bluuebunny/crossref_metadata_2025_split huggingface dataset:
Computational Study on a Transfer Hydrogenation Catalysed by a Ru(II) Bis‐Pyrazolyl Pyridine Complex
Authors: Groß Jessica , van Wüllen Christoph 
Published: April 2023

AbstractDensity functional calculations were performed to investigate the Ru‐catalysed transfer hydrogenation of acetophenone to 1‐phenylethanol using isopropanol as the reducing agent. The catalyst is [Ru(bpp)Cl2(PPh3)], where bpp is a tridentate bis‐pyrazolyl pyridine ligand. We studied an inner sphere monohydridic mechanism where the active Ru centre binds, in addition to bpp, one of the original ligands as a spectator, which can be either chloride or triphenylphosphine. In both cases, catalyst initiation appears to be feasible (with triphenylphosphine being the preferred spectator ligand) and the catalytic cycle is efficient with a small energetic span. For which one of the cases the calculated energetic span is smaller depends on the treatment of entropy in solution. Since pathways involving dissociation of charged ligands are not preferred, the product is formed by a fast proton transfer within the Ru coordination sphere, from a coordinated isopropanol to the product alcoholate. Subsequently, both product release and catalyst regeneration can be accomplished by the dissociation of the charge neutral product alcohol. The β‐hydride transfer from a coordinated isopropanolate anion to ruthenium is slightly different depending on whether there is a chloride or phosphine present trans to the alcoholate. In both cases, this step contains the transition state with the highest Gibbs energy.
C−H Bond Activation in Ru‐Catalyzed Reactions of Arenes with Olefins: Theoretical Insights into Hydroarylation and Oxidative Coupling Mechanisms
Authors: Efremenko Irena , Martin Jan M. L. 
Published: April 2023

AbstractA detailed mechanistic density functional theory (DFT) and coupled cluster study of Csp²−H activation in benzene and methyl acrylate by the catalyst RuClm(CO)n (m=2,3; n=0–4) is presented. We trace the entire reaction pathways from the precursor to the active form of the catalysts followed by catalytic hydroarylation and oxidative coupling reactions. Our results reveal that both computational methods provide very similar qualitative pictures, but only the coupled cluster DLPNO‐CCSD(T1) results are quantitatively consistent with experiment. At the latter level of theory, the Ru(II) and Ru(III) catalyst precursors transform into the same active form of the catalyst, which explains the experimental results. Oxidative addition is extremely endergonic, especially in the presence of CO. Oxidative hydrogen migration (OHM) occurs in complexes with a low Ru coordination number and leads to olefine hydroarylation. Strongly bound carbonyl ligands suppress this interaction. Concerted metalation‐deprotonation (CMD) of the aromatic C−H bond and σ‐bond metathesis mechanisms of catalyst regeneration do not involve Ru−H bonding and form the energetically favorable catalytic cycle of the oxidative coupling reaction. The key interaction in CMD mechanisms consists of proton abstraction by an inner‐sphere Cl‐anion. Carbonyl ligands facilitate CMD by weakening the Ru−Cl bond. An excess of CO slows the interaction by leading to replacement of the reactants in the Ru coordination sphere.
Promoting reflective practice in an infant and early childhood training program
Authors: Lombardi Caitlin , Bladen Anne , Foley Mary Tabb , Galante‐DeAngelis Meg , Larrabee Kim , Robinson JoAnn 
Published: April 2023

AbstractReflective practices provide a supportive base through which preservice infant and early childhood teachers and allied professionals can achieve knowledge, skills, and professional dispositions to support young children and their families. This paper is a program description that describes the rationale for infusing reflective practices into the learning goals for preservice early childhood training, highlighting the specific reflection skills from the Infant and Early Childhood Mental Health Competency Guidelines. We describe how one university early childhood training program promotes student reflection skills referencing three distinct perspectives: (1) why reflection is essential to developing knowledge and skills; (2) the role group reflection plays in sustaining deep knowledge and skill development for students and faculty; (3) how faculty promote students’ awareness of the connection between personal experience and professional dispositions through reflection during practicum experiences. The benefits and challenges of embedding reflective practices in preservice early childhood training are also discussed.
The role of glycan characterisation in ATMP development and evaluation
Authors: Joyce Kieran , Pandit Abhay 
Published: April 2023

AbstractAdvanced therapeutic medicinal products (ATMP) aim to transform treatment strategies for unmet clinical needs. ATMP development requires product standardisation, high‐quality consistent starting materials, and safety and efficacy, while reducing adverse reactions. Glycosylation is a common post‐translational modification of glycans to specific peptide sites. Changes in glycosylation in starting materials or culture can potentially affect the bioactivity, safety and efficacy of glycosylated products. Glycan analysis is applied to few biological products, most commonly monoclonal antibodies and glycoconjugate vaccines. Regulatory authorities are starting to scrutinise the glycan profiles of biomedical products more carefully since glycosylation‐mediated activity has been recognised to lead to adverse effects in this class of therapies, including allergic/hypersensitivity reactions, anti‐drug antibodies and product heterogeneity in biologic and advanced treatments. This review highlights the impact of glycosylation in cell and tissue substrates for use in advanced therapies, identifying the need for glycan analysis to design safer, consistent products.
Carbon mitigation payments can reduce the riskiness of bioenergy crop production
Authors: Majeed Fahd , Khanna Madhu , Miao Ruiqing , Blanc‐Betes Elena , Hudiburg Tara , DeLucia Evan 
Published: April 2023

AbstractPerennial bioenergy crops provide substantial carbon mitigation benefits but have risky returns. We couple economic analysis with a biogeochemical model (DayCent) to examine the effect of carbon mitigation payments on the spatially varying bioenergy crop returns and risk profiles relative to conventional crops across the rainfed United States. These payments increase the likelihood of positive profit in the Midwest for miscanthus and southern states for switchgrass. At low biomass prices, these payments make bioenergy crops appealing to risk‐averse farmers. At moderate biomass prices, these payments make bioenergy crops appealing to all farmers regardless of risk preference.
MicroRNA‐19a‐3p Decreases with Age in Mice and Humans and Inhibits Osteoblast Senescence
Authors: Kaur Japneet , Saul Dominik , Doolittle Madison L. , Farr Joshua N. , Khosla Sundeep , Monroe David G. 
Published: April 2023

ABSTRACTAging is a major risk factor for most chronic diseases, including osteoporosis, and is characterized by an accumulation of senescent cells in various tissues. MicroRNAs (miRNAs) are critical regulators of bone aging and cellular senescence. Here, we report that miR‐19a‐3p decreases with age in bone samples from mice as well as in posterior iliac crest bone biopsies of younger versus older healthy women. miR‐19a‐3p also decreased in mouse bone marrow stromal cells following induction of senescence using etoposide, H2O2, or serial passaging. To explore the transcriptomic effects of miR‐19a‐3p, we performed RNA sequencing of mouse calvarial osteoblasts transfected with control or miR‐19a‐3p mimics and found that miR‐19a‐3p overexpression significantly altered the expression of various senescence, senescence‐associated secretory phenotype‐related, and proliferation genes. Specifically, miR‐19a‐3p overexpression in nonsenescent osteoblasts significantly suppressed p16Ink4a and p21Cip1 gene expression and increased their proliferative capacity. Finally, we established a novel senotherapeutic role for this miRNA by treating miR‐19a‐3p expressing cells with H2O2 to induce senescence. Interestingly, these cells exhibited lower p16Ink4a and p21Cip1 expression, increased proliferation‐related gene expression, and reduced SA‐β‐Gal+ cells. Our results thus establish that miR‐19a‐3p is a senescence‐associated miRNA that decreases with age in mouse and human bones and is a potential senotherapeutic target for age‐related bone loss. © 2023 The Authors. JBMR Plus published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research.
The power (and limits) of the therapeutic relationship: Working alliance, psychiatric distress, and the role of trait emotional intelligence
Authors: Rudenstine Sasha , Schulder Talia , Gvozdieva Kseniia 
Published: April 2023

AbstractObjectiveThe working alliance between therapists and patients is an important factor in the psychotherapy processes. Trait emotional intelligence has also been found to be malleable in treatment and to play a significant role in patient outcomes. The present study investigated how the relationship between measured working alliance and patient symptoms may differ depending on changes in patient trait emotional intelligence capacities.MethodsOne hundred twenty‐nine adults at a community mental health clinic completed self‐report measures at the beginning of treatment, as well as 8 months into treatment. Hierarchical linear regressions were computed to assess the interaction of working alliance and trait emotional intelligence scores on patient symptom scores. Simple slope tests were used to probe significant interactions.ResultsTrait emotional intelligence served as a significant moderator on the relationship between working alliance and patient symptoms. Specifically, the relationship between working alliance and patient symptoms was only significant for participants who reported an improvement in trait emotional intelligence over the course of treatment.ConclusionResults demonstrate that the impact of working alliance on patient symptom outcomes depended on patient improvement in trait emotional intelligence capacities. Such findings emphasize the importance of investigating the nuanced individual factors that impact the ways in which working alliance relates to treatment outcomes.
How can we design a proper trial for vitamin D treatment of diseases? Facts and numbers
Authors: Zheng Shuang , Zhu Zhaohua , Ding Changhai 
Published: April 2023

AbstractVitamin D deficiency is a globally common situation and closely related with many chronic diseases. It is a hot topic to examine if vitamin D supplementation is effective for the treatment of diseases, and there have been dozens of clinical trials published in recent years. However, most studies have not proved the extra‐skeletal benefits of vitamin D supplementation on these diseases. Some inherent shortcomings of these trials, such as inclusion with vitamin D‐sufficient and obese participants, low response rate from participants and the insensitive changes in chosen outcomes over a shorter period, may be main reasons why most studies have yet to demonstrate effects of vitamin D supplementation. In this editorial, we aim to discuss the perspectives on how can we design a proper trial for vitamin D treatment of diseases based on the evidence‐based practice framework PICOS (participants, intervention, control, outcomes and study design) in the future. First, right participants should be chosen, which is crucial for the success of vitamin D clinical trials. Participants with vitamin D sufficiency (e.g., baseline 25(OH)D of >50 nmol/L), obesity (e.g., body mass index > 30 kg/m2) and/or high vitamin D response index could be excluded from the trials. Second, intervention with vitamin D in right forms or dosages should be used. Vitamin D3 supplementation with appropriate dosages that keep 25(OH)D levels between 75 and 100 nmol/L is recommended. Third, ‘contamination’ in the control groups needs to pay attention. To diminish this, it is ideal to include participants less interfered by sun exposure (such as living in places at a high latitude) or with greater compliance (less interference by supplemental vitamin D‐containing nutrients). Fourth, the outcome measures should be sensitive to change to avoid type II error. For outcomes such as bone density, radiographic osteoarthritis and cardiovascular diseases, follow‐up period of 3–5 years may be required to observe the changes. Last, precision clinical trials may be the only way to prove the benefits of vitamin D supplementation.
Filicide in Bangladesh: A case indicating the need for psychosocial support among mothers during peripartum
Authors: Arafat S. M. Yasir , Monira Shirajum , Lily Shakila Ashfia 
Published: April 2023

AbstractWe report a case of filicide which is an under‐researched entity in Bangladesh. A 28‐year‐old lady visited with complaints of irregular eating followed by self‐induced vomiting, poor anger control, irregular sleep, hopelessness, and suicidal thoughts for the last year. On the third visit, she admitted that she killed her 32‐day‐old baby by keeping it in a refrigerator. The case raises some forensic psychiatric complexities as the patient confessed it to the psychiatrist while family members know it as an accidental aspiration. It indicates the complex nature and dire need for psychosocial support in Bangladesh.
Accuracy of models to prognosticate survival after surgery for pancreatic cancer in the era of neoadjuvant therapy
Authors: Marcinak Clayton T. , Parker William F. , Parikh Alexander A. , Datta Jashodeep , Maithel Shishir K. , Kooby David A. , Burkard Mark E. , Kim Hong Jin , LeCompte Michael T. , Afshar Majid , Churpek Matthew M. , Zafar Syed Nabeel 
Published: April 2023

AbstractBackgroundOutcomes for pancreatic adenocarcinoma (PDAC) remain difficult to prognosticate. Multiple models attempt to predict survival following the resection of PDAC, but their utility in the neoadjuvant population is unknown. We aimed to assess their accuracy among patients that received neoadjuvant chemotherapy (NAC).MethodsWe performed a multi‐institutional retrospective analysis of patients who received NAC and underwent resection of PDAC. Two prognostic systems were evaluated: the Memorial Sloan Kettering Cancer Center Pancreatic Adenocarcinoma Nomogram (MSKCCPAN) and the American Joint Committee on Cancer (AJCC) staging system. Discrimination between predicted and actual disease‐specific survival was assessed using the Uno C‐statistic and Kaplan–Meier method. Calibration of the MSKCCPAN was assessed using the Brier score.ResultsA total of 448 patients were included. There were 232 (51.8%) females, and the mean age was 64.1 years (±9.5). Most had AJCC Stage I or II disease (77.7%). For the MSKCCPAN, the Uno C‐statistic at 12‐, 24‐, and 36‐month time points was 0.62, 0.63, and 0.62, respectively. The AJCC system demonstrated similarly mediocre discrimination. The Brier score for the MSKCCPAN was 0.15 at 12 months, 0.26 at 24 months, and 0.30 at 36 months, demonstrating modest calibration.ConclusionsCurrent survival prediction models and staging systems for patients with PDAC undergoing resection after NAC have limited accuracy.
Microbial functional genes within soil aggregates drive organic carbon mineralization under contrasting tillage practices
Authors: Wang Weiyan , Zhang Houping , Vinay Nangia , Wang Dong , Mo Fei , Liao Yuncheng , Wen Xiaoxia 
Published: April 2023

AbstractSoil organic carbon (SOC) transformation is susceptible to tillage practices. Conservation tillage is known to optimize soil structure, improve microbial community diversity and increase SOC storage. However, how soil aggregate distribution and microbial community structure and function within aggregates affect SOC transformation under long‐term conservation tillage remains unclear. In this study, SOC mineralization dynamics were studied in situ and under laboratory conditions to examine the mechanisms by which C functional genes within soil aggregates of different sizes (i.e., mega‐, macro‐, and micro‐aggregates) influence SOC mineralization under long‐term tillage (i.e., zero, chisel, and plow tillage) in a dryland. The results indicated that in the winter wheat and summer maize rotation cropping system, SOC‐derived CO2‐C emissions were 143.99 and 133.29 g CO2‐C m−2 h−1 lower under chisel and zero tillage than that under plow tillage, respectively. Moreover, after 180 days of laboratory incubation, SOC mineralization in micro‐ and macro‐aggregates was 1.98 and 1.63 mg CO2‐C g−1 d−1 higher than that in mega‐aggregates, respectively. The aggregate‐associated differential modules of bacterial co‐occurring networks may be directly governed by bacterial community diversity and composition, which might play critical roles in driving SOC mineralization in response to different tillage intensities. Moreover, aggregate‐associated functional genes involved in labile and recalcitrant C compositions, which were determined by shotgun metagenomic sequencing, were associated with SOC mineralization and were significantly affected by the legacy effect of tillage intensity and aggregate size. Particularly, partial least squares path modeling revealed that genes involved in simple sugar metabolism exerted significantly positive effects on SOC mineralization, except for the effects of tillage intensity and aggregate size. Overall, this study showed that decreased abundances of labile C decomposition‐related functional genes within aggregates and community composition changes, as elucidated by the differences in bacterial network modules, under conservation tillage inhibit SOC mineralization. These findings may help in the development of adaptive soil tillage strategies for reducing carbon emissions in agroecosystems.
Analysis of risk factors affecting olfactory dysfunction in patients with chronic rhinosinusitis: Highlighting the role of metabolic syndrome
Authors: Zhang Ling , Wang Tao , Wang Zhu , Li Haifeng , Wu Yang , Guo Siquan , Li Wenjing , You Jianqiang , Chao Changjiang 
Published: April 2023

AbstractObjectiveThis study aims to evaluate the relationship between chronic sinusitis (CRS) and metabolic syndrome (MS) in a Chinese population and to explore the risk factors for olfactory dysfunction in patients with CRS.MethodsA total of 387 CRS patients were enrolled. Olfactory function was assessed by the Sniffin’ Sticks 12‐item test and MS was diagnosed according to the guidelines. Logistic regression analysis was performed on CRS patients to screen independent risk factors of olfactory dysfunction, adjusted for confounding factors.ResultsAmong 387 patients, average age of visit and duration of onset were 48.7 years and 1.8 years, respectively. The prevalence of MS was 15.0%. CRS patients with MS were more likely to be older (51.2 vs. 46.8, p = .004), predominantly male (p < .001) and have a higher proportion of olfactory dysfunction (62.1% vs. 44.1%, p = .018) than those without MS. In multivariate logistic regression analysis, MS was associated with olfactory dysfunction in CRS patients (OR: 2.06, 95% CI: 1.14–3.72, p = .016). This association remained significant after controlling for confounding factors. In addition, nasal polyps (OR: 13.41, 95% CI: 8.11–22.17, p < .001) and allergic rhinitis (OR: 3.16, 95% CI: 1.67–5.99, p < .001) were also risk factors for olfactory dysfunction after adjusting for confounding factors.ConclusionsMS is associated with olfactory dysfunction in patients with CRS. MS, nasal polyps, and allergic rhinitis are risk factors for olfactory dysfunction in CRS patients.Level of evidenceIV
Logarithmically improved extension criteria involving the pressure for the Navier–Stokes equations in Rn$\mathbb {R}^{n}$
Authors: Kanamaru Ryo , Yamamoto Tatsuki 
Published: April 2023

AbstractWe consider the Cauchy problem of the Navier–Stokes equations in ( and establish several new extension criteria involving the pressure or its gradient. In particular, we improve the previous results by means of the homogeneous Besov space with negative differential orders in the case . Our method is based on the interpolation inequality and the trilinear estimate due to Gérard–Meyer–Oru (Séminaire É. D. P. (1996–1997), Exp. No. IV, 1–8) and Guo–Kučera–Skalák (J. Math. Anal. Appl. 458 (2018) 755–766), respectively.
Gröbner deformations and F‐singularities
Authors: Koley Mitra , Varbaro Matteo 
Published: April 2023

AbstractFor polynomial ideals in positive characteristic, defining F‐split rings and admitting a squarefree monomial initial ideal are different notions. In this note, we show that, however, there are strong interactions in both directions. Moreover, we provide an overview on which F‐singularities are Gröbner deforming. Also, we prove the following characteristic‐free statement: If is a height h prime ideal such that contains at least one squarefree monomial, then is a squarefree monomial ideal.
Geometry of Prym semicanonical pencils and an application to cubic threefolds
Authors: Lahoz Martí , Naranjo Juan Carlos , Rojas Andrés 
Published: April 2023

AbstractIn the moduli space of double étale covers of curves of a fixed genus g, the locus formed by covers of curves with a semicanonical pencil consists of two irreducible divisors and . We study the Prym map on these divisors, which shows significant differences between them and has a rich geometry in the cases of low genus. In particular, the analysis of has enumerative consequences for lines on cubic threefolds.
Shear‐Triggered Release of Lipid Nanoparticles from Tissue‐Mimetic Hydrogels
Authors: Karaz Selcan , Akay Gizem , Karaoglu Ismail C. , Han Mertcan , Nizamoglu Sedat , Kizilel Seda , Senses Erkan 
Published: April 2023

AbstractShear forces are involved in many cellular processes and increase remarkably in the case of cardiovascular diseases in the human body. While various stimuli, such as temperature, pH, light, and electromagnetic fields, have been considered for on‐demand release, developing drug delivery systems that are responsive to physiological‐level shear stresses remains as a challenge. For this purpose, liposomes embedded in hydrogel matrices are promising as they can dynamically engage with their environment due to their soft and deformable structure. However, for optimal drug delivery systems, the interaction between liposomes and the surrounding hydrogel matrix, and their response to the shear should be unraveled. Herein, we used unilamellar 1,2‐Dimyristoyl‐sn‐glycero‐3phosphocholine (DMPC) liposomes as drug nanocarriers and polyethylene (glycol) diacrylate (PEGDA) hydrogels having different elasticities, from 1 to 180 Pa, as extracellular matrix (ECM)‐mimetic matrices to understand shear‐triggered liposome discharge from hydrogels. The presence of liposomes provides hydrogels with temperature‐controlled water uptake which is sensitive to membrane microviscosity. By systematically applying shear deformation from linear to nonlinear deformation regimes, the liposome release under transient and cyclic stimuli is modulated. Considering that shear force is commonly encountered in biofluid flow, these results will provide fundamental basis for rational design of shear‐controlled liposomal drug delivery systems.