bluuebunny/crossref_metadata_2025_split huggingface dataset:
Selective photoinduced charge separation in perylenediimide-pillar[5]arene rotaxanes
Authors: Pearce Nicholas , Reynolds Katherine E. A. , Kayal Surajit , Sun Xue Z. , Davies E. Stephen , Malagreca Ferdinando , Schürmann Christian J. , Ito Sho , Yamano Akihito , Argent Stephen P. , George Michael W. , Champness Neil R. 
Published: January 2022

AbstractThe ability to control photoinduced charge transfer within molecules represents a major challenge requiring precise control of the relative positioning and orientation of donor and acceptor groups. Here we show that such photoinduced charge transfer processes within homo- and hetero-rotaxanes can be controlled through organisation of the components of the mechanically interlocked molecules, introducing alternative pathways for electron donation. Specifically, studies of two rotaxanes are described: a homo[3]rotaxane, built from a perylenediimide diimidazolium rod that threads two pillar[5]arene macrocycles, and a hetero[4]rotaxane in which an additional bis(1,5-naphtho)-38-crown-10 (BN38C10) macrocycle encircles the central perylenediimide. The two rotaxanes are characterised by a combination of techniques including electron diffraction crystallography in the case of the hetero[4]rotaxane. Cyclic voltammetry, spectroelectrochemistry, and EPR spectroscopy are employed to establish the behaviour of the redox states of both rotaxanes and these data are used to inform photophysical studies using time-resolved infra-red (TRIR) and transient absorption (TA) spectroscopies. The latter studies illustrate the formation of a symmetry-breaking charge-separated state in the case of the homo[3]rotaxane in which charge transfer between the pillar[5]arene and perylenediimide is observed involving only one of the two macrocyclic components. In the case of the hetero[4]rotaxane charge separation is observed involving only the BN38C10 macrocycle and the perylenediimide leaving the pillar[5]arene components unperturbed.
Accurate determination of solvation free energies of neutral organic compounds from first principles
Authors: Pereyaslavets Leonid , Kamath Ganesh , Butin Oleg , Illarionov Alexey , Olevanov Michael , Kurnikov Igor , Sakipov Serzhan , Leontyev Igor , Voronina Ekaterina , Gannon Tyler , Nawrocki Grzegorz , Darkhovskiy Mikhail , Ivahnenko Ilya , Kostikov Alexander , Scaranto Jessica , Kurnikova Maria G. , Banik Suvo , Chan Henry , Sternberg Michael G. , Sankaranarayanan Subramanian K. R. S. , Crawford Brad , Potoff Jeffrey , Levitt Michael , Kornberg Roger D. , Fain Boris 
Published: January 2022

AbstractThe main goal of molecular simulation is to accurately predict experimental observables of molecular systems. Another long-standing goal is to devise models for arbitrary neutral organic molecules with little or no reliance on experimental data. While separately these goals have been met to various degrees, for an arbitrary system of molecules they have not been achieved simultaneously. For biophysical ensembles that exist at room temperature and pressure, and where the entropic contributions are on par with interaction strengths, it is the free energies that are both most important and most difficult to predict. We compute the free energies of solvation for a diverse set of neutral organic compounds using a polarizable force field fitted entirely to ab initio calculations. The mean absolute errors (MAE) of hydration, cyclohexane solvation, and corresponding partition coefficients are 0.2 kcal/mol, 0.3 kcal/mol and 0.22 log units, i.e. within chemical accuracy. The model (ARROW FF) is multipolar, polarizable, and its accompanying simulation stack includes nuclear quantum effects (NQE). The simulation tools’ computational efficiency is on a par with current state-of-the-art packages. The construction of a wide-coverage molecular modelling toolset from first principles, together with its excellent predictive ability in the liquid phase is a major advance in biomolecular simulation.
Artificial-intelligence-driven discovery of catalyst genes with application to CO2 activation on semiconductor oxides
Authors: Mazheika Aliaksei , Wang Yang-Gang , Valero Rosendo , Viñes Francesc , Illas Francesc , Ghiringhelli Luca M. , Levchenko Sergey V. , Scheffler Matthias 
Published: January 2022

AbstractCatalytic-materials design requires predictive modeling of the interaction between catalyst and reactants. This is challenging due to the complexity and diversity of structure-property relationships across the chemical space. Here, we report a strategy for a rational design of catalytic materials using the artificial intelligence approach (AI) subgroup discovery. We identify catalyst genes (features) that correlate with mechanisms that trigger, facilitate, or hinder the activation of carbon dioxide (CO2) towards a chemical conversion. The AI model is trained on first-principles data for a broad family of oxides. We demonstrate that surfaces of experimentally identified good catalysts consistently exhibit combinations of genes resulting in a strong elongation of a C-O bond. The same combinations of genes also minimize the OCO-angle, the previously proposed indicator of activation, albeit under the constraint that the Sabatier principle is satisfied. Based on these findings, we propose a set of new promising catalyst materials for CO2 conversion.
Enrichment of the exocytosis protein STX4 in skeletal muscle remediates peripheral insulin resistance and alters mitochondrial dynamics via Drp1
Authors: Merz Karla E. , Hwang Jinhee , Zhou Chunxue , Veluthakal Rajakrishnan , McCown Erika M. , Hamilton Angelica , Oh Eunjin , Dai Wenting , Fueger Patrick T. , Jiang Lei , Huss Janice. M. , Thurmond Debbie C. 
Published: January 2022

AbstractMitochondrial dysfunction is implicated in skeletal muscle insulin resistance. Syntaxin 4 (STX4) levels are reduced in human diabetic skeletal muscle, and global transgenic enrichment of STX4 expression improves insulin sensitivity in mice. Here, we show that transgenic skeletal muscle-specific STX4 enrichment (skmSTX4tg) in mice reverses established insulin resistance and improves mitochondrial function in the context of diabetogenic stress. Specifically, skmSTX4tg reversed insulin resistance caused by high-fat diet (HFD) without altering body weight or food consumption. Electron microscopy of wild-type mouse muscle revealed STX4 localisation at or proximal to the mitochondrial membrane. STX4 enrichment prevented HFD-induced mitochondrial fragmentation and dysfunction through a mechanism involving STX4-Drp1 interaction and elevated AMPK-mediated phosphorylation at Drp1 S637, which favors fusion. Our findings challenge the dogma that STX4 acts solely at the plasma membrane, revealing that STX4 localises at/proximal to and regulates the function of mitochondria in muscle. These results establish skeletal muscle STX4 enrichment as a candidate therapeutic strategy to reverse peripheral insulin resistance.
Formation of twelve-fold iodine coordination at high pressure
Authors: Liu Yan , Wang Rui , Wang Zhigang , Li Da , Cui Tian 
Published: January 2022

AbstractHalogen compounds have been studied widely due to their unique hypercoordinated and hypervalent features. Generally, in halogen compounds, the maximal coordination number of halogens is smaller than eight. Here, based on the particle swarm optimization method and first-principles calculations, we report an exotically icosahedral cage-like hypercoordinated IN6 compound composed of N6 rings and an unusual iodine−nitrogen covalent bond network. To the best of our knowledge, this is the first halogen compound showing twelve-fold coordination of halogen. High pressure and the presence of N6 rings reduce the energy level of the 5d orbitals of iodine, making them part of the valence orbital. Highly symmetrical covalent bonding networks contribute to the formation of twelve-fold iodine hypercoordination. Moreover, our theoretical analysis suggests that a halogen element with a lower atomic number has a weaker propensity for valence expansion in halogen nitrides.
Bio-inspired lanthanum-ortho-quinone catalysis for aerobic alcohol oxidation: semi-quinone anionic radical as redox ligand
Authors: Zhang Ruipu , Zhang Runze , Jian Ruijun , Zhang Long , Zhang Ming-Tian , Xia Yu , Luo Sanzhong 
Published: January 2022

AbstractOxidation reactions are fundamental transformations in organic synthesis and chemical industry. With oxygen or air as terminal oxidant, aerobic oxidation catalysis provides the most sustainable and economic oxidation processes. Most aerobic oxidation catalysis employs redox metal as its active center. While nature provides non-redox metal strategy as in pyrroloquinoline quinone (PQQ)-dependent methanol dehydrogenases (MDH), such an effective chemical version is unknown. Inspired by the recently discovered rare earth metal-dependent enzyme Ln-MDH, here we show that an open-shell semi-quinone anionic radical species in complexing with lanthanum could serve as a very efficient aerobic oxidation catalyst under ambient conditions. In this catalyst, the lanthanum(III) ion serves only as a Lewis acid promoter and the redox process occurs exclusively on the semiquinone ligand. The catalysis is initiated by 1e--reduction of lanthanum-activated ortho-quinone to a semiquinone-lanthanum complex La(SQ-.)2, which undergoes a coupled O-H/C-H (PCHT: proton coupled hydride transfer) dehydrogenation for aerobic oxidation of alcohols with up to 330 h−1 TOF.
Solid-state optical properties of self-assembling amyloid-like peptides with different charged states at the terminal ends
Authors: Schiattarella Chiara , Diaferia Carlo , Gallo Enrico , Della Ventura Bartolomeo , Morelli Giancarlo , Vitagliano Luigi , Velotta Raffaele , Accardo Antonella 
Published: January 2022

AbstractThe self-assembling of small peptides not only leads to the formation of intriguing nanoarchitectures, but also generates materials with unexpected functional properties. Oligopeptides can form amyloid-like cross-β assemblies that are able to emit intrinsic photoluminescence (PL), over the whole near-UV/visible range, whose origin is still largely debated. As proton transfer between the peptide chain termini within the assembly is one of the invoked interpretations of this phenomenon, we here evaluated the solid state PL properties of a series of self-assembled hexaphenylalanine peptides characterized by a different terminal charge state. Overall, our data indicate that the charge state of these peptides has a marginal role in the PL emission as all systems exhibit very similar multicolour PL associated with a violation of the Kasha’s rule. On the other hand, charged/uncharged ends occasionally produce differences in the quantum yields. The generality of these observations has been proven by extending these analyses to the Aβ16–21 peptide. Collectively, the present findings provide useful information for deciphering the code that links the spectroscopic properties of these assemblies to their structural/electronic features.
A review of some techniques for inclusion of domain-knowledge into deep neural networks
Authors: Dash Tirtharaj , Chitlangia Sharad , Ahuja Aditya , Srinivasan Ashwin 
Published: January 2022

AbstractWe present a survey of ways in which existing scientific knowledge are included when constructing models with neural networks. The inclusion of domain-knowledge is of special interest not just to constructing scientific assistants, but also, many other areas that involve understanding data using human-machine collaboration. In many such instances, machine-based model construction may benefit significantly from being provided with human-knowledge of the domain encoded in a sufficiently precise form. This paper examines the inclusion of domain-knowledge by means of changes to: the input, the loss-function, and the architecture of deep networks. The categorisation is for ease of exposition: in practice we expect a combination of such changes will be employed. In each category, we describe techniques that have been shown to yield significant changes in the performance of deep neural networks.
Deep learning-based algorithm for lung cancer detection on chest radiographs using the segmentation method
Authors: Shimazaki Akitoshi , Ueda Daiju , Choppin Antoine , Yamamoto Akira , Honjo Takashi , Shimahara Yuki , Miki Yukio 
Published: January 2022

AbstractWe developed and validated a deep learning (DL)-based model using the segmentation method and assessed its ability to detect lung cancer on chest radiographs. Chest radiographs for use as a training dataset and a test dataset were collected separately from January 2006 to June 2018 at our hospital. The training dataset was used to train and validate the DL-based model with five-fold cross-validation. The model sensitivity and mean false positive indications per image (mFPI) were assessed with the independent test dataset. The training dataset included 629 radiographs with 652 nodules/masses and the test dataset included 151 radiographs with 159 nodules/masses. The DL-based model had a sensitivity of 0.73 with 0.13 mFPI in the test dataset. Sensitivity was lower in lung cancers that overlapped with blind spots such as pulmonary apices, pulmonary hila, chest wall, heart, and sub-diaphragmatic space (0.50–0.64) compared with those in non-overlapped locations (0.87). The dice coefficient for the 159 malignant lesions was on average 0.52. The DL-based model was able to detect lung cancers on chest radiographs, with low mFPI.
The usefulness of dual mobility cups in primary total hip arthroplasty patients at a risk of dislocation
Authors: Moon Nam Hoon , Do Min Uk , Kim Jung Shin , Seo Jae Seung , Shin Won Chul 
Published: January 2022

AbstractThis study aimed to evaluate the early results of primary total hip arthroplasty (THA) using dual mobility (DM) cups in patients at a risk of dislocation and compare them with that of fixed bearing (FB) THA. This retrospective study included patients who had undergone primary THA between January 2016 and December 2018 and were at a risk of dislocation. A propensity score-matched analysis was conducted for 63 THA procedures with vitamin-E infused highly cross-linked polyethylene (VEPE) DM bearing and 63 THA procedures performed with FB from the same manufacturer for a mean follow-up period of 3.1 and 3.5 years, respectively. The radiologic outcomes at the last follow-up and incidence of postoperative complications were evaluated and compared statistically between the two groups. The modified Harris hip score (mHHS) was used to assess patient-reported outcomes. Postoperative dislocation occurred in 4 cases (6.3%) in the FB group, but did not occur in the DM group (p = 0.042). There was no difference in the radiologic outcomes and postoperative complications between the two groups. The mHHS at the last follow-up showed satisfactory outcomes in both the groups (DM group, 90.5; FB group, 88.1), without a statistical difference between the groups. The early results of THA using VEPE DM bearing showed better outcomes than that of THA with FB for patients at a risk of dislocation. A longer follow-up period is recommended to assess the stability and overall outcomes.
Lung-protective effect of Punicalagin on LPS-induced acute lung injury in mice
Authors: Zeng Yibin , Zhao Hongying , Zhang Tong , Zhang Chao , He Yanni , Du Lingbo , Zuo Fuguo , Wang Wuqing 
Published: January 2022

Abstract
Background: Punicalagin (Pun) is one of the main bioactive compounds in pomegranate peel, it possesses many properties, including antioxidant, anti-inflammation and immunosuppressive activities. The study was aimed to investigate the protective effect and mechanisms of Pun on lipopolysaccharide (LPS)-induced acute lung injury (ALI) in mice.
Methods and Results: Forty-eight BALB/c male mice were used to establish ALI by intratracheal-instilled 2.4 mg/kg LPS, the mice were randomly divided into model and Pun (10, 20, 40 mg/kg) groups. The other 12 mice were intratracheal-instilled same volume of water as control. After 2 h of receiving LPS, mice were administered drug through intraperitoneal injection. Lung index, histopathological changes, white blood cells and biomarkers in bronchoalveolar lavage fluid (BALF) were analyzed. The protein expression of total and phosphor p65, IκBα, ERK1/2, JNK and p38 in lung tissue was detected. The result showed that Pun could reduce the lung index and wet/dry weight (W/D) ratio, improve lung histopathological injury. In addition, Pun decreased the inflammation cells and regulated the biomarkers in BALF. Furthermore, Pun dose-dependently reduced the phosphor protein levels of p65, IκBα, ERK1/2, JNK and p38 in lung tissue, which exhibited that the effect of Pun related to mitogen-activated protein kinases (MAPKs) pathway. More importantly, there was no toxicity was observed in the acute toxicity study of Pun.
Conclusion: Pun improves LPS-induced ALI mainly through its anti-inflammatory properties, which is associated with nuclear factor-κB (NF-κB) and MAPKs signaling pathways. The study implied that Pun maybe a potent agent against ALI in future clinic.
Oral Care in Acute Stroke
Authors: Gurgel-Juarez Nalia , Mallet Karen , Egan Mary , Blacquiere Dylan , Laneville Anik , Perrier Marie-France , Martineau Isabelle , Flowers Heather Leslie 
Published: January 2022

Purpose:Stroke impacts independent activities, particularly personal care such as oral hygiene. Existing guidelines lack details about how to provide effective oral care. This study explores the frequency of oral care based on staff adherence to oral care policies.Method:As part of a quality improvement initiative, we conducted a retrospective chart review of 30 consecutive stroke admissions to an acute care hospital. Patients with primary intracerebral hemorrhage or ischemic stroke were eligible. Sources of information included a decision support database and an electronic chart review. Data collection included length of hospitalization, stroke type, presence of infections, oral mechanism exam, dysphagia evaluations, and daily personal care provision by nursing staff (e.g., oral care and bathing).Results:Twenty-seven patients met the inclusion criteria. They had a mean age of 74 years, and 52% were men. Most had supratentorial stroke (86%) with comparable frequencies of right (48%) and left (52%) hemisphere lesions. In over half of the cases, provision of oral care was not documented at any point during the patients' hospitalization (Mdn= 128 hr). Pericare and bathing were about twice and 4 times more frequent than oral care, respectively.Conclusions:Oral care after stroke is challenging. Existing oral care recommendations from stroke guidelines lack sufficient detail and warrant reconsideration for optimal and routine implementation particularly in acute settings. Education around oral care and associated protocols are necessary to advance oral care practices and improve stroke recovery.
A gridded modular bidirectional high voltage gain soft‐switching DC–DC converter and its multiport expansion
Authors: Sun Lejia , Xue Xuan , Zhang Shaohua , Lv Hongliang , Zhang Yuming 
Published: January 2022

AbstractHere, a novel modular bidirectional high voltage gain soft‐switching DC–DC converter is proposed. The proposed converter named gridded modular high‐gain soft‐switching DC–DC converter (GMHSC) can achieve wide range expansion of port voltage and voltage gain by gridded filling of modules and achieve voltage and current sharing among these modules. In addition, all semiconductor devices also realize full‐load soft‐switching operation in both power directions by introducing a simple auxiliary zero‐current transaction (ZCT) cell in each module. A distributed control system including a centre controller and localized module controllers is proposed to improve the converter's design flexibility and dynamic performance. Moreover, the GMHSC is able to provide multiple fixed voltage nodes, which makes it suitable to expend to a multiport converter. A 1.6 kW 200 kHz experimental prototype based on SiC device is provided to achieve an efficiency of 97.9% and 97.7% in boost and buck modes, respectively. Furthermore, the input current and output voltage ripples are greatly reduced through interleaved operation of the GMHSC.
Endoscopic diverticulotomy for Killian-Jamieson diverticulum: mid-term outcome and description of an ultra-short tunnel technique
Authors: Modayil Rani J. , Zhang Xiaocen , Ali Mohammad , Das Kanak , Gurram Krishna , Stavropoulos Stavros N. 
Published: January 2022

Abstract
Background and study aims Killian-Jamieson Diverticulum (KJD) is a rarer and more recently described upper pharyngeal diverticulum than Zenker’s diverticulum (ZD). KJD is more difficult to manage than ZD because it tends to extend lower into the upper mediastinum and the diverticulum neck is in close proximity to the recurrent laryngeal nerve. There is limited literature on KJD management and transcervical surgical diverticulectomy is the mainstay of therapy.
Patients and methods Here we describe two methods of endoscopic diverticulotomy to treat KJD – direct and tunneling diverticulotomy (with hypopharyngeal tunnel or ultra-short tunnel – the latter being our preferred technique).
Results This was a retrospective study including 13 consecutive patients between March 2015 and April 2018. Three patients received direct and 10 received tunneling diverticulotomy (7 with the hypopharyngeal tunnel and 3 with the ultra-short tunnel). All procedures were completed in 16 to 52 minutes. There was no incidence of bleeding, mediastinitis, or sign of recurrent laryngeal nerve injury. At follow up of 9 to 79 months (median 33), the clinical success rate was 92 % (12/13); 11 patients had complete symptom resolution (post-operative symptom score = 0) and one patient had near-complete symptom resolution (occasional residual dysphagia). One patient receiving direct myotomy had limited symptom relief (frequent residual dysphagia and occasional residual regurgitation), possibly related to incomplete myotomy.
Conclusions Endoscopic tunneling diverticulotomy is a feasible, safe, and effective method to treat KJD.
Initial application of deep learning to borescope detection of endoscope working channel damage and residue
Authors: Barakat Monique T. , Girotra Mohit , Banerjee Subhas 
Published: January 2022

Abstract
Background and study aims Outbreaks of endoscopy-related infections have prompted evaluation for potential contributing factors. We and others have demonstrated the utility of borescope inspection of endoscope working channels to identify occult damage that may impact the adequacy of endoscope reprocessing. The time investment and training necessary for borescope inspection have been cited as barriers preventing implementation. We investigated the utility of artificial intelligence (AI) for streamlining and enhancing the value of borescope inspection of endoscope working channels.
Methods We applied a deep learning AI approach to borescope inspection videos of the working channels of 20 endoscopes in use at our academic institution. We evaluated the sensitivity, accuracy, and reliability of this software for detection of endoscope working channel findings.
Results Overall sensitivity for AI-based detection of borescope inspection findings identified by gold standard endoscopist inspection was 91.4 %. Labels were accurate for 67 % of these working channel findings and accuracy varied by endoscope segment. Read-to-read variability was noted to be minimal, with test-retest correlation value of 0.986. Endoscope type did not predict accuracy of the AI system (P = 0.26).
Conclusions Harnessing the power of AI for detection of endoscope working channel damage and residue could enable sterile processing department technicians to feasibly assess endoscopes for working channel damage and perform endoscope reprocessing surveillance. Endoscopes that accumulate an unacceptable level of damage may be flagged for further manual evaluation and consideration for manufacturer evaluation/repair.