bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Nature of Nonclassical Carbonyl Ligands Explained by Kohn–Sham Molecular Orbital Theory
Authors: van der Lubbe Stephanie C. C. , Vermeeren Pascal , Fonseca Guerra Célia , Bickelhaupt F. Matthias 
Published: October 2020

AbstractWhen carbonyl ligands coordinate to transition metals, their bond distance either increases (classical) or decreases (nonclassical) with respect to the bond length in the isolated CO molecule. C−O expansion can easily be understood by π‐back‐donation, which results in a population of the CO's π*‐antibonding orbital and hence a weakening of its bond. Nonclassical carbonyl ligands are less straightforward to explain, and their nature is still subject of an ongoing debate. In this work, we studied five isoelectronic octahedral complexes, namely Fe(CO)62+, Mn(CO)6+, Cr(CO)6, V(CO)6− and Ti(CO)62−, at the ZORA‐BLYP/TZ2P level of theory to explain this nonclassical behavior in the framework of Kohn–Sham molecular orbital theory. We show that there are two competing forces that affect the C−O bond length, namely electrostatic interactions (favoring C−O contraction) and π‐back‐donation (favoring C−O expansion). It is a balance between those two terms that determines whether the carbonyl is classical or nonclassical. By further decomposing the electrostatic interaction ΔVelstat into four fundamental terms, we are able to rationalize why ΔVelstat gives rise to the nonclassical behavior, leading to new insights into the driving forces behind C−O contraction.
Highly Deformedo‐Carborane Functionalised Non‐linear Polycyclic Aromatics with Exceptionally Long C−C Bonds
Authors: Marsh Adam V. , Little Mark , Cheetham Nathan J. , Dyson Matthew J. , Bidwell Matthew , White Andrew J. P. , Warriner Colin N. , Swain Anthony C. , McCulloch Iain , Stavrinou Paul N. , Heeney Martin 
Published: October 2020

AbstractThe effect of substitutingo‐carborane into the most sterically hindered positions of phenanthrene and benzo(k)tetraphene is reported. Synthesised via a Bull–Hutchings–Quayle benzannulation, the crystal structures of these non‐linear acenes exhibited the highest aromatic deformation parameters observed for any reported carborane compound to date, and among the largest carboranyl C−C bond length of all organo‐substitutedo‐carboranes. Photoluminescence studies of these compounds demonstrated efficient intramolecular charge‐transfer, leading to aggregation induced emission properties. Additionally, an unusual low‐energy excimer was observed for the phenanthryl compound. These are two new members of the family of carborane‐functionalised non‐linear acenes, notable for their peculiar structures and multi‐luminescent properties.
Fuel‐Driven Biorefineries Using Hydrothermal Processes
Authors: Klemm Marco , Kröger Michael , Görsch Kati , Müller‐Langer Franziska , Majer Stefan 
Published: October 2020

AbstractRegarding the aim of a CO2‐neutral society by 2050, one target is to use the largest possible amount of the initial feedstock within the bioeconomy. In that context it is necessary to utilize also low‐value biomass in biorefineries. For wet streams, hydrothermal processes can make an efficient thermochemical application possible. To be used as transport fuel, strict limitations from national and international standards have to be fulfilled, e.g., regarding oxygen content. To reach these boundaries, commonly multistage approaches have to be applied. Within this framework utilization of hydrogen donors can be beneficial. Basic calculations of costs and greenhouse gas emissions are given for an exemplary case.
Research on multiscale features and integrated forecasting of the Belt and Road exchange rate index
Authors: Cui Yixi , Liu Zixin , Li Ziran , Guo Kun , Sun Yishan 
Published: October 2020

AbstractMassive progress and fruitful results have been achieved since the implementation of the Belt and Road Initiative (B&R). However, the risk of exchange rate between countries along the Belt and Road cannot be ignored. In this paper, we propose a B&R exchange rate index to evaluate the currency risk of countries along the B&R, along with a research on the multiscale features of the B&R exchange rate index and the effective RMB exchange rate index using the EMD algorithm. Then, we propose an integrated forecasting approach. We adopt the EMD algorithm and the Grey Relational Analysis to decompose and reconstruct the B&R exchange rate index and the effective RMB exchange rate index into three subsections with different volatility characteristics. The prediction outcome of the integrated model for the original series equals a sum of the Auto‐regressive Integrated Moving Average model for trend term and the Long Short‐Term Memory model for market fluctuation term as well as noise term. The results of our prediction demonstrate a much better performance of our proposed integrated forecasting model than pure methods. Lastly, several suggestions are put forward to help relevant enterprises effectively avoid and manage the exchange risks.
Tri‐Allelic Haplotypes Determine and Differentiate Functionally Normal Allele CYP2D6*2 and Impaired Allele CYP2D6*41
Authors: Zanger Ulrich M. , Momoi Kyoko , Hofmann Ute , Schwab Matthias , Klein Kathrin 
Published: October 2020

CYP2D6 metabolizes 20–25% of all clinically used drugs and its complex genetic polymorphism is a major determinant of drug safety and efficacy. We investigated the basis for the functional difference between the two common alleles *2 (g.2851C>T + g.4181G>C, normal function) and *41 (additional intronic g.2989G>A, reduced function). A recently reported far‐distant enhancer polymorphism rs5758550A/G linked to *2 has been suggested to play a decisive role. Genotyping of two white cohorts confirmed strong linkage of rs5758550G to *2, whereas no influence was found on metabolic ratio of sparteine or hepatic expression. Genomic plasmid constructs carrying individual variants or combinations thereof were expressed in COS1 and Huh7 cells. Both g.2851C>T(R296C) and g.2989G>A reduced enzyme activity and protein levels similarly by ~ 50–65% compared to reference (*1), whereas the double variant had only ~ 20% activity. Although the unexpected loss of function caused by g.2851C>T was compensated by g.4181G>C (mimicking the EM‐phenotype of *2), the additional loss of function due to intronic g.2989G>A in the triple variant was not compensated (mimicking the IM‐phenotype of *41). We also confirmed increased erroneous splicing in carriers of g.2989G>A but not of g.2851C>T as a likely explanation for the impaired function of *41. In conclusion, our data demonstrate g.2989G>A as causal variant of impaired allele CYP2D6*41 whereas triple‐haplotypes have to be considered to explain the functional difference between *2 and *41. These data are important for genotyping strategies and clinical implementation of CYP2D6 pharmacogenetics.
Identification of scavenger receptors and thrombospondin‐type‐1 repeat proteins potentially relevant for plastid recognition in Sacoglossa
Authors: Melo Clavijo Jenny , Frankenbach Silja , Fidalgo Cátia , Serôdio João , Donath Alexander , Preisfeld Angelika , Christa Gregor 
Published: October 2020

AbstractFunctional kleptoplasty is a photosymbiotic relationship, in which photosynthetically active chloroplasts serve as an intracellular symbiont for a heterotrophic host. Among Metazoa, functional kleptoplasty is only found in marine sea slugs belonging to the Sacoglossa and recently described in Rhabdocoela worms. Although functional kleptoplasty has been intensively studied in Sacoglossa, the fundamentals of the specific recognition of the chloroplasts and their subsequent incorporation are unknown. The key to ensure the initiation of any symbiosis is the ability to specifically recognize the symbiont and to differentiate a symbiont from a pathogen. For instance, in photosymbiotic cnidarians, several studies have shown that the host innate immune system, in particular scavenger receptors (SRs) and thrombospondin‐type‐1 repeat (TSR) protein superfamily, is playing a major role in the process of recognizing and differentiating symbionts from pathogens. In the present study, SRs and TSRs of three Sacoglossa sea slugs, Elysia cornigera, Elysia timida, and Elysia chlorotica, were identified by translating available transcriptomes into potential proteins and searching for receptor specific protein and/or transmembrane domains. Both receptors classes are highly diverse in the slugs, and many new domain arrangements for each receptor class were found. The analyses of the gene expression of these three species provided a set of species‐specific candidate genes, that is, SR‐Bs, SR‐Es, C‐type lectins, and TSRs, that are potentially relevant for the recognition of kleptoplasts. The results set the base for future experimental studies to understand if and how these candidate receptors are indeed involved in chloroplast recognition.
Sheath‐assisted focusing of microparticles on lab‐on‐a‐chip platforms
Authors: Dalili Arash , Sattati Amirmohammad , Tasnim Nishat , Hoorfar Mina 
Published: October 2020

AbstractLab‐on‐a‐chip (LOC) technologies can take advantage of sheath flows for particle/cell focusing before sensing or sorting. The integration of focusing with other microscale manipulation techniques (e.g., sorting) creates a trade‐off between the throughput of the device and its performance. Therefore, exploring the effective parameters for cells/particles focusing enables us to improve the desired output of LOC devices. A common configuration for sheath‐assisted focusing is Y junctions, which are parametrically studied in this paper. First, a computational model was developed and validated by comparing it with our experimental results. Using COMSOL Multiphysics modeling, the effects of multiple parameters were studied. These parameters include the sheath flow ratio (sheath flow over total flow), width ratio (width of the sheath inlet over the total width), junction angles, and particle size on the focusing width and the distribution of the particles within the focusing region. Then, the numerical data were used to develop two generalized linear models to predict the focusing width of the particles and the standard deviation of the position of the particles. The results showed that the focusing width is greatly impacted by the sheath flow rate ratio. Further, the standard deviation of the position of the particles, which represents the concentration of the particles, is mostly dependent on the flow rate ratio, width ratio, and particle size. Our results provide a better understanding of how the device geometrical and operational factors affect the position of the particles in the development of high‐performance on‐chip sensing and sorting of both cells and particles.
A Markovian approach to infrastructure life‐cycle analysis: Modeling the interplay of hazard effects and recovery
Authors: Dehghani Nariman L. , Fereshtehnejad Ehsan , Shafieezadeh Abdollah 
Published: October 2020

AbstractProbabilistic life‐cycle cost (LCC) analysis facilitates optimal management of infrastructure systems under uncertainty. Despite recent advancements, accurate and efficient estimation of the LCC of systems facing risk of exposure to multiple stochastic occurrences of hazards has remained a significant challenge. This paper proposes a Markovian LCC framework that substantially reduces the often very high computational cost of probabilistic LCC analysis especially for large systems. The presented methodology also enhances the accuracy of LCC estimates in multiple fronts. It captures damage accumulations due to incomplete or no repair actions over multiple stochastic hazard exposures in a system's lifetime. Moreover, it tracks the state of infrastructure vulnerability during repair processes and incorporates uncertainties in downtimes associated with damage states of the system. Finally, it estimates the entirity of loss induced by a hazard and avoids the truncation error that exists in annual loss estimates for scenarios where repair downtimes are greater than one year. With these new capabilities, the proposed LCC framework is applied to a bridge in a seismic zone to estimate the LCC and analyze complex interactions of stochastic hazards and their effects with recovery efforts. Results indicate that neglecting effects of damage accumulation and partial improvements in the course of repair can lead to 20% underestimation and 14% overestimation of the expected hazard‐induced LCC, respectively.
A Reduced Model for Bioconcentration and Biotransformation of Neutral Organic Compounds in Midge
Authors: Kuo Dave T.F. , Chen Ciara C. 
Published: October 2020

Abstract
A bioconcentration factor (BCF) database and a toxicokinetic model considering only biota–water partitioning and biotransformation were constructed for neutral organic chemicals in midge. The database contained quality-reviewed BCF and toxicokinetic data with variability constrained to within 0.5 to 1 log unit. Diverse conditions in exposure duration, flow set-up, substrate presence, temperature, and taxonomic classification did not translate into substantial variability in BCF, uptake rate constant (k1), or depuration rate constant (kT), and no systematic bias was observed in BCFs derived in unlabeled versus radiolabeled studies. Substance-specific biotransformation rate constants kM were derived by difference between the calculated biota–water partitioning coefficient (KBW) and experimental BCF for developing a midge biotransformation model. Experimental midge BCF was modeled as BCF = KBW/(1 + kM/k2) with log kM (kM in h–1) = –0.37 log KOW – 0.06T (in K) + 18.87 (root mean square error [RMSE] = 0.60), log k1 (k1 in L kgwet.wt–1 h–1) = –0.0747 W (body weight in mgwet.wt) + 2.35 (RMSE = 0.48). The KBW value was estimated using midge biochemical composition and established polyparameter linear free energy relationships, and the diffusive elimination rate constant (k2) was computed as k2 = k1/KBW. The BCF model predicted &gt;85% of BCFs that associated with neutral organic compounds (log KOW = 1.46 – 7.75) to within 1 log-unit error margin and had comparable accuracy similar to amphipod or fish models. A number of outliers and critical limitations of the kM model were identified and examined, and they largely reflected the inherent limitation of difference-derived kM, the lack of chemical diversity, and inadequate temperature variation in existing data. Future modeling efforts can benefit from more BCF and toxicokinetic observations of BCF on structurally diverse chemicals for model training, validation, and diagnosis. Environ Toxicol Chem 2021;40:57–71. © 2020 SETAC
Addition of Phenylmethylsulfonyl Fluoride Increases the Working Lifetime of the Trout Liver S9 Substrate Depletion Assay, Resulting in Improved Detection of Low Intrinsic Clearance Rates
Authors: Nichols John W. , Hoffman Alex D. , Swintek Joe A. , Droge Steven T.J. , Fitzsimmons Patrick N. 
Published: October 2020

Abstract
The activity of a trout liver S9 substrate depletion assay has been shown to decline over time, presumably due to proteolytic degradation of biotransformation enzymes. To address this problem, assay performance was evaluated following the addition of phenylmethylsulfonyl fluoride (PMSF) or a general-purpose protease inhibitor cocktail to liver homogenization buffers and/or S9 reaction mixtures. Addition of PMSF to liver homogenization buffers and/or S9 reaction mixtures had little or no effect on clearance of phenanthrene, a model cytochrome P450 substrate, in short-term (25 or 30 min) depletion experiments but resulted in significant improvements in retention of this initial activity over time. The protease inhibitor cocktail strongly inhibited initial activity when added to homogenization buffers or reaction mixtures. Taking into consideration potential effects on liver carboxylesterases, the treatment approach determined to be optimal was addition of 10 µM PMSF to the S9 reaction mixture. Addition of 10 µM PMSF to the mixture resulted in significantly higher rates of phenanthrene clearance in 2-h incubations relative to those obtained in the absence of PMSF and a 6-fold increase in the working lifetime of the preparation. The results of a statistical power analysis suggest that by increasing the working lifetime of the assay, addition of PMSF to the reaction mixture could result in substantially improved detection of low in vitro clearance rates when compared to current practice. These findings demonstrate the value of adding PMSF to the trout S9 preparation and may have broad implications for use of this assay to support chemical bioaccumulation assessments for fish. Environ Toxicol Chem 2021;40:148–161. © 2020 SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.
Adsorption and Desorption of Triclosan on Biodegradable Polyhydroxybutyrate Microplastics
Authors: Tong Huiyan , Hu Xingshuai , Zhong Xiaocong , Jiang Qianyi 
Published: October 2020

Abstract
Biodegradable plastics have been increasingly used as a solution to the problem of plastic pollution in recent years. However, there are few studies on the negative effects of biodegradable microplastics. Triclosan, a widely used disinfectant, is a highly toxic substance. In the present study, the adsorption and desorption processes of triclosan on a type of biodegradable plastics, polyhydroxybutyrate (PHB), were investigated and also compared with one conventional plastic type, polyethylene. The adsorption equilibrium quantities of polyethylene and PHB were 3431.85 and 9442.27 μg/g, respectively. The adsorption rate and equilibrium adsorption capacity of triclosan on PHB are much higher than on polyethylene. Physical adsorption of triclosan on PHB and polyethylene microplastics may play a dominant role in this process. The desorption hysteresis indices are all less than zero; this indicates that triclosan is easily released from PHB and polyethylene microplastics under physiological conditions. Our results indicate that biodegradable PHB microplastics are stronger carriers for triclosan than the conventional polyethylene microplastics in the aquatic environment. Environ Toxicol Chem 2021;40:72–78. © 2020 SETAC
Abstract
Adsorption and desorption behaviors of TCS on biodegradable PHB microplastics and conventional PE microplastics were assessed. The adsorption rate and equilibrium adsorption capacity of triclosan on PHB are much higher than PE. Biodegradable microplastics such as PHB could also be a potential carrier for contaminations, and bring the potential risks of triclosan for bioaccumulation in aquatic organisms.
Comparative study of innovative blends prepared by fortification of date powder to alleviate child malnutrition
Authors: Raza Nighat , Arshad Muhammad Umair , Saeed Farhan , Farooq Umar , Naz Ambreen , Murtaza Mian Shamas , Badar Ul Ain Huma , Tufail Tabussam , Imran Muhammad , Anjum Faqir Muhammad 
Published: October 2020

AbstractChild malnutrition is one of the biggest problems in developing countries with higher level of food insecurity. Pakistan is 5th largest producer of date fruit; therefore, its processing and products should be explored in various dimensions. Being rich source of minerals and sugars, it can contribute in weaning foods in a good manner. In current study, three blends were prepared with specific proportions of spray‐dried date powder and rich in specific proportions. They were compared with each other and control (free of date powder). The nutritional profile of the formulations revealed that 100 g of each formulation included all macronutrients in compliance with the requirements of Food and Agriculture Organization for weaning formulations; moreover, they are enriched with minerals due to presence of date powder. The iron contents reached up to 12.74 ± 0.16 mg/100 g. The phosphorus, zinc, and potassium contents also increased with the increase in date powder subsequently. Physicochemical properties exhibited in compliance with the requirement of the weaning foods. The protein quality was assessed both in vivo and in vitro. Amino acid profiling indicated that the limiting amino acid in F1 and control were lysine but in F2 and F3 were threonine. This is suggested that date powder might contain good quality protein that was further explained in biological studies, the formulations that contained higher amount of date powder reveled better PDCAAS score 86.76 ± 4.5, true digestibility 84 ± 4.36, biological value 69.45 ± 0.69, net protein utilization 73.82 ± 1.46, and protein efficiency score 1.18 ± 0.07. The sensory evaluation revealed that F2 showed better result in overall acceptability. Thus, date powder is suggested to be used as good constituent that can fortify mineral contents and sugar contents of the weaning foods.
Transoral endoscopic thyroidectomy vestibular approach vs conventional open thyroidectomy: Meta‐analysis
Authors: Wang Yichao , Zhou Shengliang , Liu Xueting , Rui Shu , Li Zhihui , Zhu Jingqiang , Wei Tao 
Published: October 2020

AbstractBackgroundTo conduct a meta‐analysis to compare the safety and efficacy of transoral endoscopic thyroidectomy vestibular approach (TOETVA) with conventional open thyroidectomy (COT).MethodsMEDLINE, EMBASE, Science Citation Index Expanded, and the Cochrane Central Register of Controlled Trials in the Cochrane Library from January 2007 to March 2020 were searched to identify studies comparing TOETVA and COT.ResultsSix eligible nonrandomized studies involving 1151 patients were included. Meta‐analysis results revealed that TOETVA group had a significantly longer operative time (weighted mean difference [WMD], 66.09; 95% confidence interval [CI], 35.22‐96.96; P < .0001) and larger amount of drainage (WMD, 98; 95% CI, 20.14‐175.86; P = .01). There were no significant differences in terms of postoperative outcomes.ConclusionTOETVA appears to be as feasible and safe as the COT for the treatment of patients with benign thyroid nodules and selected differential thyroid carcinomas.
Influence of timeliness and receipt of first treatment on geographic variation in non‐small cell lung cancer mortality
Authors: Wah Win , Stirling Rob G. , Ahern Susannah , Earnest Arul 
Published: October 2020

AbstractMortality from non‐small cell lung cancer (NSCLC) exhibits substantial geographical disparities. However, there is little evidence on whether this variation could be attributed to patients' clinical characteristics and/or socioeconomic inequalities. This study evaluated the independent and relative contribution of the individual‐ and area‐level risk factors on geographic variation in 2‐year all‐cause mortality among NSCLC patients. In the Hierarchical‐related regression approach, we used the Bayesian spatial multilevel logistic regression model to combine individual‐ and area‐level predictors with outcomes while accounting for geographically structured and unstructured correlation. Individual‐level data included 3330 NSCLC cases reported to the Victoria Lung Cancer Registry between 2011 and 2016. Area‐level data comprised socioeconomic disadvantage, remoteness and pollution data at the postal area level in Victoria, Australia. With the inclusion of significant individual‐ and area‐level risk factors, timely (≤14 days) first definitive treatment (odds ratio [OR] = 0.73, 95% credible interval [Crl] = 0.56‐0.94) and multidisciplinary meetings (MDM) (OR = 0.74, 95% Crl = 0.59‐0.93) showed an independent association with a lower likelihood of NSCLC 2‐year all‐cause mortality. Timely and delayed (>14 days) first nondefinitive treatment, no treatment, advanced clinical stage, smoking, poor performance status, public hospital insurance and area‐level deprivation were independently associated with a higher likelihood of 2‐ and 5‐year all‐cause mortality. NSCLC's 2‐year all‐cause mortality exhibited substantial geographic variation, mainly associated with timeliness and receipt of first definitive treatment, no treatment followed by patient prognostic factors with some contribution from area‐level deprivation, MDM and public hospital insurance. This study highlights NSCLC patients should receive the first definitive treatment within the recommended 14‐days from diagnosis.