bluuebunny/crossref_metadata_2025_split huggingface dataset:
Coupled Electronic and Anharmonic Structural Dynamics for Carrier Self‐Trapping in Photovoltaic Antimony Chalcogenides
Authors: Tao Weijian , Zhu Leilei , Li Kanghua , Chen Chao , Chen Yuzhong , Li Yujie , Li Xufeng , Tang Jiang , Shang Honghui , Zhu Haiming 
Published: June 2022

AbstractV–VI antimony chalcogenide semiconductors have shown exciting potentials for thin film photovoltaic applications. However, their solar cell efficiencies are strongly hampered by anomalously large voltage loss (>0.6 V), whose origin remains controversial so far. Herein, by combining ultrafast pump–probe spectroscopy and density functional theory (DFT) calculation, the coupled electronic and structural dynamics leading to excited state self‐trapping in antimony chalcogenides with atomic level characterizations is reported. The electronic dynamics in Sb2Se3 indicates a ≈20 ps barrierless intrinsic self‐trapping, with electron localization and accompanied lattice distortion given by DFT calculations. Furthermore, impulsive vibrational coherences unveil key SbSe vibrational modes and their real‐time interplay that drive initial excited state relaxation and energy dissipation toward stabilized small polaron through electron–phonon and subsequent phonon–phonon coupling. This study's findings provide conclusive evidence of carrier self‐trapping arising from intrinsic lattice anharmonicity and polaronic effect in antimony chalcogenides and a new understanding on the coupled electronic and structural dynamics for redefining excited state properties in soft semiconductor materials.
Simultaneous Near‐Surface Trace Doping and Surface Modifications by Gas–Solid Reactions during One‐Pot Synthesis Enable Stable High‐Voltage Performance of LiCoO2
Authors: Tan Xinghua , Zhao Tingqiao , Song Luting , Mao Dongdong , Zhang Yongxin , Fan Zhengwei , Wang Hanfu , Chu Weiguo 
Published: June 2022

AbstractLiCoO2 (LCO) with a high theoretical capacity of 274 mAh g–1 can rarely achieve a high practical capacity even at an upper cutoff voltage of 4.6 V due to severe structural instability and interface side reactions. Herein, an in situ strategy of gas–solid modifications during synthesis is proposed to improve the performance of LCO using sulfocompound‐contained expanded graphite (EG) as templates. In situ generated SO2 gas from EG enables the Co‐coating of coherent spinel LixCo2O4 and Li2SO4 and the trace doping of high‐valence S mainly in the near‐surface regions via its reactions with the precursors. The modified LCO possesses excellent structural reversibility, interfacial stability, slight dissolution of Co2+, high diffusion coefficients of Li+, and low O 2p band top. This endows LCO with remarkably improved high‐voltage performance, 222 and 143 mAh g‐1 at 0.1 and 20 C, respectively, and 88% capacity retention over 100 cycles at 1 C for LCO/Li half cells between 2.8 and 4.6 V, and 202 mAh g–1 at 1 C and 87% capacity retention over 1000 cycles between 2.8 and 4.5 V for LCO/graphite full cells. This study provides a unique, simple, and upscalable strategy for performance improvement of electrode materials.
Precision surgery for colorectal liver metastases: Current knowledge and future perspectives
Authors: Margonis Georgios Antonios , Vauthey Jean‐Nicolas 
Published: June 2022

AbstractPrecision surgery for colorectal liver metastases (CRLM) includes optimal selection of both the patient and surgery. Initial attempts of using clinical risk scores to identify patients for whom technically feasible surgery is oncologically futile failed. Since then, patient selection for single‐stage hepatectomy followed three distinct approaches, all of which incorporated biomarkers. The BRAF V600E mutation, the G12V KRAS variant, and the triple mutation of RAS, TP53, and SMAD4 appear to be the most promising, but none can be used in isolation to deny surgery in otherwise resectable cases. Combining biomarkers with clinicopathologic factors that predict poor prognosis may be used to select patients for surgery, but external validation and matched analyses with medically treated counterparts are needed. Patient selection for special surgical procedures (two‐stage hepatectomy [TSH], Associating Liver Partition and Portal vein Ligation for staged hepatectomy [ALPPS], and liver transplant [LT]) has been recently refined. Specifically, BRAF mutations and right‐sided laterality have been proposed as separate contraindications to LT. A similar association of right‐sided laterality, particularly when combined with RAS mutations, with very poor outcomes has been observed for ALPPS and has been suggested as a biologic contraindication. Data are scarce for TSH but RAS mutations may portend very poor survival following TSH completion. The selection of the best single‐stage hepatectomy (optimal margin and type of resection) based on biomarkers remains debated, although there is some evidence that RAS may play a significant role. Lastly, although there are currently no criteria to select among the three special techniques based on their efficacy or appropriateness in different settings, RAS mutational status may be used to select patients for TSH, while right‐sided tumor in conjunction with a RAS mutation may be a contraindication to LT and ALPPS.
Improving CH4 uptake and CH4/N2 separation in pillar‐layered metal–organic frameworks using a regulating strategy of interlayer channels
Authors: Chen Yang , Wang Yi , Wang Yong , Xiong Qizhao , Yang Jiangfeng , Li Libo , Li Jinping , Mu Bin 
Published: June 2022

AbstractA pore engineering strategy involving the regulation of pillars in a series of pillar‐layered metal–organic frameworks was presented to promote pore size adjustment and pore environment optimization for efficient separation of CH4 from coal‐mine methane. Compared with the original Ni(BTC)(BPY) and Ni(BTC)(TED), the suitable pore size and rich supply of carboxylate oxygens in the newly constructed Ni(BTC)(PIZ) resulted in the strongest recognition of CH4, leading to both high CH4 uptake (1.62 mmol/g) and CH4/N2 (50/50) selectivity (7.32) at 298 K and 1 bar. Its optimal balance performance between uptake and selectivity was better than most reported adsorbents, which further led to the most efficient separation of CH4 from CH4/N2 mixtures. The stability of the structure and performance was verified by repeated cycle tests. Overall, it is believed the structure constructed based on the regulation strategy of the interlayer channel would enable the application of promising metal–organic frameworks in industrial gas separation processes.
Intramolecular Chloro–Sulfur Interaction and Asymmetric Side‐Chain Isomerization to Balance Crystallinity and Miscibility in All‐Small‐Molecule Solar Cells
Authors: Gao Wei , Jiang Mengyun , Wu Ziang , Fan Baobing , Jiang Wenlin , Cai Ning , Xie Hua , Lin Francis R. , Luo Jingdong , An Qiaoshi , Woo Han Young , Jen Alex K.‐Y. 
Published: June 2022

AbstractIntramolecular Cl−S non‐covalent interaction is introduced to modify molecular backbone of a benzodithiophene terthiophene rhodamine (BTR) benchmark structure, helping planarize and rigidify the molecular framework for improving charge transport. Theoretical simulations and temperature‐variable NMR experiments clearly validate the existence of Cl−S non‐covalent interaction in two designed chlorinated donors and explain its important role in enhancing planarity and rigidity of the molecules for enhancing their crystallinity. The asymmetric isomerization of side‐chains further optimizes the molecular orientation and surface energy to strike a balance between its crystallinity and miscibility. This carefully manipulated molecular design helps result in increased carrier mobility and suppressed charge recombination to obtain simultaneously enhanced short‐circuit current (Jsc) and fill factor (FF) and a very high efficiency of 15.73 % in binary all‐small‐molecule organic solar cells.
PlyAB Nanopores Detect Single Amino Acid Differences in Folded Haemoglobin from Blood**
Authors: Huang Gang , Voorspoels Aderik , Versloot Roderick Corstiaan Abraham , van der Heide Nieck Jordy , Carlon Enrico , Willems Kherim , Maglia Giovanni 
Published: June 2022

AbstractThe real‐time identification of protein biomarkers is crucial for the development of point‐of‐care and portable devices. Here, we use a PlyAB biological nanopore to detect haemoglobin (Hb) variants. Adult haemoglobin (HbA) and sickle cell anaemia haemoglobin (HbS), which differ by just one amino acid, were distinguished in a mixture with more than 97 % accuracy based on individual blockades. Foetal Hb, which shows a larger sequence variation, was distinguished with near 100 % accuracy. Continuum and Brownian dynamics simulations revealed that Hb occupies two energy minima, one near the inner constriction and one at the trans entry of the nanopore. Thermal fluctuations, the charge of the protein, and the external bias influence the dynamics of Hb within the nanopore, which in turn generates the unique ionic current signal in the Hb variants. Finally, Hb was counted from blood samples, demonstrating that direct discrimination and quantification of Hb from blood using nanopores, is feasible.
Efficient 1400–1600 nm Circularly Polarized Luminescence from a Tuned Chiral Erbium Complex
Authors: Willis Oliver G. , Petri Filippo , Pescitelli Gennaro , Pucci Andrea , Cavalli Enrico , Mandoli Alessandro , Zinna Francesco , Di Bari Lorenzo 
Published: June 2022

AbstractNovel chiral Er complexes based on both enantiomers of extended iPrPyBox (2,6‐Bis[4‐isopropyl‐4,5‐dihydrooxazol‐2‐yl)]pyridine) show strong near‐infrared circularly polarized luminescence (CPL) within the 1400 to 1600 nm spectral region under 450 nm irradiation. CPL activity in this region, despite being particularly rare, would open the way to potential applications in the domain, e.g., of fiber‐optic telecommunications and free‐space long‐distance optical communications employing circularly polarized light. Moreover, the long wavelength excitation is advantageous for applications in the field of (circularly polarized) microscopy and bioimaging.
Down Syndrome: A Review of Key Perioperative Implications
Authors: Hines Cheryl B. , Simmons Staci A. 
Published: June 2022

ABSTRACTDown syndrome (DS) is the most common chromosomal abnormality in humans that is compatible with life. This syndrome occurs when there is an extra copy of the 21st chromosome. Down syndrome is associated with numerous comorbidities that can pose challenges for the perioperative nurse caring for a patient with DS undergoing surgery. These challenges can affect the patient assessment, communication with the patient, and patient safety (eg, preventing complications). As the life expectancy of people with DS has increased, so too have the chances that perioperative nurses will care for a patient with this disorder. This article reviews the pathophysiology of DS, discusses common comorbidities that may directly affect perioperative care, and reviews an exemplar case study that demonstrates how personnel with knowledge of DS can positively influence surgical team decision making for these patients in the perioperative setting.
Clinical Issues—July 2022
Authors: deKay Karen 
Published: June 2022

THIS MONTH
Surgical hand antisepsis recommendations
Key words: surgical hand scrub, alcohol‐based hand rub, dry scrub, wet scrub, antimicrobial.
Surgical hand rub preparation
Key words: surgical hand antiseptic, hand wash, nail pick, hand hygiene, scrub personnel.
Use of a closing tray
Key words: clean‐contaminated, isolation technique, gastrointestinal tract, wound class, wound closure.
Hemostatic agent classification
Key words: Class III medical devices, absorbable hemostatic agents, product classification, medical specialty panels, Code of Federal Regulations (CFR).
Jointly pooling aggregated effect sizes and their standard errors from studies with continuous clinical outcomes
Authors: Almalik Osama , Zhan Zhuozhao , Heuvel Edwin R. van den 
Published: June 2022

AbstractThe DerSimonian–Laird (DL) weighted average method for aggregated data meta‐analysis has been widely used for the estimation of overall effect sizes. It is criticized for its underestimation of the standard error of the overall effect size in the presence of heterogeneous effect sizes. Due to this negative property, many alternative estimation approaches have been proposed in the literature. One of the earliest alternative approaches was developed by Hardy and Thompson (HT), who implemented a profile likelihood instead of the moment‐based approach of DL. Others have further extended this likelihood approach and proposed higher‐order likelihood inferences (e.g., Bartlett‐type corrections). In addition, corrections factors for the estimated DL standard error, like the Hartung–Knapp–Sidik–Jonkman (HKSJ) adjustment, and the restricted maximum likelihood (REML) estimation have been suggested too. Although these improvements address the uncertainty in estimating the between‐study variance better than the DL method, they all assume that the true within‐study standard errors are known and equal to the observed standard errors of the effect sizes. Here, we will treat the observed standard errors as estimators for the within‐study variability and we propose a bivariate likelihood approach that jointly estimates the overall effect size, the between‐study variance, and the potentially heteroskedastic within‐study variances. We study the performance of the proposed method by means of simulation, and compare it to DL (with and without HKSJ), HT, their higher‐order likelihood methods, and REML. Our proposed approach seems to have better or similar coverages compared to the other approaches and it appears to be less biased in the case of heteroskedastic within‐study variances when this heteroskedasticty is correlated with the effect size.
Ovarian thecoma presenting with acute ovarian torsion in pregnancy; report of a rare case
Authors: Maleki Asieh , Khosravi Maedeh , Masrouri Azaadeh 
Published: June 2022

AbstractThecoma is a commonly benign ovarian tumor of the group “Sex cord‐stromal neoplasms.” This group represents <5 percent of ovarian tumors. Thecoma is extremely rare in pregnancy. Here, we describe a 17‐week pregnant woman presenting with acute ovarian pedicle torsion as a result of an ovarian thecoma.
A Red‐Light‐Driven CO‐Releasing Complex: Photoreactivities and Excited‐State Dynamics of Highly Distorted Tricarbonyl Rhenium Phthalocyanines
Authors: Wang Mengfei , Murata Kei , Koike Yosuke , Jonusauskas Gediminas , Furet Amaury , Bassani Dario M. , Saito Daisuke , Kato Masako , Shimoda Yuushi , Miyata Kiyoshi , Onda Ken , Ishii Kazuyuki 
Published: June 2022

AbstractA complex comprising one [Re(CO)3]+ unit and a phthalocyanine (Pc) ligand (Re1Pc) is shown to function as a photo‐induced CO‐releasing molecule (photoCORM) in the presence of O2 and a coordinative solvent under irradiation with red light, which can deeply penetrate living tissues. Transient absorption spectroscopic measurements indicate very short excited‐state lifetimes and ultrafast intersystem crossing for Re1Pc and Re2Pc, which contains two [Re(CO)3]+ units. The excited‐state properties are ascribed to efficient spin–orbit coupling and large Franck–Condon factors originating from the complexes’ distorted structures, that is, unsymmetric coordination of [Re(CO)3]+ unit(s), one of which was confirmed by single‐crystal X‐ray analysis of a symmetrically substituted Pc with two [Re(CO)3]+ units. Re1Pc represents a promising red‐light‐driven photoCORM that can be applied in biological environments or therapeutic applications.
Suppression of Liquid‐Liquid Phase Separation and Aggregation of Antibodies by Modest Pressure Application
Authors: Fetahaj Zamira , Jaworek Michel W. , Oliva Rosario , Winter Roland 
Published: June 2022

AbstractThe high colloidal stability of antibody (immunoglobulin) solutions is important for pharmaceutical applications. Inert cosolutes, excipients, are generally used in therapeutic protein formulations to minimize physical instabilities, such as liquid–liquid phase separation (LLPS), aggregation and precipitation, which are often encountered during manufacturing and storage. Despite their widespread use, a detailed understanding of how excipients modulate the specific protein‐protein interactions responsible for these instabilities is still lacking. In this work, we demonstrate the high sensitivity to pressure of globulin condensates as a suitable means to suppress LLPS and subsequent aggregation of concentrated antibody solutions. The addition of excipients has only a minor effect. The high pressure sensitivity observed is due to the fact that these flexible Y‐shaped molecules create a considerable amount of void volume in the condensed phase, leading to an overall decrease in the volume of the system upon dissociation of the droplet phase by pressure already at a few tens of to hundred bar. Moreover, we show that immunoglobulin molecules themselves are highly resistant to unfolding under pressure, and can even sustain pressures up to about 6 kbar without conformational changes. This implies that immunoglobulins are resistant to the pressure treatment of foods, such as milk, in high‐pressure food‐processing technologies, thereby preserving their immunological activity.
Peri‐Decoration of a Tetraazaperylene with Urea Units: Chiral Octaazaperopyrenedioxides (OAPPDOs) and Their Optical and Chiroptical Properties
Authors: Wesp Tobias , Bruckhoff Tim , Wadepohl Hubert , Gade Lutz H. 
Published: June 2022

AbstractOctaazaperopyrenedioxides (OAPPDOs) are a new class of fluorescent polycyclic aromatic hydrocarbons based on a tetraazaperylene core that is formally condensed with N‐substituted urea units in the two opposite peri positions. Here, we report the synthesis of series of substituted OAPPDO derivatives with different N‐substitution patterns (H, alkyl, benzyl) in the peri positions, including bay‐chlorinated OAPPDOs. Starting from the latter, a series of bay‐arylated OAPPDOs was synthesized by Suzuki cross coupling, which resulted in the formation of helically chiral OAPPDO derivatives. The electrochemical and photophysical properties were investigated by UV/Vis and fluorescence spectroscopy as well as cyclic voltammetry. The P and M enantiomers of a phenylated OAPPDO were separated by semipreparative HPLC and further analyzed by CD spectroscopy. The frontier orbital energies, the mechanism of the isomerization, the electronic excitation and the CD spectrum (TD‐DFT) were computed and compared to the experimental data. The reversible 1e− oxidation of the OAPPDOs generates the corresponding radical cations, one of which was characterized by EPR spectroscopy. The reversible oxidation process was also systematically investigated by spectro‐electrochemistry.
Recent Advances in Type I Photoinitiators for Visible Light Induced Photopolymerization
Authors: Müller Stefanie Monika , Schlögl Sandra , Wiesner Tanja , Haas Michael , Griesser Thomas 
Published: June 2022

AbstractPhotopolymerization and its application in the dental, three‐dimensional (3D) printing, coating and electronic industry has become increasingly popular over the last decades. A huge variety of photoinitiators (PIs) and photoinitiating systems (PISs) have been developed that are able to generate reactive species, e. g. radicals, radical cations, and cations upon light absorption. In this Review, we focus on radical‐generating Type I PIs which undergo homolytic cleavage after irradiation with visible light. The possibility to utilize electromagnetic irradiation above 400 nm for the initiation of polymerization reactions provides several advantages such as a lower energy demand and higher curing depths in pigmented reactive systems. Recent developments of PIs based on phosphorus and group 14 elements as well as other selected concepts for Type I visible light initiators are outlined and discussed within this review.
Production and Purification of Phosphatidylinositol Mannosides from Mycobacterium smegmatis Biomass
Authors: Nobre Rodrigo N. , Esteves Ana M. , Borges Nuno , Rebelo Sara , Liu Yaqi , Mancia Filippo , Santos Helena 
Published: June 2022

AbstractMycobacterium tuberculosis, the etiological agent of tuberculosis, is regarded as the most successful pathogen of humankind and a major threat to global health. The mycobacterial cell wall is vital for cell growth, virulence, and resistance to antibiotics, and thus constitutes a unique target for drug development. To characterize the enzymes catalyzing the synthesis of the cell wall components, considerable amounts of substrates are required. Since many mycobacterial cell wall lipids, particularly phosphatidylinositol mannosides (PIMs), are not commercially available, isolation from cell biomass is the most straightforward way to obtain these compounds. In this study, we optimized a protocol to extract and purify PIM species, in particular Ac1PIM2 and Ac1PIM4, which can be further used for the identification and characterization of target enzymes. PIMs were extracted from Mycobacterium smegmatis mc2155 ΔPimE using organic solvents, and purified through three consecutive chromatography steps. Thin‐layer chromatography (TLC) was used in‐between purification steps to evaluate the success of lipid separation, and nuclear magnetic resonance (NMR) was used for product quantification and to assess purity. Typically, from a 60 g batch of M. smegmatis biomass we were able to isolate approximately 9 mg of Ac1PIM2 and 1.8 mg of Ac1PIM4. This is the first time the purification of phosphatidylinositol tetramannoside has been reported. © 2022 Wiley Periodicals LLC.Basic Protocol 1: Growth of M. smegmatis mc2155 ∆PimEBasic Protocol 2: Extraction of lipids from M. smegmatis mc2155 ∆PimEBasic Protocol 3: Treatment of the lipid extract for isolation of phospholipidsBasic Protocol 4: Isolation of phosphatidylinositol mannosidesBasic Protocol 5: Quantification of phosphatidylinositol mannosides
Modelling the tumor immune microenvironment for precision immunotherapy
Authors: Mackenzie Nathan J , Nicholls Clarissa , Templeton Abby R , Perera Mahasha PJ , Jeffery Penny L , Zimmermann Kate , Kulasinghe Arutha , Kenna Tony J , Vela Ian , Williams Elizabeth D , Thomas Patrick B 
Published: June 2022

AbstractThe complexity of the cellular and acellular players within the tumor microenvironment (TME) allows for significant variation in TME constitution and role in anticancer treatment response. Spatial alterations in populations of tumor cells and adjacent non‐malignant cells, including endothelial cells, fibroblasts and tissue‐infiltrating immune cells, often have a major role in determining disease progression and treatment response in cancer. Many current standard systemic antineoplastic treatments target the cancer cells and could be further refined to directly target commonly dysregulated cell populations of the TME. Recent developments in immuno‐oncology and bioengineering have created an attractive potential to model these complexities at the level of the individual patient. These developments, along with the increasing momentum in precision medicine research and application, have catalysed exciting new discoveries in understanding drug–TME interactions, target identification, and improved efficacy of therapies. While rapid progress has been made, there are still many challenges to overcome in the development of accurate in vitro, in vivo and ex vivo models incorporating the cellular interactions that take place in the TME. In this review, we describe how advances in immuno‐oncology and patient‐derived models, such as patient‐derived organoids and explant cultures, have enhanced the landscape of personalised immunotherapy prediction and treatment of solid organ malignancies. We describe and compare different immunological targets and perspectives on two‐dimensional and three‐dimensional modelling approaches that may be used to better rationalise immunotherapy use, ultimately providing a knowledge base for the integration of the autologous TME into these predictive models.