bluuebunny/crossref_metadata_2025_split huggingface dataset:
Influence of the Linker Chemistry on the Photoinduced Charge‐Transfer Dynamics of Hetero‐dinuclear Photocatalysts
Authors: Zedler Linda , Müller Carolin , Wintergerst Pascal , Mengele Alexander K. , Rau Sven , Dietzek‐Ivanšić Benjamin 
Published: April 2022

AbstractTo optimize light‐driven catalytic processes, light‐mediated multi‐electron transfer dynamics in molecular dyads need to be studied and correlated with structural changes focusing on the catalytically active metastable intermediates. Here, spectro‐electrochemistry has been employed to investigate the structure‐dependent photoelectron transfer kinetics in catalytically active intermediates of two Ru−Rh catalysts for light‐driven NAD+ reduction. The excited‐state reactivity of short‐lived intermediates was studied along different photoreaction pathways by resonance Raman and time‐resolved transient absorption spectro‐electrochemistry with sub‐picosecond time resolution under operando conditions. The results demonstrate, for the first time, how the bridging ligand serves as a (multi‐)electron storage structure, mediates the strength of the electronic coupling of catalytic and photocenter and impacts the targeted electron transfer as well as parasitic electron‐transfer kinetics.
Sequential Nucleophilic Substitution of Phosphorus Trichloride with Alcohols in a Continuous‐Flow Reactor and Consideration of a Mechanism for Reduced Over‐reaction through the Addition of Imidazole
Authors: Kitamura Hiroshi , Otake Yuma , Sugisawa Naoto , Sugisawa Hiroki , Ida Tomonori , Nakamura Hiroyuki , Fuse Shinichiro 
Published: April 2022

AbstractWe demonstrate a sequential nucleophilic substitution of highly electrophilic and inexpensive phosphorus trichloride with three different alcohols in a continuous‐flow reactor. A variety of alcohols including ones that contained acid‐ and/or basic‐labile functionalities were rapidly reacted. A over nucleophilic substitution that occurred during reaction of the second alcohol was suppressed by the addition of imidazole. Density functional theory calculations of the sequential nucleophilic substitutions of alcohols were performed both with and without imidazole, and Berry pseudorotation was suggested as a rate‐limiting step in both cases. Herein, we discuss the reasons for the decreased selectivity in the absence of imidazole as well as those for improved selectivity in the presence of imidazole during the second nucleophilic substitution.
A Photoresponsive Receptor with a 105 Magnitude of Reversible Anion‐Binding Switching
Authors: Einkauf Jeffrey D. , Bryantsev Vyacheslav S. , Moyer Bruce A. , Custelcean Radu 
Published: April 2022

AbstractInvited for the cover of this issue are Jeffrey Einkauf, Vyacheslav Bryantsev, Bruce Moyer, and Radu Custelcean from Oak Ridge National Laboratory. The image depicts an anion receptor functionalized with a new photoswitchable chromophore, the diiminoguanidinium group, with exceptionally strong sulfate‐binding affinity that can be turned off by photoirradiation with UV light. Read the full text of the article at 10.1002/chem.202200719.
Process Combination of VPP‐LED and Vacuum Die Casting for Producing Complex Ceramic 3D‐MID
Authors: Schubert Johannes , Weisser Philipp , Rosen Marcus , Zanger Frederik , Schulze Volker 
Published: April 2022

AbstractFuture developments lead to increasing demands on mechatronic integrated devices (MID). Therefore, ceramics have to be used as substrate material and conductor tracks have to be located in the interior of components to be sufficiently protected. A process combination of vat photopolymerization (VPP‐LED) and vacuum die casting is investigated for realizing such structures. First, optimized process parameters are derived by studying the filling behavior of straight capillaries. Subsequently, the results are transferred to complex additively manufactured substrates to derive design guidelines.
Impact of post‐pyrolysis wash on biochar properties
Authors: Fazzalari Anthony , Abou‐Zaid Mamdouh , Briens Cedric , Briens Lauren 
Published: April 2022

AbstractWashing biochar modifies its properties for use as a soil amendment. The important biochar properties for use as a soil amendment are hydrophilicity, adsorption, and stability. Biochar was obtained with intermediate pyrolysis at 400°C of three different feedstocks: woodchips, Bayview Flowers Digestate, and Storm Fisher Digestate biomass. A simple wash with an aqueous surfactant solution improved the properties of the biochar for soil amendment, with a non‐ionic surfactant combined with oxidizing hydrogen peroxide being the most effective. The improved properties included the removal of tars and possible modification of surface properties that increased hydrophilicity and adsorption and decreased leaching of any hydrocarbons that could negatively impact the surroundings. As a result, the washed biochar will exhibit better water retention and a more hospitable environment for the growth of beneficial microorganisms. In addition, by making the biochar more hydrophilic, a wash will make its granulation easier, reducing dust emissions during its application and allowing its formulation with enhancement additives. Although many post‐pyrolysis treatments of biochars have been investigated, the proposed wash is simple and effective, with beneficial advantages for downstream processing and application as a soil amendment.
Comparison of Nitrogen Activation on Trinuclear Niobium and Tungsten Sulfide Clusters Nb3Sn and W3Sn (n=0–3): A DFT Study
Authors: Gurti Joseph Israel , Ding Xun‐Lei , Wang Ya‐Ya , Chen Yan , Li Wei , Wang Xin 
Published: April 2022

AbstractThe reaction of N2 with trinuclear niobium and tungsten sulfide clusters Nb3Sn and W3Sn (n=0–3) was systematically studied by density functional theory calculations with TPSS functional and Def2‐TZVP basis sets. Dissociations of N−N bonds on these clusters are all thermodynamically allowed but with different reactivity in kinetics. The reactivity of Nb3Sn is generally higher than that of W3Sn. In the favorite reaction pathways, the adsorbed N2 changes the adsorption sites from one metal atom to the bridge site of two metal atoms, then on the hollow site of three metal atoms, and at that place, the N−N bond dissociates. As the number of ligand S atoms increases, the reactivity of Nb3Sn decreases because of the hindering effect of S atoms, while W3S and W3S2 have the highest reactivity among four W3Sn clusters. The Mayer bond order, bond length, vibrational frequency, and electronic charges of the adsorbed N2 are analyzed along the reaction pathways to show the activation process of the N−N bond in reactions. The charge transfer from the clusters to the N2 antibonding orbitals plays an essential role in N−N bond activation, which is more significant in Nb3Sn than in W3Sn, leading to the higher reactivity of Nb3Sn. The reaction mechanisms found in this work may provide important theoretical guidance for the further rational design of related catalytic systems for nitrogen reduction reactions (NRR).
Photochromic Performance of Donor‐Acceptor Stenhouse Adducts in Polymer Binders and Solution
Authors: McDonough Rowan , Rudgley Nick , Majewski Oskar , Perkins Michael V. , Evans Richard A. , Lewis David A. 
Published: April 2022

AbstractDonor‐acceptor Stenhouse adducts (DASAs) are an exciting new class of negative photochromic compounds, offering high colouration and rapid photo‐switching speeds, however the relationship between binder properties and photo‐switching behaviour of DASAs in films is poorly understood. The determination and analysis of rate constants of seven DASAs in five polymer binders showed a complex relationship between the glass transition temperature (Tg) of the binder, the solubility parameters of the matrix and the push‐pull nature of the donor and acceptor moieties. The rate constants of photo‐switching steps that require large degrees of molecular motion such as the actinic and thermal carbon‐carbon double bond rotations (kbleach and k−1) were found to be highly dependent on the Tg of the polymer binder, with higher Tg binders restricting these processes, resulting in slower switching rates and impacting changes in colour intensity. Correlation of rate constants with the Hansen solubility parameter for solvents and binders revealed strong relationships between the sum of the polarity and hydrogen bonding parameters (δP+δH) and the actinic and thermal carbon‐carbon double bond rotations (kbleach and k−1). This is attributed to changes in the zwitterionic resonance contributions of the triene with increases in these two solubility parameters.
A high step‐up dc‐dc converter based on P‐impedance source with reduced voltage stress
Authors: Lahooti Eshkevari Alireza , Mosallanjed Ali , Sepasian Mohammadsadegh 
Published: April 2022

AbstractThis paper proposes a new step‐up dc‐dc converter designed based on the P‐impedance source. High boost factor, single‐stage design, continuous input current, and low‐voltage stresses on switching devices, common‐ground, operating with low duty cycles, and high efficiency are the main advantages of the proposed unidirectional topology. Although the topology comprises two power switches, these are encountered with low‐voltage stresses. Thus, they can be readily picked up from low‐cost and low‐voltage rating semiconductors with low resistive losses. Moreover, operating with low duty cycles undoubtedly decreases the conduction losses of these switches and the converter. The input and output sections have the same ground line called the common‐ground feature. This circuit also operates with a continuous input current. In this article, the operating principle of the proposed topology has been investigated in detail. In order to examine the claims, simulation and experimental results are represented and evaluated. For this purpose, a 72 V/400 V/320 W prototype has been designed. Results show that the converter efficiency is almost equal to 95%. Higher boost factors, above six times, are obtained, and the voltage stresses on semiconductors are reduced by up to 80%, subject to the output voltage.
The two sides of a coin: Pathogenicity and potential therapeutic of LDLRQ722*
Authors: Zhou Yingchao , Tu Xin 
Published: April 2022

AbstractFamilial hypercholesterolemia (FH) is a severe inherited lipid metabolism dysfunction, characterized by high low‐density lipoprotein (LDL) cholesterol levels, mostly due to mutations in the LDL receptor (LDLR) gene. Whole exome sequencing was performed on a consanguineous Chinese FH family and identified a novel homozygous pathogenic mutation LDLR c.C2164T (p. Q722*), forming a novel truncated soluble LDLRQ722*. LDLRQ722* was secreted via the small extracellular vesicles (sEV) and located on the surface of sEV. LDLRQ722*exhibit ∼6% of the wild‐type LDLR activity. sEV containing LDLRQ722* protein reconstructed the lipid metabolism via heparan sulfate proteoglycans (HSPG) and clathrin‐mediated endocytosis. Currently, statins and PCSK9 inhibitors therapy are the mainstay treatment for FH. However, statins and PCSK9 inhibitors substantially vary depending on the residual LDLR activity, while LDLRQ722* reduced circulating LDL‐C levels independently of LDLR residual activity. The study provided new insight into the treatments of FH.
Insights into Streptomyces coelicolor A3(2) growth and pigment formation with high‐throughput online monitoring
Authors: Finger Maurice , Sentek Fabio , Hartmann Lukas , Palacio‐Barrera Ana M. , Schlembach Ivan , Rosenbaum Miriam A. , Büchs Jochen 
Published: April 2022

AbstractStreptomyces species are intensively studied for their ability to produce a variety of natural products. However, conditions influencing and leading to product formation are often not completely recognized. Therefore, in this study, high‐throughput online monitoring is presented as a powerful tool to gain in‐depth understanding of the cultivation of the model organism Streptomyces coelicolor A3(2). Through online measurements of oxygen transfer rate and autofluorescence, valuable information about availability of nutrients and product formation patterns of the pigments actinorhodin and undecylprodigiosin can be obtained and explained. Therefore, it is possible to determine the onset of pigmentation and to study in detail the influencing factors thereof. One factor identified in this study is the filling volume of the cultivation vessel. Slight variations led to varying pigmentation levels. By combining optical and metabolic online monitoring techniques, the correlation of the filling volume with pigmentation could be explained as a result of different growth trajectories caused by varying specific power inputs and their influence on the pellet formation of the filamentous system. Finally, experiments with the addition of supernatant from unpigmented and pigmented cultures could highlight the applicability of the presented approach to study quorum sensing and cell‐cell interaction.
Gene‐environment interaction in type 2 diabetes in Korean cohorts: Interaction of a type 2 diabetes polygenic risk score with triglyceride and cholesterol on fasting glucose levels
Authors: Lim Ji Eun , Kang Ji‐one , Ha Tae‐Woong , Jung Hae‐Un , Kim Dong Jun , Baek Eun Ju , Kim Han Kyul , Chung Ju Yeon , Rhee Sang Youl , Kim Mi Kyung , Kim Yeon‐Jung , Park Taesung , Oh Bermseok 
Published: April 2022

AbstractType 2 diabetes (T2D) is caused by genetic and environmental factors as well as gene‐environment interactions. However, these interactions have not been systematically investigated. We analyzed these interactions for T2D and fasting glucose levels in three Korean cohorts, HEXA, KARE, and CAVAS, using the baseline data with a multiple regression model. Two polygenic risk scores for T2D (PRST2D) and fasting glucose (PRSFG) were calculated using 488 and 82 single nucleotide polymorphisms (SNP) for T2D and fasting glucose, respectively, which were extracted from large‐scaled genome‐wide association studies with multiethnic data. Both lifestyle risk factors and T2D‐related biochemical measurements were assessed. The effect of interactions between PRST2D‐triglyceride (TG) and PRST2D‐total cholesterol (TC) on fasting glucose levels was observed as follows: β ± SE = 0.0005 ± 0.0001, p = 1.06 × 10−19 in HEXA, β ± SE = 0.0008 ± 0.0001, p = 2.08 × 10−8 in KARE for TG; β ± SE = 0.0006 ± 0.0001, p = 2.00 × 10−6 in HEXA, β ± SE = 0.0020 ± 0.0004, p = 2.11 × 10−6 in KARE, β ± SE = 0.0007 ± 0.0004, p = 0.045 in CAVAS for TC. PRST2D‐based classification of the participants into four groups showed that the fasting glucose levels in groups with higher PRST2D were more adversely affected by both the TG and TC. In conclusion, blood TG and TC levels may affect the fasting glucose level through interaction with T2D genetic factors, suggesting the importance of consideration of gene‐environment interaction in the preventive medicine of T2D.
The steatosis‐associated fibrosis estimator (SAFE) score: A tool to detect low‐risk NAFLD in primary care
Authors: Sripongpun Pimsiri , Kim W. Ray , Mannalithara Ajitha , Charu Vivek , Vidovszky Anna , Asch Steven , Desai Manisha , Kim Sun H. , Kwong Allison J. 
Published: April 2022

Background:
NAFLD is common in primary care. Liver fibrosis stage 2 or higher (≥F2) increases future risk of morbidity and mortality. We developed and validated a score to aid in the initial assessment of liver fibrosis for NAFLD in primary care.

Methods:
Data from patients with biopsy‐proven NAFLD were extracted from the NASH Clinical Research Network observational study (n = 676). Using logistic regression and machine‐learning methods, we constructed prediction models to distinguish ≥F2 from F0/1. The models were tested in participants in a trial (“FLINT,” n = 280) and local patients with NAFLD with magnetic resonance elastography data (n = 130). The final model was applied to examinees in the National Health and Nutrition Examination Survey (NHANES) III (n = 11,953) to correlate with long‐term mortality.

Results:
A multivariable logistic regression model was selected as the Steatosis‐Associated Fibrosis Estimator (SAFE) score, which consists of age, body mass index, diabetes, platelets, aspartate and alanine aminotransferases, and globulins (total serum protein minus albumin). The model yielded areas under receiver operating characteristic curves ≥0.80 in distinguishing F0/1 from ≥F2 in testing data sets, consistently higher than those of Fibrosis‐4 and NAFLD Fibrosis Scores. The negative predictive values in ruling out ≥F2 at SAFE of 0 were 88% and 92% in the two testing sets. In the NHANES III set, survival up to 25 years of subjects with SAFE < 0 was comparable to that of those without steatosis (p = 0.34), whereas increasing SAFE scores correlated with shorter survival with an adjusted HR of 1.53 (p < 0.01) for subjects with SAFE > 100.

Conclusion:
The SAFE score, which uses widely available variables to estimate liver fibrosis in patients diagnosed with NAFLD, may be used in primary care to recognize low‐risk NAFLD.
Intestinal barrier dysfunction mediates Whipple's disease immune reconstitution inflammatory syndrome (IRIS)
Authors: Friebel Julian , Schinnerling Katina , Geelhaar‐Karsch Anika , Allers Kristina , Schneider Thomas , Moos Verena 
Published: April 2022

AbstractBackground & AimsClassical Whipple's disease (CWD) affects the gastrointestinal tract and causes chronic diarrhea, malabsorption, and barrier dysfunction with microbial translocation (MT). Immune reconstitution inflammatory syndrome (IRIS) is a serious complication during antimicrobial treatment of CWD. The pathomechanisms of IRIS have not been identified and mucosal barrier integrity has not been studied in patients with IRIS CWD.MethodsIn 96 CWD patients (n = 23 IRIS, n = 73 non‐IRIS) and 30 control subjects, we analysed duodenal morphology by histology, measured serum markers of MT, and proinflammatory cytokines in biopsy supernatants, and correlated microbial translocation with T cell reconstitution and activation.ResultsBefore treatment, duodenal specimens from patients who later developed IRIS exhibited a more pronounced morphological transformation that suggested a disturbed barrier integrity when compared with the non‐IRIS group. Villous atrophy was mediated by increased apoptosis of epithelial cells, which was insufficiently counterbalanced by regenerative proliferation of crypt cells. Pretreatment deficiencies in the mucosal secretion of proinflammatory cytokines and chemokines (e.g., IL‐6, CCL2) in these patients markedly resolved after therapy induction. High serum levels of lipopolysaccharides (LPS), soluble CD14 (sCD14), and LPS‐binding protein (LBP) combined with low endotoxin core antibody (EndoCAb) titres suggested systemic MT in CWD patients developing IRIS. CD4+ T cell count and activation in IRIS CWD patients correlated positively with sCD14 levels and negatively with EndoCAb titres. Furthermore, the degree of intestinal barrier dysfunction and MT was predictive for the onset of IRIS.ConclusionProlonged MT across a dysfunctional intestinal mucosal barrier due to severe tissue damage favors dysbalanced immune reconstitution and systemic immune activation in IRIS CWD. Therefore, the monitoring of inflammatory and MT markers in CWD patients might be helpful in identifying patients who are at risk of developing IRIS. Therapeutic strategies to reconstitute the mucosal barrier and control inflammation could assist in the prevention of IRIS.
An improved invasive weed optimization enabled Shepard convolutional neural network for classification of breast cancer
Authors: Salim Samla , R. Sarath 
Published: April 2022

AbstractOne of the most predominant types of cancer affecting women is breast cancer. In computer‐assisted analysis of pathology, the most crucial task is classifying breast cancer automatically from the histopathological images. Most of the patients experienced everlasting effects and loss of life because of the absence of timely detection and thereby delay in treatment. Thus, the timely detection as well as precise identification of breast cancer using the histopathological image is highly required. An improved invasive weed water wave optimization (IIWWWO) algorithm is devised here, which is employed in training the Shepard convolutional neural networks (ShCNN) classifier. The developed optimization algorithm combines the improved invasive weed optimization algorithm and water wave optimization algorithm. Initially, the Bayesian filtering process is applied in the input image to remove the noises present in the input image. Moreover, the Hessian‐based Laplacian of Gaussian texture feature model is utilized in segmenting blood cells for an effective classification process. The shape features, namely shape area, diameter, and perimeter, are effectively extracted for better performance. Besides, ShCNN classifier is the most important one for classifying breast cancers. The proposed IIWWWO optimization technique is utilized in tuning the employed classifier termed as ShCNN classifier. Classification of breast cancer is accomplished using two levels, such as malignant and benign. The developed IIWWWO‐based ShCNN model is compared with various metrics, like accuracy, true negative rate (TNR) and true positive rate (TPR). The developed technique used to classify breast cancer obtained better accuracy of 95.83%, maximal TPR of 94.72%, and high TNR of 93.15%.
Consequences of Chinese tariff and US MFP payments on world soybean‐complex markets
Authors: Baryshpolets Andrii , Devadoss Stephen , Sabala Ethan 
Published: April 2022

AbstractThis study develops a theoretical and empirical spatial equilibrium model to determine the effects of removing the Chinese soybean tariff and US MFP payments on world soybean‐complex markets. The model includes vertical and horizontal linkages of the soybean, soy oil, and soy meal markets, thus capturing the downstream effects of tariff and MFP payment removal. The study finds that removing these policies generates overall gains for the United States and the world, but China incurs welfare losses due primarily to reduced tariff revenues. These impacts of tariff and MFP payment elimination reverberate to all countries participating in soybean, soy oil, or soy meal trade.
Oxidative stress‐mediated up‐regulation of ABC transporters in lung cancer cells
Authors: Yuan Tongkuo , Hu Jia , Zhu Xiaoming , Yin Huancai , Yin Jian 
Published: April 2022

AbstractThis paper aimed to evaluate the role of oxidative stress in the regulation of ABC transporters in human lung cancer (A549) cells facing substrate (doxorubicin, DOX) and nonsubstrate (ethanol, ETH and hydrogen peroxide, HP) chemicals. After 24‐h treatment, all the chemicals caused significant cytotoxicity as reflected by the reduction in cell viability and the increase in reactive oxygen species (ROS) levels. Depending on the rescuing effects of ROS scavenger including glutathione (GSH) and Vitamin C, the toxicity dependence on oxidative stress were found to be HP > ETH > DOX. The addition of transporter inhibitors significantly enhanced the ROS levels and death‐inducing effects of chemicals, indicating the universal detoxification function of ABC transporters. At moderate ROS levels (about 3–4‐folds of control levels, caused by 10 μM DOX, 400 mM ETH, and 400 μM HP), all the three chemicals induced the gene expressions and activities of ABC transporters, but these values decreased at too high ROS levels (8.36‐folds of control levels) caused by HP at LC50 (800 μM). Such induction could be attenuated by GSH and KCZ, and was completely abolished by 50 μM KCZ, indicating an important role of oxidative stress and pregnane X receptor (PXR) in the induction of ABC transporters. Finally, this paper revealed the critical role of oxidative stress in the modulation of ABC transporters by either substrate or nonsubstrate chemicals during 24‐h treatment. Such information should be beneficial for overcoming ABC transporter‐mediated multidrug resistance.