bluuebunny/crossref_metadata_2025 huggingface dataset:
Banana‐shaped electron acceptors with an electron‐rich core fragment and 3D packing capability
Authors: Li Pengqi , Meng Xianyi , Jin Ke , Xu Zhiwei , Zhang Jianqi , Zhang Lixiu , Niu Chuang , Tan Furui , Yi Chenyi , Xiao Zuo , Feng Yaqing , Wang Guan‐Wu , Ding Liming
Published: June 2022

The emergence of Y6‐type nonfullerene acceptors has greatly enhanced the power conversion efficiency (PCE) of organic solar cells (OSCs). However, which structural feature is responsible for the excellent photovoltaic performance is still under debate. In this study, two Y6‐like acceptors BDOTP‐1 and BDOTP‐2 were designed. Different from previous Y6‐type acceptors featuring an A–D–Aʹ–D–A structure, BDOTP‐1, and BDOTP‐2 have no electron‐deficient Aʹ fragment in the core unit. Instead, there is an electron‐rich dibenzodioxine fragment in the core. Although this modification leads to a marked change in the molecular dipole moment, electrostatic potential, frontier orbitals, and energy levels, BDOTP acceptors retain similar three‐dimensional packing capability as Y6‐type acceptors due to the similar banana‐shaped molecular configuration. BDOTP acceptors show good performance in OSCs. High PCEs of up to 18.51% (certified 17.9%) are achieved. This study suggests that the banana‐shaped configuration instead of the A–D–Aʹ–D–A structure is likely to be the determining factor in realizing high photovoltaic performance.
Calibrating Catalytic DNA Nanostructures for Site‐Selective Protein Modification**
Authors: Keijzer Jordi F. , Zuilhof Han , Albada Bauke
Published: June 2022

Many biomedical fields rely on proteins that are selectively modified. These can be attached using reactive or catalytic moieties, but the position where these moieties are attached is often poorly controlled. We assessed how catalyst position affects the efficiency and selectivity of protein modification. For this, we anchored a template DNA strand to three different proteins, which were subsequently hybridized to DNA strands that contained catalysts at different positions. We found a strong correlation between the catalyst‐to‐protein distance and the efficiency of protein modification for acyl transfer catalysts, which operate via a covalently bound reactant intermediate. Additionally, we found that the catalyst's distance and orientation with respect to the protein surface, also influences its site‐selectivity. A catalyst operating with unbound reactant intermediates showed only enhanced efficiency. Our results are rationalized using computational simulations, showing that one‐point anchoring of the DNA construct leads to notable differences in the site of modification.
Isolation of Elusive Phosphinidene‐Chlorotetrylenes: The Heavier Cyanogen Chloride Analogues
Authors: Nag Ekta , Francis Maria , Battuluri Sridhar , Sinu Bhavya Bini , Roy Sudipta
Published: June 2022

The elusive phosphinidene‐chlorotetrylenes, [PGeCl] and [PSiCl] have been stabilized by the hetero‐bileptic cyclic alkyl(amino) carbene (cAAC), N‐heterocyclic carbene (NHC) ligands, and isolated in the solid state at room temperature as the first neutral monomeric species of this class with the general formulae (L)P‐ECl(L′) (E=Ge, 3 a–3 c; E=Si, 6; L=cAAC; L′=NHC). Compounds 3 a–3 c have been synthesized by the reaction of cAAC‐supported potassium phosphinidenides [cAAC=PK(THF)x]n (1 a–1 c) with the adduct NHC:→GeCl2 (2). Similarly, compound 6 has been synthesized via reaction of 1 a with NHC:→SiCl2 adduct (4). Compounds 3 a–3 c, and 6 have been structurally characterized by single‐crystal X‐ray diffraction, NMR spectroscopy and mass spectrometric analysis. DFT calculations revealed that the heteroatom P in 3 bears two lone pairs; the non‐bonding pair with 67.8 % of s‐ and 32 % of p character, whereas the other lone pair is involved in π backdonation to the CcAAC‐N π* of cAAC. The Ge atom in 3 contains a lone pair with 80 % of s character, and slightly involved in the π backdonation to CNHC. EDA‐NOCV analyses showed that two charged doublet fragments {(cAAC)(NHC)}+, and {PGeCl}− prefer to form one covalent electron‐sharing σ bond, one dative σ bond, one dative π bond, and a charge polarized weak π bond. The covalent electron‐sharing σ bond contributes to the major stabilization energy to the total orbital interaction energy of 3, enabling the first successful isolations of this class of compounds (3, 6) in the laboratory.
On the Evolutionary History of the Twenty Encoded Amino Acids
Authors: Kirschning Andreas
Published: June 2022

α‐Amino acids are essential molecular constituents of life, twenty of which are privileged because they are encoded by the ribosomal machinery. The question remains open as to why this number and why this 20 in particular, an almost philosophical question that cannot be conclusively resolved. They are closely related to the evolution of the genetic code and whether nucleic acids, amino acids, and peptides appeared simultaneously and were available under prebiotic conditions when the first self‐sufficient complex molecular system emerged on Earth. This report focuses on prebiotic and metabolic aspects of amino acids and proteins starting with meteorites, followed by their formation, including peptides, under plausible prebiotic conditions, and the major biosynthetic pathways in the various kingdoms of life. Coenzymes play a key role in the present analysis in that amino acid metabolism is linked to glycolysis and different variants of the tricarboxylic acid cycle (TCA, rTCA, and the incomplete horseshoe version) as well as the biosynthesis of the most important coenzymes. Thus, the report opens additional perspectives and facets on the molecular evolution of primary metabolism.
From CsKTaF7 to CsNaTaF7: Alkali Metal Cations Regulation to Generate SHG Activity**
Authors: Tang Ru‐Ling , Lian Xin , Li Xiao‐Hui , Huai Lei , Liu Wenlong , Guo Sheng‐Ping
Published: June 2022

Inorganic metal halides play important roles in wide range of areas including fluorescence, X‐ray detection, and nonlinear‐optics. Herein, two new mixed alkali metal tantalum fluorides, CsKTaF7 and CsNaTaF7, have been obtained based on the strategy of cations regulation in A2MF7 (A represents monovalent cations and M is d0 transition‐metal cation) system by a conventional hydrothermal route. CsKTaF7 crystallizes in the centric Pnma space group, while CsNaTaF7 crystallizes in the polar Cmc21 space group and exhibits moderate and phase‐matchable NLO activity. Both halides possess large optical band gaps above 5.0 eV. The crystal structure evolution, optical properties, and detailed theory calculations of these two halides were elucidated in this work.
Regulating Extra‐Framework Cations in Faujasite Zeolites for Capture of Trace Carbon Dioxide
Authors: Liu Shanshan , Chen Yinlin , Yue Bin , Wang Chang , Qin Bin , Chai Yuchao , Wu Guangjun , Li Jiangnan , Han Xue , da‐Silva Ivan , Manuel Pascal , Day Sarah J. , Thompson Stephen P. , Guan Naijia , Yang Sihai , Li Landong
Published: June 2022

The development of cost‐effective sorbents for direct capture of trace CO2 (<1 %) from the atmosphere is an important and challenging task. Natural or commercial zeolites are promising sorbents, but their performance in adsorption of trace CO2 has been poorly explored to date. A systematic study on capture of trace CO2 by commercial faujasite zeolites reveals that the extra‐framework cations play a key role on their performance. Under dry conditions, Ba−X displays high dynamic uptake of 1.79 and 0.69 mmol g−1 at CO2 concentrations of 10000 and 1000 ppm, respectively, and shows excellent recyclability in the temperature‐swing adsorption processes. K−X exhibits perfect moisture resistance, and >95 % dry CO2 uptake can be preserved under relative humidity of 74 %. In situ solid‐state NMR spectroscopy, synchrotron X‐ray diffraction and neutron diffraction reveal two binding sites for CO2 in these zeolites, namely the basic framework oxygen atoms and the divalent alkaline earth metal ions. This study unlocks the potential of low‐cost natural zeolites for applications in direct air capture.
Blastic plasmacytoid dendritic cell neoplasm (BPDCN): A promising future in the era of targeted therapeutics
Authors: Adimora Ijele J. , Wilson Nathaniel R. , Pemmaraju Naveen
Published: June 2022

Blastic plasmacytoid dendritic cell neoplasm (BPDCN) is a rare hematologic malignancy arising from precursor dendritic cells. BPDCN cells characteristically express several markers on their cell surfaces including CD123, CD4, and CD56. Because of its rarity and challenging clinical presentation, there was no standard of care in managing BPDCN for decades and its prognosis overall was poor. However, as understanding of this rare neoplasm has increased, so have treatment options. The conventional cytotoxic chemotherapy regimens once used in the treatment of BPDCN were modest in their impact on disease relapse until paired with hematopoietic stem cell transplant. Although recent data suggest that there still remains a role for chemotherapeutic agents, targeted modalities have expanded the overall BPDCN treatment landscape. The CD123‐targeted agent, tagraxofusp, was the first Food and Drug Administration–approved monotherapy in the treatment of BPDCN. Since its inception, several CD123‐targeted and other cell‐surface agents have been investigated, with many agents still in the preclinical stages. Although relapsed/refractory disease and central nervous system disease both remain formidable areas of research, there are several promising therapeutic approaches that could have a significant impact on the trajectory of treatment. This review will provide detailed insight on the novel drugs currently in use and those being explored in the management of BPDCN.
Benzenetriimide‐Based Molecular Conductor with Antiferro‐ to Ferromagnetic Switching Induced by Structural Change of π‐stacked Array
Authors: Koyama Shohei , Horii Yoji , Sato Tetsu , Takaishi Shinya , Hoshino Norihisa , Akutagawa Tomoyuki , Iguchi Hiroaki
Published: June 2022

Benzenetriimide (BTI) is a promising building block for materials chemistry due to its characteristic 3‐fold symmetry and redox properties, whereas little is known about its conductive and magnetic properties. In this study, we synthesized three charge‐transfer complexes based on N,N’,N’’‐trimethylbenzenetriimide (BTI‐Me). One of the complexes contains isolated dimers of BTI‐Me radical anion (BTI‐Me⋅−), while the other two have the infinite π‐stacked array of BTI‐Me with the formal charge of −0.5. The latter two complexes did not show metallic behavior but showed semiconducting behavior probably due to the characteristic insulation in one‐dimensional electron system, so‐called charge ordering and dimer‐Mott insulation. The magnetic susceptibility of the complex in dimer‐Mott state exhibits an unusual transition from antiferromagnetic to ferromagnetic spin states with the hysteresis loop of 15 K derived from the structural phase transition around 130 K. These properties were also supported by DFT calculations.
Simple Halogen‐Free, Biobased Organic Salts Convert Glycidol to Glycerol Carbonate under Atmospheric CO2 Pressure
Authors: Poolwong Jitpisut , Aomchad Vatcharaporn , Del Gobbo Silvano , Kleij Arjan W. , D'Elia Valerio
Published: June 2022

Glycerol carbonate (GC) has emerged as an attractive synthetic target due to various promising technological applications. Among several viable strategies to produce GC from CO2 and glycerol and its derivatives, the cycloaddition of CO2 to glycidol represents an atom‐economic an efficient strategy that can proceed via a halide‐free manifold through a proton‐shuttling mechanism. Here, it was shown that the synthesis of GC can be promoted by bio‐based and readily available organic salts leading to quantitative GC formation under atmospheric CO2 pressure and moderate temperatures. Comparative and mechanistic experiments using sodium citrate as the most efficient catalyst highlighted the role of both hydrogen bond donor and weakly basic sites in the organic salt towards GC formation. The citrate salt was also used as a catalyst for the conversion of other epoxy alcohols. Importantly, the discovery that homogeneous organic salts catalyze the target reaction inspired us to use metal alginates as heterogeneous and recoverable bio‐based catalysts for the same process.
A proposed theoretical framework for retinal biomarkers
Authors: MacCormick Ian James Callum , Zhang Bo , Hill Daniel , Cordeiro Maria Francesca , Small Dylan S.
Published: June 2022

Objective

Propose a theoretical framework for retinal biomarkers of Alzheimer's disease (AD).

Background

The retina and brain share important biological features that are relevant to AD. Developing retinal biomarkers of AD is a strategic priority but as yet none have been validated for clinical use. Part of the reason may be that fundamental inferential assumptions have been overlooked. Failing to recognize these assumptions will disadvantage biomarker discovery and validation, but incorporating them into analyses could facilitate translation.

New theory

The biological assumption that a disease causes analogous effects in the brain and retina can be expressed within a Bayesian network. This allows inferences about abstract theory and individual events, and provides an opportunity to falsify the foundational hypothesis of retina–brain analogy. Graphical representation of the relationships between variables simplifies comparison between studies and facilitates judgements about whether key assumptions are valid given the current state of knowledge.

Major challenges

The framework provides a visual approach to retinal biomarkers and may help to rationalize analysis of future studies. It suggests possible reasons for inconsistent results in existing literature on AD biomarkers.

Linkage to other theories

The framework can be modified to describe alternative theories of retinal biomarker biology, such as retrograde degeneration resulting from brain disease, and can incorporate confounding factors such as co‐existent glaucoma or macular degeneration. Parallels with analogue confirmation theory and surrogate marker validation suggest strengths and weaknesses of the framework that can be anticipated when developing analysis plans.

Highlights

Retinal biomarkers hold great promise for Alzheimer's disease (AD), but none are currently used clinically.

Assumptions about the cause of retinal and brain changes are often overlooked, and this may disadvantage biomarker discovery and validation.

We present a new approach to retinal biomarkers that describes cause and effect graphically in a Bayesian network.

We show how this allows a more complete assessment of how well a biomarker might reflect the brain, and how data from right and left eyes can be used to rule out poor biomarker candidates.
A case of obstructive jaundice caused by metastasis of breast cancer to the intra/extrahepatic bile duct
Authors: Suzuki Yuka , Hoshi Koki , Tominaga Keiichi , Inaba Yasunori , Yoshinaga Tomonori , Kojimahara Shunsuke , Maki Ryuichi , Nemoto Rena , Tetsuka Yugo , Kawata Yosuke , Yamamiya Akira , Sugaya Takeshi , Iso Yukihiro , Takada‐Owada Atsuko , Ishida Kazuyuki , Goda Kenichi , Irisawa Atsushi
Published: June 2022

A 38‐year‐old woman was admitted to our hospital for a detailed examination of jaundice. Three years before, she had undergone a right total mastectomy and axillary lymph node dissection of her right breast because of cancer. Histopathological evaluation revealed invasive ductal carcinoma. Postoperatively, because multiple bone metastases were found, she underwent chemoradiotherapy. Endoscopic retrograde cholangiopancreatography was performed, which revealed widespread multiple stenoses with a smooth surface from the intrahepatic to the extrahepatic bile duct. A transpapillary biliary biopsy was performed. Histopathological examination revealed adenocarcinoma extending into the subepithelium of the bile duct. The obtained cancer cells were similar to those of the earlier invasive breast cancer. This rare case demonstrates bile duct metastasis of breast cancer with specific endoscopic retrograde cholangiopancreatography findings.
A head‐to‐head comparison between Guardian Connect and FreeStyle Libre systems and an evaluation of user acceptability of sensors in patients with type 1 diabetes
Authors: Yeoh Ester , Png Doanna , Khoo Jonathon , Chee Ying Jie , Sharda Puja , Low Serena , Lim Su Chi , Subramaniam Tavintharan
Published: June 2022

Aims

A user‐calibrated real‐time continuous glucose monitoring (rt‐CGM) system is compared to a factory‐calibrated flash glucose monitoring (FGM) system and assessed in terms of accuracy and acceptability in patients with type 1 diabetes (T1D).

Methods

Ten participants with T1D were enroled from a specialist diabetes centre in Singapore and provided with the Guardian Connect with Enlite Sensor (Medtronic, Northridge, CA, USA) and first‐generation Freestyle Libre System (Abbott Diabetes Care, Witney, UK), worn simultaneously. Participants had to check capillary blood glucose four times per day. At the end of week 1 and week 2, participants returned for data download and were given a user evaluation survey.

Results

Accuracy evaluation between Guardian Connect and Freestyle Libre includes the overall mean absolute relative difference value (9.7 ± 11.0% vs. 17.5 ± 10.9%), Clarke Error Grid zones A + B (98.6% vs. 98.1%), sensitivity (78.9% vs. 63.4%), and specificity (93.4% vs. 81.0%). Notably, time below range (<3.9 mmol/L) was 10.5% for FGM versus 2% for rt‐CGM. From the evaluation survey, 90% of participants perceived rt‐CGM to be accurate versus 40% for FGM, although the majority found both devices to be easy to use, educational, and useful in improving glycaemic control. However, due to the cost of sensors, only 30% were keen to use either device for continuous monitoring.

Conclusions

Although rt‐CGM was superior to FGM in terms of accuracy, the value of glucose trends in both devices is still useful in diabetes self‐management. Patients and clinicians may consider either technology depending on their requirements.
Precipitation versus temperature as phenology controls in drylands
Authors: Currier Courtney M. , Sala Osvaldo E.
Published: June 2022

Cycles of plant growth, termed phenology, are tightly linked to environmental controls. The length of time spent growing, bounded by the start and end of season, is an important determinant of the global carbon, water, and energy balance. Much focus has been given to global warming and consequences for shifts in growing‐season length in temperate regions. In conjunction with warming temperatures, altered precipitation regimes are another facet of climate change that have potentially larger consequences than temperature in dryland phenology globally. We experimentally manipulated incoming precipitation in a semiarid grassland for over a decade and recorded plant phenology at the daily scale for 7 years. We found precipitation to have a strong relationship with the timing of grass greenup and senescence but temperature had only a modest effect size on grass greenup. Pre‐season drought strongly resulted in delayed grass greenup dates and shorter growing‐season lengths. Spring and summer drought corresponded with earlier grass senescence, whereas higher precipitation accumulation over these seasons corresponded with delayed grass senescence. However, extremely wet conditions diluted this effect and caused a plateaued response. Deep‐rooted woody shrubs showed few effects of variable precipitation or temperature on phenology and displayed consistent annual phenological timing compared with grasses. Whereas rising temperatures have already elicited phenological consequences and extended growing‐season length for mid and high‐latitude ecosystems, precipitation change will be the major driver of phenological change in drylands that cover 40% of the land surface with consequences for the global carbon, water, and energy balance.
Foundational biodiversity effects propagate through coastal food webs via multiple pathways
Authors: Ramus Aaron P. , Lefcheck Jonathan S. , Long Zachary T.
Published: June 2022

Relatively few studies have attempted to resolve the pathways through which the effects of biodiversity on ecosystem functioning cascade from one trophic level to another. Here, we manipulated the richness of habitat‐forming seaweeds in a western Atlantic estuary to explore how changes in foundation species diversity affect the structure and functioning of the benthic consumer communities that they support. Structural equation modeling revealed that macroalgal richness enhanced invertebrate abundance, biomass, and diversity, both directly by changing the quality and palatability of the foundational substrate and indirectly by increasing the total biomass of available habitat. Consumer responses were largely driven by a single foundational seaweed, although stronger complementarity among macroalgae was observed for invertebrate richness. These findings with diverse foundational phyla extend earlier inferences from terrestrial grasslands by showing that biodiversity effects can simultaneously propagate through multiple independent pathways to maintain animal foodwebs. Our work also highlights the potential ramifications of human‐induced changes in marine ecosystems.
Water availability dictates how plant traits predict demographic rates
Authors: Stears Alice E. , Adler Peter B. , Blumenthal Dana M. , Kray Julie A. , Mueller Kevin E. , Ocheltree Troy W. , Wilcox Kevin R. , Laughlin Daniel C.
Published: June 2022

A major goal in ecology is to make generalizable predictions of organism responses to environmental variation based on their traits. However, straightforward relationships between traits and fitness are rare and likely to vary with environmental context. Characterizing how traits mediate demographic responses to the environment may enhance the predictions of organism responses to global change. We synthesized 15 years of demographic data and species‐level traits in a shortgrass steppe to determine whether the effects of leaf and root traits on growth and survival depended on seasonal water availability. We predicted that (1) species with drought‐tolerant traits, such as lower leaf turgor loss point (TLP) and higher leaf and root dry matter content (LDMC and RDMC), would be more likely to survive and grow in drier years due to higher wilting resistance, (2) these traits would not predict fitness in wetter years, and (3) traits that more directly measure physiological mechanisms of water use such as TLP would best predict demographic responses. We found that graminoids with more negative TLP and higher LDMC and RDMC had higher survival rates in drier years. Forbs demonstrated similar yet more variable responses. Graminoids grew larger in wetter years, regardless of traits. However, in both wet and dry years, graminoids with more negative TLP and higher LDMC and RDMC grew larger than less negative TLP and low LDMC and RDMC species. Traits significantly mediated the impact of drought on survival, but not growth, suggesting that survival could be a stronger driver of species' drought response in this system. TLP predicted survival in drier years, but easier to measure LDMC and RDMC were equal or better predictors. These results advance our understanding of the mechanisms by which drought drives population dynamics, and show that abiotic context determines how traits drive fitness.
Stream and ocean hydrodynamics mediate partial migration strategies in an amphidromous Hawaiian goby
Authors: Lisi Peter J. , Hogan J. Derek , Holt Galen , Moody Kristine N. , Wren Johanna L. K. , Kobayashi Donald R. , Blum Michael J. , McIntyre Peter B.
Published: June 2022

Partial migration strategies, in which some individuals migrate but others do not, are widely observed in populations of migratory animals. Such patterns could arise via variation in migratory behaviors made by individual animals, via genetic variation in migratory predisposition, or simply by variation in migration opportunities mediated by environmental conditions. Here we use spatiotemporal variation in partial migration across populations of an amphidromous Hawaiian goby to test whether stream or ocean conditions favor completing its life cycle entirely within freshwater streams rather than undergoing an oceanic larval migration. Across 35 watersheds, microchemical analysis of otoliths revealed that most adult Awaous stamineus were freshwater residents (62% of n = 316 in 2009, 83% of n = 274 in 2011), but we found considerable variation among watersheds. We then tested the hypothesis that the prevalence of freshwater residency increases with the stability of stream flows and decreases with the availability of dispersal pathways arising from ocean hydrodynamics. We found that streams with low variation of daily discharge were home to a higher incidence of freshwater residents in each survey year. The magnitude of the shift in freshwater residency between survey years was positively associated with predicted interannual variability in the success of larval settlement in streams on each island based on passive drift in ocean currents. We built on these findings by developing a theoretical model of goby life history to further evaluate whether mediation of migration outcomes by stream and ocean hydrodynamics could be sufficient to explain the range of partial migration frequency observed across populations. The model illustrates that the proportion of larvae entering the ocean and differential survival of freshwater‐resident versus ocean‐going larvae are plausible mechanisms for range‐wide shifts in migration strategies. Thus, we propose that hydrologic variation in both ocean and stream environments contributes to spatiotemporal variation in the prevalence of migration phenotypes in A. stamineus. Our empirical and theoretical results suggest that the capacity for partial migration could enhance the persistence of metapopulations of diadromous fish when confronted with variable ocean and stream conditions.
Enantioselective Dual Catalysis of N‐Heterocyclic Carbene and Hydrogen‐Bond Donor Organocatalysts
Authors: Wang Hongling , Chi Yonggui Robin , Huang Xuan
Published: June 2022

N‐heterocyclic carbene (NHC) catalysis has become a versatile catalysis strategy for building molecules via unique reaction modes. Dual catalytic processes using NHCs in combination with additional modulating agents such as another organocatalyst or transition‐metal catalyst have also been studied. The clear selection of cocatalysts has led to enhanced reactivity, increased yields, and/or improved stereoselectivity. This minireview is to provide readers with a brief overview of the development and applications of NHC and hydrogen‐bond donor for dual catalytic reactions.
A meta‐analysis of the associations of elements of the fear‐avoidance model of chronic pain with negative affect, depression, anxiety, pain‐related disability and pain intensity
Authors: Rogers Andrew H. , Farris Samantha G.
Published: June 2022

Background and objective

Biopsychosocial conceptualizations of clinical pain conditions recognize the multi‐faceted nature of pain experience and its intersection with mental health. A primary cognitive‐behavioural framework is the Fear‐Avoidance Model, which posits that pain catastrophizing and fear of pain (including avoidance, cognitions and physiological reactivity) are key antecedents to, and drivers of, pain intensity and disability, in addition to pain‐related psychological distress. This study aimed to provide a comprehensive analysis of the magnitude of the cross‐sectional association between the primary components of the Fear‐Avoidance Model (pain catastrophizing, fear of pain, pain vigilance) with negative affect, anxiety, depression, pain intensity and disabilities in studies of clinical pain.

Databases and data treatment

A search of MEDLINE and PubMed databases resulted in 335 studies that were evaluated in this meta‐analytic review, which represented 65,340 participants.

Results

Results from the random effect models indicated a positive, medium‐ to large‐sized association between fear of pain, pain catastrophizing, and pain vigilance measures and outcomes (pain‐related negative affect, anxiety, depression and pain‐related disability) and medium‐sized associations with pain intensity. Fear of pain measurement type was a significant moderator of effects across all outcomes.

Conclusions

These findings provide empirical support, aligned with the components of the fear‐avoidance (FA) model, for the relevance of both pain catastrophizing and fear of pain to the pain experience and its intersection with mental health. Implications for the conceptualization of the pain catastrophizing and fear of pain construct and its measurement are discussed.

Significance

This meta‐analysis reveals that, among individuals with various pain conditions, pain catastrophizing, fear of pain, and pain vigilance have medium to large associations with pain‐ related negative affect, anxiety, and depression, pain intensity and disability. Differences in the strength of the associations depend on the type of self‐report tool used to assess fear of pain.
How the characteristics of pediatric neurologists in Latin America influence the communication of sudden unexpected death in epilepsy to patients and caregivers
Authors: Venegas Viviana , Manterola Carla , De Pablo Jose , Garcia Mariano , de León Sonia Ponce , Cavada Gabriel
Published: June 2022

Objective

This study aimed to describe the characteristics of pediatric neurologists (PNs) in Latin America (LA) who attend to children and adolescents with epilepsy and convey to them the risk of sudden unexpected death in epilepsy (SUDEP).

Methods

Personal data and details of discussion of SUDEP with families, including relevance of SUDEP disclosure, frequency of such communication, perceived benefits and risks of disclosure, extent of training received on such disclosure, and professional experience with SUDEP, were collected through an online survey of PNs from LA. Their personal experience in carrying out this conversation was obtained through responses to an open question, further used to identify the main barriers.

Results

Of the 442 surveys received, 367 (83%) were analyzed. Most participants (73.8%) responded that the communication of SUDEP risk was relevant or very relevant; however, only 17.9% reported communicating it always or very frequently. Factors that increased the frequency of SUDEP communication included patients with higher levels of complexity (OR = 2.18, P = .003) and the physician's personal experience with SUDEP (OR = 2.305, P < .001). Direct questions from the family and avoiding scaring them about a rare outcome were the main motivations behind discussing and not discussing SUDEP, respectively. In the open question, respondents identified worries about the patient's ability to understand the information and cultural gaps as barriers. “Informing with the intention of improving adherence to treatment” and “establishing an empathic relationship” were significantly related. Further, the concept of “do not scare” was significantly related to “personal difficulties in discussing SUDEP.”

Significance

Although most PNs agree that communication about SUDEP is relevant, only a minority actually engages in it. Participants identified a lack of appropriate training in such communication as a barrier. A better understanding of communication expectations, education of health professionals, and communication techniques have a strong relevance in diminishing the gap between guidelines and practice.
Internal flow field and rock‐breaking characteristics of a straight‐swirling mixed jet and its influential factors in radial jet drilling
Authors: Du Peng , Peng Xiaofan , Wei Zhidong , Fan Qinglong
Published: June 2022

The use of radial jet drilling (RJD) to exploit unconventional natural gas is an attractive study area. A self‐propelled bit enormously affects the drilling efficiency. Herein, for a straight‐swirling mixed jet (SSMJ) bit, the internal and external velocity fields were analyzed using a simulation to reveal a jet mixed mechanism. The rock‐breaking characteristics of different bit structures were investigated using laboratory experiments. A straight jet and a swirling jet were independent flowing through the impeller and were gradually mixed together in the mixing chamber inside the bit. The jets' boundary gradually dissipated along the radial direction, and the swirling jet distribution along the circumferential direction tended to be uniform. The velocity vector gradually decreased from the center to the periphery, and the energies were slowly concentrated due to the cluster‐narrowing by the conical wall until the velocity at the nozzle outlet reached its peak. Different flow fields were modulated by changing the bit structures. The diameters ratio greatly affected the distribution proportion of straight and swirling; the length‐diameter ratio primarily affected the contribution of the swirling jet to its center, and the width‐diameter ratio chiefly affected the initial formation velocity of the swirling jet, which all directly affected the depth variation along the radial and diameter of a borehole. The hole depth and diameter, erosion volume, and bottom flatness were combined to evaluate the rock‐breaking performance. The bit with a diameters ratio of 0.67, a length‐radius ratio of 0.57, and the width‐radius ratio of 0.13 had the best erosion effect. The simulation and experimental results achieved good mutual verifications. Overall, this study can guide research on the SSMJ rock‐breaking mechanism and bit design for RJD.
The impact of excessive protein consumption on human wastewater nitrogen loading of US waters
Authors: Almaraz Maya , Kuempel Caitlin D , Salter Andrew M , Halpern Benjamin S
Published: June 2022

Total and per capita protein consumption rates in US diets, whether from plant or animal sources, rank among the highest in the world. When protein consumption outpaces physiologic protein demands, excess amino acids are degraded in the human body and nitrogen (N) is excreted and released to the environment, mainly in the form of urea. Such excess reactive N can enter downstream environments, thereby impairing human and ecosystem health as well as contributing to economic losses. We show that matching protein consumption with physiologic requirements would reduce US hydrologic N losses to aquatic ecosystems by 12% and overall (atmospheric and hydrologic) N losses to ecosystems by 4%. Were US citizens to consume protein at recommended rates, projected N excretion rates in 2055 would be 27% less than they are today, despite population growth. Optimizing US protein consumption to levels that meet human health standards has environmental benefits on par with improving wastewater treatment using existing technology, while also generating impactful economic benefits.
Phase‐resolving direct numerical simulations of particle transport in liquids—From microfluidics to sediment
Authors: Fröhlich Jochen , Hafemann Thomas E. , Jain Ramandeep
Published: June 2022

The article describes direct numerical simulations using an Euler–Lagrange approach with an immersed‐boundary method to resolve the geometry and trajectory of particles moving in a flow. The presentation focuses on own work of the authors and discusses elements of physical and numerical modeling in some detail, together with three areas of application: microfluidic transport of spherical and nonspherical particles in curved ducts, flows with bubbles at different void fraction ranging from single bubbles to dense particle clusters, some also subjected to electro‐magnetic forces, and bedload sediment transport with spherical and nonspherical particles. These applications with their specific requirements for numerical modeling illustrate the versatility of the approach and provide condensed information about main findings.
Post‐entry internationalization speed, learning speed, and performance: A meta‐analytic review and theory extension
Authors: Huang Sheng , Ding Zhenkuo , Lin Xiaoman , Zhu Yunxia
Published: June 2022

Research Summary

The impact of post‐entry internationalization speed (PIS) on firm performance has become a central issue in global strategy research. This paper conducts a meta‐analysis concerning the relationships between two dimensions (i.e., international commitment speed and international scope speed) of PIS and performance, and the moderating effects of learning speed on these relationships among international firms. Empirical evidence from 60 independent samples reveals that international commitment speed positively influences performance, while international scope speed has an inverted U‐shaped impact on performance. Our results also indicate that learning speed negatively moderates the link between international commitment speed and performance, whereas it positively moderates the association between international scope speed and performance. Based on the findings, we discuss the contributions to the global strategy literature, organizational learning theory and time‐based competition view, and point at future research directions systematically.

Managerial Summary

We analyze the relationships between two types (i.e., international commitment speed and international scope speed) of post‐entry internationalization speed (PIS) and performance among international firms. We find that accelerating international commitment speed facilitates performance, while expediting international scope speed first facilitates and then inhibits performance. We also find that learning speed weakens the positive influence of international commitment speed on performance, whereas it strengthens the association between international scope speed and performance. These findings have important implications for managers in international firms seeking to achieve superior firm performance.
Noncellular components in the liver cancer stem cell niche: Biology and potential clinical implications
Authors: Lam Ka‐Hei , Ma Stephanie
Published: June 2022

Cancer stem cells (CSCs) are now recognized as one of the major root causes of therapy failure and tumor recurrence in hepatocellular carcinoma (HCC). Early studies in the field focused primarily on the intrinsic regulators of CSC maintenance, but in recent years, mounting evidence has demonstrated the presence and role of extrinsic regulators in the tumor microenvironment (TME) in the control of liver CSCs. In addition to direct interaction with cellular components, noncellular components, including the extracellular matrix, hypoxia, nutrient deprivation, and secreted molecules within the tumor stroma and hepatitis viruses, also play a critical role in shaping the CSC niche. In this review, we highlight how various noncellular components in the TME play a role in regulating CSCs and how CSCs secrete components to interact with the TME to generate their own niche, working hand in hand to drive tumor physiology in HCC. In addition, we describe the potential clinical applications of these findings and propose perspectives on future research of noncellular components in the liver CSC niche.
Acute portal hypertension using portal vein ligation abrogates TRAIL expression of liver‐resident NK cells
Authors: Imaoka Yuki , Sato Koki , Ohira Masahiro , Imaoka Kouki , Yano Takuya , Nakano Ryosuke , Tanaka Yuka , Ohdan Hideki
Published: June 2022

The effects of acute portal hypertension (PHT), which is reported as poor prognostic factors in patients with hepatocellular carcinoma, are not well known on the liver immune system, including natural killer (NK) cells. The aim of this study, therefore, was to investigate how acute PHT influences the functions and characteristics of liver‐resident NK (lr‐NK) cells using an acute PHT mouse model. Acute PHT decreased the number of tumor necrosis factor–related apoptosis‐inducing ligand (TRAIL+) lr‐NK cells by about 20% and attenuated cytotoxic activity against the Hepa1‐6 cell line by about 40%. Among various cytokine, only interleukin‐33 (IL‐33), which inhibits NK activity, significantly increased after portal vein ligation (PVL). Because lr‐NK cells highly expressed ST2/IL‐33R, IL‐33 co‐culture significantly suppressed TRAIL expression on lr‐NK cells by about 50%, and IL‐33 administration markedly decreased TRAIL expression and cytotoxic activity of lr‐NK cells. Furthermore, the TRAIL+ NK cells population was maintained by anti‐IL33 antibody or following portosystemic shunt procedure even after PVL. Finally, we demonstrated that IL‐33 decreased TRAIL expression in lr‐NK cells via AKT–forkhead box O (FoxO) and mitogen‐activated protein kinase (MAPK) signaling. Conclusion: This work demonstrates that PHT suppresses the TRAIL+ lr‐NK cell population and antitumor activities in the liver. Additionally, Akt‐FoxO and MAPK signaling pathways attenuate the TRAIL expression in lt‐NK cells via IL‐33 receptor in mice.
Recent Developments in the Applications of Biomass‐Derived Sulfonated Carbonaceous Solid Acid Catalysts
Authors: Kirdant Swapnali P. , Biradar Tamboli Asma T. , Jadhav Vrushali H.
Published: June 2022

Recently, carbon‐based materials are gaining a lot of attraction. It is considered as an emerging area of research and has gained significant importance as an efficient catalyst/material in various fields. Biomass is abundantly available, cheap and a renewable carbon resource. Sulfonated carbonaceous solid acid catalyst can be derived by sulfonation of various sources of biomass such as sugars, lignin, fruit waste, agro‐waste, bio‐char, etc. Sulfonated carbonaceous solid acid catalysts can be used as a substitute to liquid acids. These catalysts possess a stable carbon skeleton and are insoluble in almost all organic solvents as well as under acidic/basic conditions. This review covers details about biomass‐derived sulfonated carbonaceous solid acid catalysts and its catalytic activities in many important transformations such as hydrolysis of cellulose, synthesis of biodiesel, synthesis of various important chemicals and for various organic transformations.
Gram‐Scale Synthesis, Isolation and Characterisation of Sodium Organometallics:nBuNa and NaTMP
Authors: Tortajada Andreu , Anderson David E. , Hevia Eva
Published: June 2022

Organolithium compounds represent one of the most widely utilised commodity reagents in synthetic chemistry. However, their analogues with the heavier alkali‐metal sodium are much less utilised and their reactivity is less understood. Recent studies have shown the excellent potential of organosodium reagents in synthesis, finding widespread applications in cornerstone organic transformations such as deprotonative metalation, metal‐halogen exchange or Pd catalysed C−C bond formation. However, detailed procedures for the preparation of these compounds are scarce. Therefore, we report a step‐by‐step synthesis of two organosodium reagents:nBuNa and NaTMP (TMP=2,2,6,6‐tetramethylpiperidide) as key building blocks in sodium organometallics, which allows the easy access to other sodiated compounds and enables chemical reactivity that is not feasible with organolithium compounds. Both can be prepared in high yields (up to 92 %), and isolated as pure solids that can be stored under argon for long periods of time (up to six months) without observed degradation. Here we further illustrate the synthetic utility of NaTMP as an efficient metalating reagent for 1‐methoxynaphthalene which can be subsequently employed inSuzuki–Miyauracouplings, as well as a precursor for sodium zincate [(TMEDA)NaZn(TMP)Et2], which has been obtained by co‐complexation of NaTMP, ZnEt2and TMEDA in hexane, for which a structure has been established by X‐ray crystallography.
Insights from a computational analysis of the SARS‐CoV‐2 Omicron variant: Host–pathogen interaction, pathogenicity, and possible drug therapeutics
Authors: Parvez Md Sorwer Alam , Saha Manash Kumar , Ibrahim Md. , Araf Yusha , Islam Md. Taufiqul , Ohtsuki Gen , Hosen Mohammad Jakir
Published: June 2022

Introduction

Prominently accountable for the upsurge of COVID‐19 cases as the world attempts to recover from the previous two waves, Omicron has further threatened the conventional therapeutic approaches. The lack of extensive research regarding Omicron has raised the need to establish correlations to understand this variant by structural comparisons. Here, we evaluate, correlate, and compare its genomic sequences through an immunoinformatic approach to understand its epidemiological characteristics and responses to existing drugs.

Methods

We reconstructed the phylogenetic tree and compared the mutational spectrum. We analyzed the mutations that occurred in the Omicron variant and correlated how these mutations affect infectivity and pathogenicity. Then, we studied how mutations in the receptor‐binding domain affect its interaction with host factors through molecular docking. Finally, we evaluated the drug efficacy against the main protease of the Omicron through molecular docking and validated the docking results with molecular dynamics simulation.

Results

Phylogenetic and mutational analysis revealed the Omicron variant is similar to the highly infectious B.1.620 variant, while mutations within the prominent proteins are hypothesized to alter its pathogenicity. Moreover, docking evaluations revealed significant differences in binding affinity with human receptors, angiotensin‐converting enzyme 2 and NRP1. Surprisingly, most of the tested drugs were proven to be effective. Nirmatrelvir, 13b, and Lopinavir displayed increased effectiveness against Omicron.

Conclusion

Omicron variant may be originated from the highly infectious B.1.620 variant, while it was less pathogenic due to the mutations in the prominent proteins. Nirmatrelvir, 13b, and Lopinavir would be the most effective, compared to other promising drugs that were proven effective.
Intratracheal instillation of graphene oxide decreases anti‐virus responses and lipid contents via suppressing Toll‐like receptor 3 in mouse livers
Authors: Tang Xiaomin , Song Fengmei , Zhao Weichao , Zhang Zhaohui , Cao Yi
Published: June 2022

Recent studies revealed a causal relationship between Toll‐like receptors (TLRs) and lipid droplet biogenesis. Interestingly, it has been reported before that nanomaterials (NMs) were capable to modulate TLRs, but it remains unclear if NMs could affect lipid levels via TLR signaling pathways. In this study, we investigated the influences of airway exposure to graphene oxide (GO) on TLR3 signaling pathways and lipid levels in mouse livers. Intratracheal instillation of GO (0.1, 1, and 5 mg/kg, once a day, totally 5 days) induced inflammatory cell infiltrations as indicated by hematoxylin–eosin (H&E) staining and fibrosis as indicated by Masson staining in lungs, accompanying with decreased TLR3 proteins. Consistently, a TLR3‐regulated anti‐virus protein, namely interferon induced protein with tetratricopeptide repeats 1 (IFIT1), as well as two TLR3‐regulated lipid proteins, namely radical S‐adenosyl methionine domain containing 2 (RSAD2) and perilipin 2 (PLIN2), were decreased in lungs. The protein levels of interferon‐β in serum were also decreased. In livers, GO exposure induced disorganization of liver cells but not fibrosis. In agreement with the trends observed in lungs, TLR3, IFIT1, RSAD2, and PLIN2 proteins were decreased in livers. As a possible consequence, GO exposure dose‐dependently decreased lipid levels in livers as indicated by oil red O and BODIPY 493/503 staining. We concluded that airway exposure to GO decreased anti‐virus responses and lipid levels in mouse livers via the suppression of TLR3.