bluuebunny/crossref_metadata_2025_split huggingface dataset:
Mechanistic Insights into the Synergistic Effect of Palladium(0) and Copper(I) on the Selective Transformation of Isocyanate to Indole
Authors: Ding Cai‐Yun , Li Man , Liao Rong‐Zhen 
Published: February 2023

AbstractDensity functional theory calculations have been utilized to investigate the synergistic effect of palladium(0) and copper(I) catalyzed selective formation of allylated indole from (2‐alkynyl)‐phenylisocyanate and allyl methyl carbonate. The main competing reaction yielding theN‐allyl carbamate was also considered. Calculated results indicate that using the Pd(0)‐complex alone, the generation of indole is kinetically much less favored than producing theN‐allyl carbamate compound. However, the co‐addition of Cu(I) catalyst can considerably decrease the barrier for the intramolecular cyclization step, leading to the formation of the indole product. Analysis of the cyclization process suggests that Cu(I) complex can act as a Lewis acid to activate the linear alkyne group via a π‐coordination manner prior to the formation of a 5‐membered ring transition state toward indole formation. Altogether, the mechanistic insights revealed in the present study aim at a better understanding of the mechanism and the factors governing the selectivity in synergistic Pd/Cu catalysis.
Photometric BVR observations of comet C/2012 J1 (Catalina) before and after perihelion
Authors: Betzler A. S. , de Sousa O. F. 
Published: February 2023

AbstractWe analyzed the BVR photometry of comet C/2012 J1 (Catalina) taken between March 2013 and May 2014 with telescopes ranging from 0.20 to 2.0 m aperture in Australia, Europe, and the United States. We found an absolute magnitude in the R‐band of H0 = 7.2 ± 0.1 measured with a photometric aperture radius ρ of 42.4 arcsec, corresponding to projected distances in the sky of 7.2 × 104–1.5 × 105 km. Comet C/2012 J1 (Catalina) shows an asymmetric secular light curve, which is typical for comets. The nucleus has a minimum radius of 3.3 km admitting an albedo of 0.04. The inner coma exhibited radial pulsations before perihelion related to the dust rate proxy Afρ. The Afρ parameter was inversely proportional to the photometric aperture radius ρ because the angular diameter of the coma was small compared with the aperture radii used. The comet had three outbursts with brightness variations between 0.2 and 2.99 magnitudes per event. The median normalized reflectivity gradient S′ is 4.4 with an amplitude of 22.9%/100 nm in the spectral range between 440 and 647 nm. The dispersion of the gradient S′ means that 20% of the measurements are bluer than the solar color.
Self‐reported quality of life in symptomatic and asymptomatic women with X‐linked adrenoleukodystrophy
Authors: Schäfer Lisa , Roicke Hannes , Bergner Christa‐Caroline , Köhler Wolfgang 
Published: February 2023

AbstractBackgroundUp to 80% of women with X‐linked adrenoleukodystrophy (X‐ALD) develop symptoms of myelopathy and peripheral neuropathy during their lifetime. The study's objective was to compare symptomatic versus asymptomatic women with X‐ALD regarding their physical and mental well‐being and quality of life.MethodsData were obtained from a prospective, international, cross‐sectional cohort study of women with X‐ALD recruited both clinically and population based. Symptoms, quality of life, and physical and mental co‐morbidities were assessed by questionnaires. Women were considered symptomatic if they reported any sign of myelopathy or peripheral neuropathy. Group differences between symptomatic versus asymptomatic women and between age groups were examined using χ2 tests for categorical and independent sample t tests or analysis of variance for continuous variables.ResultsComplete data were available from N = 180 women (mean age: 51.2 ± 13.6 years, range: 18–85), of whom 71.7% were classified as symptomatic, with prevalence increasing with age. Symptomatic versus asymptomatic women reported poorer physical and mental health, with 26.4% meeting the criteria for a clinical depression, 73.6% reporting chronic pain, 80.6% sleeping disturbances, 38.2% sexual dysfunction, and 47.3% restless legs syndrome. Large group differences were found on the physical health, but not on the mental health component of quality of life, where symptomatic women only differed when controlling for having a boy affected by X‐ALD (small effect) and treatment frequency (medium effect).ConclusionsSymptomatic women with X‐ALD present with physical and psychological co‐morbidities significantly reducing individuals’ quality of life. The findings emphasize the need to develop new multi‐disciplinary treatment options tailored to women's specific needs.
The association between HDL‐C and stroke in the middle‐aged and elderly: A cross‐sectional study
Authors: Hu Yang , Song Min , Wu Dongmei , Zhang Yuqing , Li Gongbo , Luo Haiyan 
Published: February 2023

AbstractBackgroundPrevious epidemiological studies have indicated that high‐density lipoprotein cholesterol (HDL‐C) is inversely associated with the risk of cardiovascular disease. However, this issue has aroused controversy in recent years. Besides, the relationship between HDL‐C and the risk of total stroke in sex and race is less clear. Thus, we aimed to examine the association between different ranges of HDL‐C and the risk of total stroke in adults over 40 years old.MethodsThis cross‐sectional study was conducted on a sample of 8643 participants (4222 men and 4421 women) aged ≥40 years old from the National Health and Nutrition Examination Survey 2007–2016. HDL‐C was an independent variable and stroke was a dependent variable in this study, with the other variables as potential effect modifiers. To examine the associations between them, we used multivariate logistical regression models and smooth curve fittings, as well as subgroup analyses.ResultsHDL‐C was inversely associated with stroke when HDL‐C was less than 1.55 mmol/L (odds ratio [OR] = 0.36, 95% confidence interval [CI] :0.21–0.62, p < .05). However, above 1.55 mmol/L, the incidence of stroke was not significant (OR = 1.29, 95% CI: 0.79–2.09, p>.05). Stratified by race/ethnicity and sex, the subgroup analyses demonstrated that HDL‐C was inversely associated with stroke in men and Whites, but no significant differences among women, Mexicans, blacks, and other races.ConclusionWe found a nonlinear relationship between HDL‐C and total stroke. Our study reveals a range of inverse associations between HDL‐C and stroke (HDL‐C<1.55 mmol/L), especially among men and Whites. This finding suggested that maintaining an appropriate HDL‐C range may be beneficial in reducing the incidence of stroke.
Predicted resting metabolic rate and prognosis in patients with ischemic stroke
Authors: Lin Xiaoyu , Cheng Aichun , Pan Yuesong , Wang Mengxing , Meng Xia , Wang Yongjun 
Published: February 2023

AbstractPurposeResting metabolic rate (RMR) could represent metabolic health status. This study aims to examine the association of the predicted RMR with 1‐year poor functional outcome and all‐cause mortality in patients with ischemic stroke as a proxy of metabolic profile.MethodsA total of 15,166 patients with ischemic stroke or transient ischemic attack (TIA) from the Third China National Stroke Registry (CNSR‐III) were enrolled in this study. The Harris–Benedict equation based on sex, age, weight, and height was used to predict RMR. The primary endpoints were poor functional outcome defined as ≥3 modified Rankin Scale (mRS) score and all‐cause mortality within 1 year. The association between predicted RMR and prognosis was assessed by multivariable regression analysis. Besides that, subgroup analysis of age, sex, and body mass index (BMI) with predicted RMR was also performed.Results12.85% (1657) individuals had poor functional outcome and 2.87% (380) died of whatever causes within 1 year. An inverse association was found between predicted RMR with poor functional outcome and all‐cause mortality. Compared to the lowest quartile, the highest quartile was significantly associated with lower risk of poor functional outcome (adjusted odds ratio [OR], 0.43 [95% confidence interval (CI) 0.33–0.56]) and all‐cause mortality (adjusted hazard ratio [HR], 0.44 [95% CI 0.28–0.71]). No significant interaction was between predicted RMR and specified subgroup.ConclusionsPredicted RMR by the Harris–Benedict equation seems to be an independent protective predictor of poor functional outcome and all‐cause mortality after ischemic stroke as a metabolic proxy.
Role, race, and place: Prostate cancer disparities in Patients' and Partners' health outcomes and psychosocial factors
Authors: Song Lixin , Keyserling Thomas C. , Chen Ronald C. , Ma Chunxuan , Xu Shenmeng , Shieh Karl , Fuller Gail P. , Nielsen Matthew E. , Northouse Laurel L. , Tan Xianming , Rini Christine 
Published: February 2023

AbstractPurposeThis study aimed to examine the effects of participant role (patient vs. partner), race (white vs. non‐white), and place (less vs. more neighborhood deprivation) on health outcomes (quality of life [QOL] and symptoms) and stress‐coping‐related psychosocial factors (appraisals of illness and coping resources).MethodsThis descriptive study included 273 patients and their partners (dyads) who transitioned from PCa treatment to self‐management. We used established, psychometrically sound measures to assess health outcomes and psychosocial factors and conducted multilevel modeling analyses.ResultsCompared to partners, patients reported worse physical QOL; less frequent anxiety; less pain and fatigue; less bothersome hormonal problems; more bothersome urinary and sexual problems; greater self‐efficacy; and more instrumental support. Compared to their white counterparts, non‐white dyads reported better overall, emotional, and functional QOL; less depression; more positive appraisals, and greater self‐efficacy. Compared to dyads in low ADI neighborhoods, dyads in high ADI (more deprived) neighborhoods reported worse social QOL; more bothersome urinary, sexual, and hormonal symptoms; and less interpersonal support. White patients reported the highest emotional support among all groups, while white partners reported the lowest emotional support.ConclusionOur findings underscore the need to consider social determinants of health at multiple levels when investigating PCa disparities. Considering neighborhood‐level socioeconomic factors, in addition to race and role, improves our understanding of the PCa disparities in QOL, symptoms, and psychosocial factors among patients and partners. Targeted multilevel supportive care interventions should tailor to the needs of racially diverse PCa patients and partners residing in deprived neighborhoods are needed.
Do young adults with cancer receive information about treatment‐related impact on sex life? Results from a population‐based study
Authors: Bergström Charlotta , Lampic Claudia , Roy Ricky , Hedman Christel , Ahlgren Johan , Ståhl Olof , Smedby Karin E. , Hellman Kristina , Henriksson Roger , Eriksson Lars E. , Wettergren Lena 
Published: February 2023

AbstractBackgroundSexual dysfunction is common following a cancer diagnosis in young adulthood (18–39 years) and problems related to sex life are ranked among the core concerns in this age group. Yet, few studies have investigated to what extent adults younger than 40, receive information from healthcare providers about the potential impact of cancer and its treatment on their sex life.MethodsA population‐based cross‐sectional survey study was conducted with 1010 young adults 1.5 years after being diagnosed with cancer (response rate 67%). Patients with breast, cervical, ovarian and testicular cancer, lymphoma, and brain tumors were identified in national quality registries. Sociodemographic and clinical factors associated with receiving information were examined using multivariable binary logistic regression.ResultsMen to a higher extent than women reported having received information about potential cancer‐related impact on their sex life (68% vs. 54%, p < 0.001). Receipt of information varied across diagnoses; in separate regression models, using lymphoma as reference, both women and men with brain tumors were less likely to receive information (women: OR 0.10, CI = 0.03–0.30; men: OR 0.37, CI = 0.16–0.85). More intensive treatment was associated with higher odds of receiving information in both women (OR 1.89; CI = 1.28–2.79) and men (OR 2.08; CI = 1.09–3.94). None of the sociodemographic factors were associated with receipt of information.ConclusionsTo improve sexual health communication to young adults with cancer, we recommend diagnosis‐specific routines that clarify when in the disease trajectory to discuss these issues with patients and what to address in these conversations.
DNA Morphology: Global Alteration of DNA Topological States Induced by Chemotherapeutic Agents and Its Implication in Cancer
Authors: Ahammed Khondakar Sayef , Pachal Sangita , Majumdar Papiya , Dutta Sanjay 
Published: February 2023

AbstractThe dynamic topological states of chromosomal DNA regulate many cellular fundamental processes universally in all three domains of life, that is, bacteria, archaea, and eukaryotes. DNA‐binding proteins maintain the regional and global supercoiling of the chromosome and thereby regulate the chromatin architecture that ultimately influences the gene expression network and other DNA‐centric molecular events in various microenvironments and growth phases. DNA‐binding small molecules are pivotal weapons for treating a wide range of cancers. Recent advances in single‐molecule biophysical tools have uncovered the fact that many DNA‐binding ligands not only alter the regional DNA supercoiling but also modulate the overall morphology of DNA. Here we provide insight into recent advances in atomic force microscopy (AFM) acquired DNA structural change induced by therapeutically important mono‐ and bis‐intercalating anticancer agents as well as DNA‐adduct‐forming anticancer drugs. We also emphasize the growing evidence of the mechanistic relevance of changes in DNA topology in the anticancer cellular responses of DNA‐targeting chemotherapeutic agents.
Theranostic Nanoprobes with Aggregation‐Induced NIR‐II Emission: from Molecular Design to Biomedical Application
Authors: Jiang Yajing , Zhu Linlin , Wu Wenbo 
Published: February 2023

AbstractThe development of fluorophores with other powerful features has received much attention for the diagnosis and treatment of diseases. Nanoprobes (NPs) with aggregation‐induced emission (AIE) have demonstrated superior performance in deeper penetration depth with better resolution, higher signal‐to‐noise ratio, and lower side effects in the second near‐infrared window (NIR‐II, 1000–1700 nm) than in any other range. Herein, the latest advances in NIR‐II AIE NPs in cancer theranostics are summarized. In particular, we focus on the design of multifunctional AIE agents with both strong NIR‐II emission and effective photothermal conversion or reactive oxygen species (ROS) production, as well as their translational biomedical applications, including imaging diagnosis, image‐guided surgery, and image‐guided phototherapy, etc. At the end of this review, the opportunities and challenges of this field are also discussed.
Crosslinked Aggregates of Fusion Enzymes in Microaqueous Organic Media
Authors: Vernet Guillem , Ma Yu , Zhang Ningning , Kara Selin 
Published: February 2023

AbstractBaeyer‐Villiger monooxygenases (BVMOs) are attractive for selectively oxidizing various ketones using oxygen into valuable esters and lactones. However, the application of BVMOs is restrained by cofactor dependency and enzyme instability combined with water‐related downsides such as low substrate loading, low oxygen capacity, and water‐induced side reactions. Herein, we described a redox‐neutral linear cascade with in‐situ cofactor regeneration catalyzed by fused alcohol dehydrogenase and cyclohexanone monooxygenase in aqueous and microaqueous organic media. The cascade conditions have been optimized regarding substrate concentrations as well as the amounts of enzymes and cofactors with the Design of Experiments (DoE). The carrier‐free immobilization technique, crosslinked enzyme aggregates (CLEAs), was applied to fusion enzymes. The resultant fusion CLEAs were proven to function in microaqueous organic systems, in which the enzyme ratios, water contents (0.5–5 vol. %), and stability have been systematically studied. The fusion CLEAs showed promising operational (up to 5 cycles) and storage stability.
The evolution of medical resident training and healthcare delivery: Good riddance to the “July effect”
Authors: Iyengar Amrita , Moliterno David J. 
Published: February 2023

Key Points
The present observational study from the National Inpatient Sample found no evidence of a “July effect” associated with acute myocardial infarction (AMI) in‐hospital mortality rates in teaching hospitals.
Multifactorial quality improvement in the delivery of care for AMI patients has ameliorated potentially detrimental effects of trainee inexperience historically observed in high‐risk admissions.
Efforts to minimize unnecessary variability in care delivery and to consistently implement guideline‐directed medical therapy are ongoing via electronic health record software.
Experimental and Theoretical Exploration of ESIPT in a Systematically Constructed Series of Benzimidazole Based Schiff Base Probes: Application as Chemosensors
Authors: Bag Riya , Sikdar Yeasin , Sahu Sutapa , Majharul Islam Md , Mandal Sukhendu , Goswami Sanchita 
Published: February 2023

AbstractHerein, we have utilized 2‐(2‐hydroxyphenyl)benzimidazole (HBI) to synthesize 3‐(1H‐benzoimidazol‐2‐yl)‐2‐hydroxy‐5‐methyl‐benzaldehyde (HBIA) followed by three Schiff bases by using –ortho (H2BIo), ‐meta (H3BIdm) and ‐para (H2BIp) substituted amino benzoic acids and studied their photophysical properties. We have successfully derived molecular structures of HBI, HBIA and H3BIdm which reveals that in HBI and HBIA, the phenolic −OH is intramolecularly hydrogen bonded with sp2 N of benzimidazole group whereas in H3BIdm, it is hydrogen bonded with imine C=N of Schiff base moiety, which is responsible for different solid state emission properties of the reported compounds. Extensive experimental and theoretical studies show that for all three Schiff bases, in solution due to activation of C=N isomerization, ESIPT operates through benzimidazole site and displays different emission from the solid state. Furthermore, H2BIo, H3BIdm and H2BIp selectively sense Cu2+ in semi aqueous medium with nano‐molar detection limit and in HuH‐7 cells through the inhibition of ESIPT of process.
Orientational Control of Circularly Polarized Luminescence from Pyrene Clusters by Using a DNA Scaffold
Authors: Kashida Hiromu , Ito Yuka , Kakuta Takahiro , Ogoshi Tomoki , Asanuma Hiroyuki 
Published: February 2023

AbstractWe have investigated the chiroptical activities of pyrene clusters incorporated within a DNA duplex. Three pyrene derivatives were prepared on d‐threoninol linkers to allow incorporation within a DNA strand. DNA scaffolds containing dimers, tetramers, and hexamers of the pyrene derivatives were prepared. The homodimers of 1‐ and of 4‐pyrenecarboxylic acid, but not 2‐pyrenecarboxylic acid, emitted intense circularly polarized luminescence signals. Although increasing the number of pyrene units weakened the signal, insertion of natural base pairs between two dimers enhanced its intensity. Interestingly, circularly polarized luminescence intensities varied non‐monotonically depending on the number of intervening base pairs, thus indicating the importance of orientation between pyrene dimers. The results presented here could lead to the development of bright circularly polarized luminescence materials and probes.
Funneled Depolymerization of Ionic Liquid‐Based Biorefinery “Heterogeneous” Lignin into Guaiacols over Reusable Palladium Catalyst
Authors: Choudhary Hemant , Das Lalitendu , Pelton Jeffrey G. , Sheps Leonid , Simmons Blake A. , Gladden John M. , Singh Seema 
Published: February 2023

AbstractThe efficient utilization of lignin, the direct source of renewable aromatics, into value‐added renewable chemicals is an important step towards sustainable biorefinery practices. Nevertheless, owing to the random heterogeneous structure and limited solubility, lignin utilization has been primarily limited to burning for energy. The catalytic depolymerization of lignin has been proposed and demonstrated as a viable route to sustainable biorefinery, however, low yields and poor selectivity of products, high char formation, and limited to no recycling of transition‐metal‐based catalyst involved in lignin depolymerization demands attention to enable practical‐scale lignocellulosic biorefineries. In this study, we demonstrate the catalytic depolymerization of ionic liquid‐based biorefinery poplar lignin into guaiacols over a reusable zirconium phosphate supported palladium catalyst. The essence of the study lies in the high conversion (>80 %), minimum char formation (7–16 %), high yields of guaiacols (up to 200 mg / g of lignin), and catalyst reusability. Both solid residue, liquid stream, and gaseous products were thoroughly characterized using ICP‐OES, PXRD, CHN analysis, GC‐MS, GPC, and 2D NMR to understand the hydrogenolysis pathway.
Orbital Nature of Carboionic Monoradicals Made from Diradicals
Authors: Valdivia Abel Cardenas , Dai Yasi , Rambaldi Filippo , Barker Joshua E. , Dressler Justin J. , Zhou Zheng , Zhu Yikun , Wei Zheng , Petrukhina Marina A. , Haley Michael M. , Negri Fabrizia , Casado Juan 
Published: February 2023

AbstractThe electronic, optical, and solid state properties of a series of monoradicals, anions and cations obtained from starting neutral diradicals have been studied. Diradicals based ons‐indacene and indenoacenes, with benzothiophenes fused and in different orientations, feature a varying degree of diradical character in the neutral state, which is here related with the properties of the radical redox forms. The analysis of their optical features in the polymethine monoradicals has been carried out in the framework of the molecular orbital and valence bond theories. Electronic UV‐Vis‐NIR absorption, X‐ray solid‐state diffraction and quantum chemical calculations have been carried out. Studies of the different positive‐/negative‐charged species, both residing in the same skeletalπ‐conjugated backbone, are rare for organic molecules. The key factor for the dual stabilization is the presence of the starting diradical character that enables to indistinctively accommodate a pseudo‐hole and a pseudo‐electron defect with certainly small reorganization energies for ambipolar charge transport.