catalysts. 2,6‐di(pentan‐3‐yl)aniline (IPent)‐based NHC coordinated PhS‐IPent‐CYPOH acted as a highly efficient catalyst for the 1,2‐addition of (hetero)arylboronates to a large number of aldehydes and ketones, including unactivated ketones, under base‐free conditions.magnified image
Imaging Tumor Heterogeneity and the Variations in Nanoparticle Accumulation Using Perfluorooctyl Bromide Nanocapsule X‐Ray Computed Tomography Contrast
Authors: Beringhs André O'Reilly , Ndaya Dennis , Bosire Reuben , Kasi Rajeswari M. , Lu Xiuling 
Published: April 2022

AbstractSystemically administered nanoparticles can extravasate into solid tumors through active or passive processes, showing high inter‐ and intraindividual variability, leading to inconsistent nanomedicine disposition in tumor lesions and variable therapeutic outcomes. Radio‐opaque Perfluorooctyl bromide‐loaded PEGylated cholesteryl‐functionalized polycaprolactone (PEG‐b‐PCL(Ch)) nanocapsules (PFOB NC) are assessed as imaging probes via X‐ray Computed Tomography (CT) as means to estimate nanoparticle disposition in solid tumors. This imaging platform can enable precision medicine by screening tumors for likelihood of nanoparticle accumulation prior to treatment. Single‐ and double‐lateral xenograft models are employed for imaging‐based nanoparticle accumulation assessment using a preclinical multimodal imaging system. Differences in tumor accumulation and spatial distribution are verified as a function of xenograft type via X‐ray CT and further corroborated by optical imaging. Slow growing OVCAR‐8 xenografts display granular distribution pattern and higher levels of PFOB NC disposition on a volume‐normalized basis. A549 xenografts, displaying faster growth, are less susceptible to PFOB NC accumulation and show only a diffuse‐like spatial distribution of the nanocapsule contrast. A direct correlation between tumor dispositions of PFOB NC and a commercial PEGylated liposomal doxorubicin formulation is found. This study highlights the potential of using nanoparticle‐based radio‐opaque contrasts to better understand nanoparticle disposition and foster improved therapeutic outcomes in cancer nanomedicine.
Optimized Cycle and Safety Performance of Lithium–Metal Batteries with the Sustained‐Release Effect of Nano CaCO3
Authors: Peng Qingkui , Liu Ziyi , Jiang Lihua , Wang Qingsong 
Published: April 2022

AbstractThe capacity attenuation and poor safety caused by lithium dendrite and interface side reactions have hindered the application of lithium–metal batteries (LMBs) for a long time. To solve this problem, some liquid or salt additives have been added to the electrolyte to promote the uniform stripping/plating of lithium, however, the consumption of electrolyte during cycles reduces the concentration of active components, resulting in the gradual failure of additives. Herein, a new solid additive (nano CaCO3) working under the principle of sustained release is proposed: the homo‐dispersed nano CaCO3 particles can continuously absorb the decomposition by‐products generated during the side reaction and release Ca2+, which cannot only inhibit the tip deposition of Li+ through electrostatic shielding effect but also effectively promote the formation of stable F‐rich solid–electrolyte interphase (SEI). As the consequence, a notably optimized electrochemical performance for commercial carbonate electrolyte after adding 3 wt.% nano CaCO3 is observed, and the cycle life of symmetric Li||Li cells is extended from <400 h to over 800 h at 1 mA cm−2. In addition, the modified emulsion‐like electrolyte has lower volatility and its protective effect on the separator is confirmed by ex situ optical observation, reflecting the safety improvement of LMBs.
Advances and Challenges in Photoelectrochemical Redox Batteries for Solar Energy Conversion and Storage
Authors: Feng Hao , Liu Dong , Zhang Ying , Shi Xingyi , Esan Oladapo Christopher , Li Qiang , Chen Rong , An Liang 
Published: April 2022

AbstractThe photoelectrochemical redox battery (PRB) has been regarded as an alternative candidate for large‐scale solar energy capture, conversion, and storage as it combines the superior advantages of photoelectrochemical devices and redox batteries. As an emerging solar energy utilization technology, significant progress has been made towards promoting and proliferating the practical applications of PRBs. However, wide market penetration of PRBs is still being significantly inhibited by limited photocatalytic activity, low efficiency, among other critical issues. Furthermore, the integration of each component, including solar materials, redox couples, and membranes and their interaction in PRBs play vital roles towards achieving smooth operation and high performance. Herein, the materials, mechanisms, recent advances, and challenges in the use of PRBs are presented. The crucial influence of redox couples, photoelectrode materials, membranes on the performance of the system including how they affect solar energy capture, reaction kinetics, and internal losses are systematically discussed. In addition, the recent advances of a single‐battery of photoelectrode mode and an integrated device of solar cell mode are summarized. Furthermore, the state of the art performance of PRBs and their upscaling progress are also discussed. Finally, the challenges and perspectives for the future development of PRBs are highlighted.
Synergistic Engineering of Sulfur Vacancies and Heterointerfaces in Copper Sulfide Anodes for Aqueous Zn‐Ion Batteries with Fast Diffusion Kinetics and an Ultralong Lifespan
Authors: Lei Qi , Zhang Jiaqian , Liang Zhaofeng , Yue Yang , Ren Zhiguo , Sun Yuanhe , Yao Zeying , Li Ji , Zhao Yuanxin , Yin Yaru , Huai Ping , Lv Zhengxing , Li Jiong , Jiang Zheng , Wen Wen , Li Xiaolong , Zhou Xingtai , Zhu Daming 
Published: April 2022

AbstractAqueous Zn‐ion batteries (AZIBs) are promising candidates for implementing large‐scale energy storage, but the adverse side reactions and unsatisfactory cycle life brought by Zn‐metal anodes limit their potential in applications. Herein, an ingenious synthesized CuS1–x@polyaniline (PANI) is proposed as an attractive conversion‐type Zn‐metal‐free anode for AZIBs, in which appropriate S‐vacancies and PANI heterointerfaces can be simultaneously constructed. This “killing three birds with one stone” strategy stabilizes the anode structure by utilizing organic–inorganic heterointerfaces and enhances Zn2+ storage, benefiting from abundant S‐vacancies, as well as initiating fast Zn2+ transport kinetics based on the joint effect of the two. Operando X‐ray absorption fine structure and synchrotron X‐ray diffraction further reveal the highly reversible conversion reaction of CuS1–x@PANI via a distinct crystallization–amorphous transformation mechanism. These features endow CuS1–x@PANI with sufficient zinc‐ion storage capacity (215 mA h g−1 at 100 mA g−1) and reliable current abuse tolerance (154.3 mA h g−1 at 1 A g−1 after 1000 cycles). Moreover, when matched with the optimized ZnxMnO2 cathode, the full battery achieves a record‐high cycling performance of 10 000 cycles (80% capacity retention) at a superhigh current density of 10 A g−1. This study provides new opportunities for developing high‐performance rocking‐chair AZIBs.
Environmentally Friendly AgBiS2 Nanocrystal Inks for Efficient Solar Cells Employing Green Solvent Processing
Authors: Wang Yongjie , Peng Lucheng , Wang Zhuoran , Konstantatos Gerasimos 
Published: April 2022

AbstractSilver bismuth sulfide nanocrystals (AgBiS2 NCs) are emerging absorber materials for low‐cost solar cells, owing to their solution‐processability, environmentally friendliness, earth abundance, and high absorption coefficients. When it comes to green manufacturing technologies, besides the semiconductor materials, solvents play an equally important role. Here, solution‐phase ligand‐exchanged (SPLE) AgBiS2 nanocrystal inks employing 3‐mercaptopropionic (MPA) in methanol as a ligand solution are introduced. The resultant MPA capped AgBiS2 nanocrystals can be fully dissolved in water, forming completely environmentally friendly nanocrystal inks. These nanocrystal inks allow the fabrication of fully green‐processed photovoltaic devices with a power conversion efficiency up to 7.3%. This method not only demonstrates the potential of solution‐phase ligand‐exchanged AgBiS2 nanocrystal inks, but also paves a path toward fully green‐processed nanocrystal devices.
Employing 2D‐Perovskite as an Electron Blocking Layer in Highly Efficient (18.5%) Perovskite Solar Cells with Printable Low Temperature Carbon Electrode
Authors: Zouhair Salma , Yoo So‐Min , Bogachuk Dmitry , Herterich Jan Philipp , Lim Jaekeun , Kanda Hiroyuki , Son Byoungchul , Yun Hyung Joong , Würfel Uli , Chahboun Adil , Nazeeruddin Mohammad Khaja , Hinsch Andreas , Wagner Lukas , Kim Hobeom 
Published: April 2022

AbstractInterface engineering and passivating contacts are key enablers to reach the highest efficiencies in photovoltaic devices. While printed carbon–graphite back electrodes for hole‐transporting material (HTM)‐free perovskite solar cells (PSCs) are appealing for fast commercialization of PSCs due to low processing costs and extraordinary stability, this device architecture so far suffers from severe performance losses at the back electrode interface. Herein, a 2D perovskite passivation layer as an electron blocking layer (EBL) at this interface to substantially reduce interfacial recombination losses is introduced. The formation of the 2D perovskite EBL is confirmed through X‐ray diffraction, photoemission spectroscopy, and an advanced spectrally resolved photoluminescence microscopy mapping technique. Reduced losses that lead to an enhanced fill factor and VOC are quantified by electrochemical impedance spectroscopy and JSC–VOC measurements. This enables reaching one of the highest reported efficiencies of 18.5% for HTM‐free PSCs using 2D perovskite as an EBL with a significantly improved device stability.
Immunoglobulin light chain amyloidosis: 2022 update on diagnosis, prognosis, and treatment
Authors: Gertz Morie A. 
Published: April 2022

AbstractDisease overviewImmunoglobulin light chain amyloidosis is a clonal, nonproliferative plasma cell disorder in which fragments of immunoglobulin light or heavy chain are deposited in tissues. Clinical features depend on organs involved but can include heart failure with preserved ejection fraction, nephrotic syndrome, hepatic dysfunction, peripheral/autonomic neuropathy, and “atypical smoldering multiple myeloma or monoclonal gammopathy of undetermined significance (MGUS).”DiagnosisTissue biopsy stained with Congo red demonstrating amyloid deposits with apple‐green birefringence is required for the diagnosis of AL amyloidosis. Invasive organ biopsy is not required in 85% of patients. Verification that amyloid is composed of immunoglobulin light chains is mandatory. The gold standard is laser capture mass spectroscopy.PrognosisN‐terminal pro–brain natriuretic peptide (NT‐proBNP or BNP), serum troponin T (or I), and difference between involved and uninvolved immunoglobulin free light chain values are used to classify patients into four groups of similar size; median survivals are 73, 35, 15, and 5 months.TherapyAll patients with a systemic amyloid syndrome require therapy to prevent deposition of amyloid in other organs and prevent progressive organ failure. Current first‐line therapy with the best outcome is daratumumab, bortezomib, cyclophosphamide, and dexamethasone. The goal of therapy is a complete response (CR). In patients failing to achieve this depth of response options for consolidation include pomalidomide, stem cell transplantation, venetoclax, and bendamustine.Future challengesDelayed diagnosis remains a major obstacle to initiating effective therapy prior to the development of end‐stage organ failure. Trials of antibodies to catabolize deposited fibrils are underway.
Impact of parental relatedness on reproductive outcomes among the Old Order Amish of Lancaster County
Authors: Lynch Megan T. , Maloney Kristin A. , Pollin Toni I. , Streeten Elizabeth A. , Puffenberger Erik G. , Strauss Kevin A. ,   Regeneron Genetics Center, Shuldiner Alan R. , Mitchell Braxton D. 
Published: April 2022

AbstractGenetically isolated populations that arise due to recent bottleneck events have reduced genetic variation reflecting the common set of founders. Increased genetic relatedness among members of isolated populations puts them at increased risk for some recessive disorders that are rare in outbred populations. To assess the burden on reproductive health, we compared frequencies of adverse reproductive outcomes between Amish couples who were both heterozygous carriers of a highly penetrant pathogenic or likely pathogenic variant and noncarrier couples from the same Amish community. In addition, we evaluated whether overall genetic relatedness of parents was associated with reproductive outcomes. Of the 1824 couples included in our study, 11.1% were at risk of producing a child with an autosomal recessive disorder. Carrier couples reported a lower number of miscarriages compared to noncarrier couples (p = 0.02), although the number of stillbirths (p = 0.3), live births (p = 0.9), and number of pregnancies (p = 0.9) did not differ significantly between groups. In contrast, higher overall relatedness between spouses was positively correlated with number of live births (p < 0.0001), pregnancies (p < 0.0001), and stillbirths (p = 0.03), although not with the number of miscarriages (p = 0.4). These results highlight a complex association between relatedness of parents and reproductive health outcomes in this community.
Structural properties of humeral diaphyses of East Asian modern humans from the Late Pleistocene to Early Holocene
Authors: Zhao Yuhao , Wei Pianpian , Zhang Xinglong , Lu Hongliang , He Kunyu , Yuan Haibing , Xing Song 
Published: April 2022

AbstractObjectivesThis study aims to explore the structural properties along entire humeral diaphyses of Late Pleistocene and Early Holocene East Asian modern humans relative to the contemporaneous Neandertal specimen Regourdou 1 to provide insight into adaptive behaviors within temporal and regional hominin contexts.Materials and methodsThe humeri of three individuals from East Asia securely dated from the Late Pleistocene to Early Holocene were selected: Tianyuan 1, Zhaoguo M1, and Qihe M2. These specimens were scanned using microcomputed tomography to evaluate structural properties: cortical bone thickness (CBT), second moment of area (SMA), external radius (ER), and polar moment of area (J).ResultsThe distribution patterns of CBT, ER, and J were similar across all specimens. However, the magnitude of these variables was notably large in Regourdou 1 right humerus. The SMA, ER, and J of left humerus of Tianyuan 1 were less than that of other East Asian specimens, whereas those from the right humerus of the Qihe M2 individual were slightly larger than two other East Asian individuals. Additionally, the humeral asymmetry of Tianyuan 1 was greater than that of Zhaoguo M1 and Qihe M2.DiscussionCompared to Regourdou 1, East Asian specimens had reduced humeral robusticity. Within East Asia, the Late Pleistocene modern humans exhibit greater humeral asymmetry than the Early Holocene humans, indicating a universal reduction of humeral asymmetry related to technological changes across Eurasia during this time. The current study contributes to developing a more thorough understanding of intergroup humeral structural variation across Eurasia during the Late Pleistocene and Early Holocene.
Adverse events of emergency surgical front of neck airway access: an observational descriptive study
Authors: Okada Asami , Okada Yohei , Kandori Kenji , Ishii Wataru , Narumiya Hiromichi , Iizuka Ryoji 
Published: April 2022

AimEmergency front of neck access (eFONA), such as scalpel cricothyroidotomy, is a rescue technique used to open the airway during “cannot intubate, cannot oxygenate” situations. However, little is known about the adverse events associated with the procedure. This study aimed to describe the adverse events that occur in patients who undergo eFONA and their management.MethodsThis retrospective observational cohort study included emergency patients who underwent eFONA between April 2012 and August 2020. We described the patients’ characteristics and the adverse events during or immediately after the procedure.ResultsAmong 75,529 emergency patients during the study period, 31 (0.04%) underwent an eFONA. The median (interquartile range) age was 53 (39–67) years, and 23 patients (74.2%) were men. Of all cases, 13 (41.9%) experienced adverse events. Of these, three cases (23.2%) were cephalad misplacement of the intubation tube, one case (7.7%) was cuff injury, one case (7.7%) was tube obstruction due to vomiting, and one case (7.7%) was tube kink. In cases with these adverse events, the initial attempt of eFONA failed, and alternative immediate action was necessary to secure the airway.ConclusionThis single‐center retrospective observational study described several adverse events of eFONA. In particular, it is important to understand the possible life‐threatening adverse events that lead to failure of securing airways such as cephalad displacement, tube obstruction, and tube kink and respond promptly to ensure a secure definitive airway for patients’ safety.
The Optimal Target and Connectivity for Deep Brain Stimulation in Lennox–Gastaut Syndrome
Authors: Warren Aaron E.L. , Dalic Linda J. , Bulluss Kristian J. , BAppSci Annie Roten , Thevathasan Wesley , Archer John S. 
Published: April 2022

ObjectiveDeep brain stimulation (DBS) can reduce seizures in Lennox–Gastaut syndrome (LGS). However, little is known about the optimal target and whether efficacy depends on connectivity of the stimulation site. Using outcome data from the ESTEL trial, we aimed to determine the optimal target and connectivity for DBS in LGS.MethodsA total of 20 patients underwent bilateral DBS of the thalamic centromedian nucleus (CM). Outcome was percentage seizure reduction from baseline after 3 months of DBS, defined using three measures (monthly seizure diaries, 24‐hour scalp electroencephalography [EEG], and a novel diary‐EEG composite). Probabilistic stimulation mapping identified thalamic locations associated with higher/lower efficacy. Two substitute diffusion MRI datasets (a normative dataset from healthy subjects and a “disease‐matched” dataset from a separate group of LGS patients) were used to calculate structural connectivity between DBS sites and a map of areas known to express epileptic activity in LGS, derived from our previous EEG‐fMRI research.ResultsResults were similar across the three outcome measures. Stimulation was most efficacious in the anterior and inferolateral “parvocellular” CM border, extending into the ventral lateral nucleus (posterior subdivision). There was a positive association between diary‐EEG composite seizure reduction and connectivity to areas of a priori EEG‐fMRI activation, including premotor and prefrontal cortex, putamen, and pontine brainstem. In contrast, outcomes were not associated with baseline clinical variables.InterpretationEfficacious CM‐DBS for LGS is linked to stimulation of the parvocellular CM and the adjacent ventral lateral nucleus, and is associated with connectivity to, and thus likely modulation of, the “secondary epileptic network” underlying the shared electroclinical manifestations of LGS. ANN NEUROL 2022;92:61–74
Amphiphilic Polycarbonate Micellar Rhenium Catalysts for Efficient Photocatalytic CO2 Reduction in Aqueous Media
Authors: Ren Fang‐Yu , Chen Kaihong , Qiu Li‐Qi , Chen Jin‐Mei , Darensbourg Donald J. , He Liang‐Nian 
Published: April 2022

AbstractA triblock amphiphilic polymer derived from the copolymerization of CO2 and epoxides containing a bipyridine rhenium complex in its backbone is shown to effectively catalyze the visible‐light‐driven reduction of CO2 to CO. This polymer provides uniformly spherical micelles in aqueous solution, where the metal catalyst is sequestered in the hydrophobic portion of the nanostructured micelle. CO2 to CO reduction occurs in an efficient visible‐light‐driven process in aqueous media with turnover numbers up to 110 (>99 % selectivity) in the absence of a photosensitizer, which is a 37‐fold enhancement over the corresponding molecular rhenium catalyst in organic solvent. Notably, the amphiphilic polycarbonate micelle rhenium catalyst suppresses H2 generation, presumably by preventing deactivation of the active catalytic center by water.