Miracle-dz/UniFAR-FTUs huggingface dataset:
Making ATRP More Practical: Oxygen Tolerance.

ConspectusAtom-transfer radical polymerization (ATRP) is a well-known technique for the controlled polymerization of vinyl monomers under mild conditions. However, as with any other radical polymerization, ATRP typically requires rigorous oxygen exclusion, making it time-consuming and challenging to use by nonexperts. In this Account, we discuss various approaches to achieving oxygen tolerance in ATRP, presenting the overall progress in the field.Copper-mediated ATRP, which we first discovered in the late 1990s, uses a CuI/L activator that reversibly reacts with the dormant C(sp3)-X polymer chain end, forming a X-CuII/L deactivator and a propagating radical. Oxygen interferes with activation and chain propagation by quenching the radicals and oxidizing the activator. At ATRP equilibrium, the activator is present at a much higher concentration than the propagating radicals. Thus, oxidation of the activator is the dominant inhibition pathway. In conventional ATRP, this reaction is irreversible, so oxygen must be strictly excluded to achieve good results.Over the last two decades, our group has developed several ATRP techniques based on the concept of regenerating the activator. When the oxidized activator is continuously converted back to its active reduced form, then the catalytic system itself can act as an oxygen scavenger. Regeneration can be accomplished by reducing agents and photo-, electro-, and mechanochemical stimuli. This family of methods offers a degree of oxygen tolerance, but most of them can tolerate only a limited amount of oxygen and do not allow polymerization in an open vessel.More recently, we discovered that enzymes can be used in auxiliary catalytic systems that directly deoxygenate the reaction medium and protect the polymerization process. We developed a method that uses glucose oxidase (GOx), glucose, and sodium pyruvate to very effectively scavenge oxygen and enable open-vessel ATRP. By adding a second enzyme, horseradish peroxidase (HPR), we managed to extend the role of the auxiliary enzymatic system to generating carbon-based radicals and changed ATRP from an oxygen-sensitive to an oxygen-fueled reaction.While performing control experiments for the enzymatic methods, we noticed that using sodium pyruvate under UV irradiation triggers polymerization without the presence of GOx. This serendipitous discovery allowed us to develop the first oxygen-proof, small-molecule-based, photoinduced ATRP system. It has oxygen tolerance similar to that of the enzymatic methods, exhibits superior compatibility with both aqueous media and organic solvents, and avoids problems associated with purifying polymers from enzymes. The system was able to rapidly polymerize N-isopropylacrylamide, a challenging monomer, with a high degree of control.These contributions have substantially simplified the use of ATRP, making it more practical and accessible to everyone.
Higher Emotion Dysregulation and Coping Motives in Alcoholand Marijuana Users

Abstract Background: Prior research indicates that difficulties in emotion regulation may contribute to the use of substances (e.g. alcohol and marijuana) to alleviate negative affect. Therefore, we hypothesized that coping motives for alcohol and marijuana use would serve as an intermediary in the relationship between emotion dysregulation and alcohol/marijuana-related outcomes. Methods: The sample comprised 241 college students who used both alcohol and marijuana and 378 college students who used alcohol only. Parallel indirect effects models were estimated to test the hypothesis that emotion dysregulation is associated with alcohol and marijuana use/problems through alcohol and marijuana coping motives. Results: Coping motives were consistently identified as the driving intermediary when it came to alcohol and marijuana problems, as well as marijuana consumption. Enhancement motives were only implicated in the relationship between emotion dysregulation and alcohol consumption among the alcohol-only group. Conclusion: Overall, the pattern of results suggests that, as hypothesized, alcohol and/or marijuana users higher in emotion dysregulation are more likely to use alcohol or marijuana to alleviate negative affect. Although further research is warranted, individuals who use substances for coping purposes may benefit from interventions designed to improve emotion regulation skills.
Phytochemistry, pharmacodynamics, and pharmacokinetics of a classic Chinese herbal formula Danggui Beimu Kushen Wan: A review

Danggui Beimu Kushen Wan (DBKW) is a classic herbal formula for difficult urination and has been widely used for urinary‐related disorders and cancers in current clinical practice. This study aimed to comprehensively review the phytochemistry, pharmacodynamics, and pharmacokinetics of DBKW in experimental studies. We searched 21 databases to identify experimental studies of DBKW. We also searched 11 databases to identify and summarize compounds from DBKW's ingredients. A total of 423 studies of DBKW were identified and 15 studies were included. For Angelicae Sinensis Radix (ASR) and Sophorae Flavescentis Radix (SFR), 2,425 and 2,843 studies were identified, and 42 and 33 studies were included, respectively. Eight compounds were found in the whole formula, 408 compounds from ASR, and 277 compounds from SFR. DBKW may have anticancer effects (inhibiting the growth of tumors, regulating cell proliferation, inducing tumor cell apoptosis, suppressing invasion and metastasis of cancer, enhancing the therapeutic effects of chemotherapy, and relieving toxicity of chemotherapy) and have benefits on chronic prostatitis (reducing inflammation, inhibiting oxidation, regulating sex hormone, and stimulating immune system). The pharmacokinetics of the seven primary compounds from DBKW were also summarized. DBKW contains multiple compounds that may act on more than one pathway of the conditions simultaneously.
Metabarcoding Reveals Changes in Benthic Eukaryote and Prokaryote Community Composition along a Tropical Marine Sediment Nickel Gradient

The Southeast Asia and Melanesia region has extensive nickel (Ni)‐rich lateritic regoliths formed from the tropical weathering of ultramafic rocks. As the global demand for Ni continues to rise, these lateritic regoliths are increasingly being exploited for their economic benefit. Mining of these regoliths contributes to the enrichment of coastal sediments in trace metals, especially Ni. The present study used high‐throughput sequencing (metabarcoding) to determine changes in eukaryote (18s v7 recombinant DNA [rDNA] and diatom‐specific subregion of the 18s v4 rDNA) and prokaryote (16s v4 rDNA) community compositions along a sediment Ni concentration gradient offshore from a large lateritized ultramafic regolith in New Caledonia (Vavouto Bay). Significant changes in the eukaryote, diatom, and prokaryote community compositions were found along the Ni concentration gradient. These changes correlated most with the dilute‐acid extractable concentration of Ni in the sediments, which explained 26, 23, and 19% of the variation for eukaryote, diatom, and prokaryote community compositions, respectively. Univariate analyses showed that there was no consistent change in indices of biodiversity, evenness, or richness. Diatom richness and diversity did, however, decrease as sediment acid extractable‐Ni concentrations increased. Threshold indicator taxa analysis was conducted separately for each of the 3 targeted genes to detect changes in taxa whose occurrences decreased or increased along the acid extractable‐Ni concentration gradient. Based on these data, 46 mg acid extractable‐Ni/kg was determined as a threshold value where sensitive species began to disappear. In the case of the estuarine sediments offshore from lateritized ultramafic regolith in New Caledonia, this is recommended as an interim threshold value until further lines of evidence can contribute to a region‐specific Ni sediment quality guideline value. Environ Toxicol Chem 2021;40:1892–1905. © 2021 SETAC
Ashmole's hypothesis and the latitudinal gradient in clutch size

One enduring priority for ecologists has been to understand the cause(s) of variation in reproductive effort among species and localities. Avian clutch size generally increases with increasing latitude, both within and across species, but the mechanism(s) driving that pattern continue to generate hypotheses and debate. In 1961, a Ph.D. student at Oxford University, N. Philip Ashmole, proposed the influential hypothesis that clutch size varies in direct proportion to the seasonality of resources available to a population. Ashmole's hypothesis has been widely cited and discussed in the ecological literature. However, misinterpretation and confusion has been common regarding the mechanism that underlies Ashmole's hypothesis and the testable predictions it generates. We review the development of well‐known hypotheses to explain clutch size variation with an emphasis on Ashmole's hypothesis. We then discuss and clarify sources of confusion about Ashmole's hypothesis in the literature, summarise existing evidence in support and refutation of the hypothesis, and suggest some under‐utilised and novel approaches to test Ashmole's hypothesis and gain an improved understanding of the mechanisms responsible for variation in avian clutch size and fecundity, and life‐history evolution in general.
On phase equilibrium at the gas‐liquid interface during absorption

That phase equilibrium exists at the gas-liquid interface during gas absorption is usually assumed in the analysis and design of absorption equipment, but the validity of this assumption has been in doubt since Higbie's pioneering gas-absorption studies. Accurate measurements are reported herein of the absorption rates at 25°C. of carbon dioxide into short water jets in which the liquid was in laminar flow. The jets issued from circular nozzles of about 1.5-mm. diam. , flowed intact downward through an atmosphere of carbon dioxide at average velocities of from 75 to 550 cm. /sec. over distances of 1 to 15 cm. , and were collected in a receiver slightly larger in diameter than the nozzles. The measured absorption rates are in excellent agreement with predictions based on unsteady state diffusion theory, when one assumes interfacial equilibrium. It is concluded from these results and those of other investigators that equilibrium prevails at a freshly formed, relatively clean, carbon dioxide–water interface and that the same statement probably applies to the absorption of other slightly soluble gases in water. Evidence is discussed which indicates that an accumulation of minute quantitities of surface-active materials may seriously reduce the rate of gas absorption, either by affecting the hydrodynamic characteristics of the system or perhaps by offering resistance to the transfer of solute molecules across the interface.
Template-Directed Rapid Synthesis of Pd-Based Ultrathin Porous Intermetallic Nanosheets for Efficient Oxygen Reduction.

Atomically ordered intermetallic nanoparticles often exhibit improved catalytic activity and durability relative to their random alloy counterparts due to the intensified interatomic interaction. However, the conventional methods that involve the time-consuming and high-temperature syntheses only have rudimentary capability in controlling over the structure of intermetallic nanoparticles, hindering the advances of intermetallic nanocatalysts. Herein, we report a template-directed strategy for rapid synthesis of Pd-based (PdM, M = Pb, Sn and Cd) ultrathin porous intermetallic nanosheets (UPINs) with tunable sizes. The essence of this strategy lies in the use of preformed seeds in the synthesis, which act as the template to control the deposition of foreign atoms and the subsequent interatomic diffusion. Using the oxygen reduction reaction (ORR) as a model reaction, the as-synthesized Pd 3 Pb UPINs exhibit superior activity, durability, and methanol tolerance. The favored geometrical structure and interatomic interaction between Pd and Pb in Pd 3 Pb UPINs are concluded to account for the enhanced ORR performance. We believe this template-directed synthetic strategy is a universal route for shape-controlled synthesis of intermetallic nanocrystals and will provide new opportunities for intermetallic nanocatalysts.
How Comparable are Microbial Electrochemical Systems around the Globe? An Electrochemical and Microbiological Cross‐Laboratory Study

Abstract A cross‐laboratory study on microbial fuel cells (MFC) which involved different institutions around the world is presented. The study aims to assess the development of autochthone microbial pools enriched from domestic wastewater, cultivated in identical single‐chamber MFCs, operated in the same way, thereby approaching the idea of developing common standards for MFCs. The MFCs are inoculated with domestic wastewater in different geographic locations. The acclimation stage and, consequently, the startup time are longer or shorter depending on the inoculum, but all MFCs reach similar maximum power outputs (55±22 μW cm−2) and COD removal efficiencies (87±9 %), despite the diversity of the bacterial communities. It is inferred that the MFC performance starts when the syntrophic interaction of fermentative and electrogenic bacteria stabilizes under anaerobic conditions at the anode. The generated power is mostly limited by electrolytic conductivity, electrode overpotentials, and an unbalanced external resistance. The enriched microbial consortia, although composed of different bacterial groups, share similar functions both on the anode and the cathode of the different MFCs, resulting in similar electrochemical output.
‘That decision really was mine…’. Insider perspectives on health care controversies about intersex/diverse sex development

Abstract After 20 years of debate on intersex care, there has been a slight movement away from the paradigm of ‘optimal gender’ including early genital modification to conform to predicted gender identity towards a paradigm of ‘full consent’ including the provision of full information about the risks, benefits and alternatives to interventions and the postponement of irreversible interventions on minors too young to give informed consent. However, controversy continues. Against this background, the aim of this study was to analyse core aspects of current debates in intersex care. Focus was placed on controversies about surgery on external genitalia; gonadectomies; the expressed wishes of patients under the age of consent; and how to deal with intersex within the family. Eight guideline-based interviews were conducted with two people with intersex/diverse sex development conditions who had been subjected to surgery, two parents of children with an intersex/dsd condition, two medical doctors, and two psychologists. Data were analysed thematically. Findings indicate that while ‘full consent’ influenced actions and debate, the persons involved held differing opinions about how this policy can or should be achieved. In addition, the data illustrated how concepts such as normalcy, identity and sexuality are relevant when dealing with intersex issues.
Randomized multi-reader evaluation of automated detection and segmentation of brain tumors in stereotactic radiosurgery with deep neural networks

Abstract Background Stereotactic radiosurgery (SRS), a validated treatment for brain tumors, requires accurate tumor contouring. This manual segmentation process is time-consuming and prone to substantial inter-practitioner variability. Artificial intelligence (AI) with deep neural networks have increasingly been proposed for use in lesion detection and segmentation but have seldom been validated in a clinical setting. Methods We conducted a randomized, cross-modal, multi-reader, multispecialty, multi-case study to evaluate the impact of AI assistance on brain tumor SRS. A state-of-the-art auto-contouring algorithm built on multi-modality imaging and ensemble neural networks was integrated into the clinical workflow. Nine medical professionals contoured the same case series in two reader modes (assisted or unassisted) with a memory washout period of 6 weeks between each section. The case series consisted of 10 algorithm-unseen cases, including five cases of brain metastases, three of meningiomas, and two of acoustic neuromas. Among the nine readers, three experienced experts determined the ground truths of tumor contours. Results With the AI assistance, the inter-reader agreement significantly increased (Dice similarity coefficient [DSC] from 0.86 to 0.90, P < 0.001). Algorithm-assisted physicians demonstrated a higher sensitivity for lesion detection than unassisted physicians (91.3% vs 82.6%, P = .030). AI assistance improved contouring accuracy, with an average increase in DSC of 0.028, especially for physicians with less SRS experience (average DSC from 0.847 to 0.865, P = .002). In addition, AI assistance improved efficiency with a median of 30.8% time-saving. Less-experienced clinicians gained prominent improvement on contouring accuracy but less benefit in reduction of working hours. By contrast, SRS specialists had a relatively minor advantage in DSC, but greater time-saving with the aid of AI. Conclusions Deep learning neural networks can be optimally utilized to improve accuracy and efﬁciency for the clinical workflow in brain tumor SRS.
The Relationship between Early Alcohol Use Behaviors and Adolescent Pubertal and Psychosocial Development: A Latent Growth Analysis

Abstract Objective The present longitudinal study examines how age of alcohol initiation and regular use (weekly drinking for ≥6 months) relates to adolescent physiological development, social behaviors, psychological functioning, and substance use patterns. Method: Data are drawn from a prospective sample of 295 youth (42% female) who completed a 15-year longitudinal study. The current investigation uses data collected at 4 timepoints from ages 12–19. Results: Latent growth modeling revealed earlier age of alcohol initiation is associated with (1) a more advanced stage of pubertal development, more self-reported dating experience, and greater externalizing behaviors at ages 12–13 (study entry); (2) a slower rate of change in pubertal development; and (3) greater rate of increase in externalizing and internalizing symptoms from ages 12 to 19. These relationships were not moderated by gender. Conclusion: Early alcohol initiation appears to be associated with early onset pubertal development and dating behaviors. Over time, early alcohol use behaviors may delay pubertal development while exacerbating psychological risk behaviors (i.e. externalizing and internalizing behaviors). These findings suggest the importance of delaying alcohol initiation and may be beneficial for improving existing adolescent substance use prevention efforts.
The structure of the native cardiac thin filament at systolic Ca2+ levels

Significance Heartbeats rely on cyclical interactions between myosin thick and actin thin filaments orchestrated by rising and falling Ca2+. During systole, Ca2+ binds to the thin filament and allows its interaction with the thick filament to produce force required for contraction. The structure of the thin filament at physiological Ca2+ levels is unknown, which limits our understanding of the thin filament regulation by Ca2+. Here, we directly observe thin filament structural states along individual filaments at systolic Ca2+ levels to show that the thin filament is activated stochastically with short-range cooperativity evident only on one strand of the thin filament. We suggest how cardiac muscle can be regulated by a narrow range of Ca2+ levels upon transition from diastole to systole. Every heartbeat relies on cyclical interactions between myosin thick and actin thin filaments orchestrated by rising and falling Ca2+ levels. Thin filaments are comprised of two actin strands, each harboring equally separated troponin complexes, which bind Ca2+ to move tropomyosin cables away from the myosin binding sites and, thus, activate systolic contraction. Recently, structures of thin filaments obtained at low (pCa ∼9) or high (pCa ∼3) Ca2+ levels revealed the transition between the Ca2+-free and Ca2+-bound states. However, in working cardiac muscle, Ca2+ levels fluctuate at intermediate values between pCa ∼6 and pCa ∼7. The structure of the thin filament at physiological Ca2+ levels is unknown. We used cryoelectron microscopy and statistical analysis to reveal the structure of the cardiac thin filament at systolic pCa = 5.8. We show that the two strands of the thin filament consist of a mixture of regulatory units, which are composed of Ca2+-free, Ca2+-bound, or mixed (e.g., Ca2+ free on one side and Ca2+ bound on the other side) troponin complexes. We traced troponin complex conformations along and across individual thin filaments to directly determine the structural composition of the cardiac native thin filament at systolic Ca2+ levels. We demonstrate that the two thin filament strands are activated stochastically with short-range cooperativity evident only on one of the two strands. Our findings suggest a mechanism by which cardiac muscle is regulated by narrow range Ca2+ fluctuations.
Genetic pleiotropy and the shared pathological features of corticobasal degeneration and progressive supranuclear palsy: a case report and a review of the literature

ABSTRACT Though distinct pathological entities, corticobasal degeneration (CBD) and progressive supranuclear palsy (PSP) share multiple biochemical and genetic features suggesting overlapping pathophysiology. We report the case of a patient with an 18-year clinical course consistent with behavioral variant frontotemporal dementia. The neuropathological assessment revealed unclassifiable frontotemporal lobar degeneration with tau-immunoreactive inclusions sharing features of both CBD and PSP. Whole-genome sequencing revealed a unique combination of pleiotropic genetic risk variants associated with both PSP and CBD. These findings support the observation that CBD and PSP share genetic co-expression networks that influence neurodegenerative pathogenesis common to 4R tauopathies.
Recent Developments in Raman Optical Activity of Biopolymers

Recent advances in Raman optical activity (ROA) instrumentation are outlined which have enhanced significantly the quality of vibrational ROA spectra of biopolymers in aqueous solution. Peptides, proteins, carbohydrates, glycoproteins, and nucleic acids now provide excellent ROA spectra which contain detailed information about solution structure. ROA spectra can be measured just as easily in D2O as in H2O solution, and, as illustrated for bovine serum albumin and concanavalin A, a comparison of the two can be highly informative. In addition to signatures of extended secondary structure, protein ROA spectra also contain signatures related to loops and turns which are valuable for studying tertiary structure and dynamics, exemplified here by a comparison of the ROA spectra of reduced lysozyme and unordered poly-L-lysine, by the ROA spectra of acid molten globule α-lactalbumin at different temperatures, which reveal a native-like tertiary fold, and by changes in the ROA spectrum of native lysozyme on binding to a saccharide inhibitor. Carbohydrate ROA spectra contain signatures of all the central features of their stereochemistry and, as shown by a comparison of laminaribiose with laminarin, can also probe extended secondary structure in polysaccharides. Results on a glycoprotein, orosomucoid, suggest that ROA can provide information about both the protein and the carbohydrate components. Preliminary results on nucleic acids are outlined with the ROA spectra of Poly(rA)·Poly(rU) and Poly(rI)·Poly(rC) shown as examples.