bluuebunny/crossref_metadata_2025 huggingface dataset:
Структурный анализ дефектов в слоистых двойных гидроксидах и оксидах смешанного состава на их основе
Authors: Leont’eva N.N. , Drozdov V.A. , Belskaya O.B. , Cherepanova S.V.
Published: February 2019

В данной статье представлен обзор результатов исследования дефектов структуры MgAl и NiAl слоистых двойных гидроксидов и продуктов их терморазложения до 1000 °С, полученных за последние 10 лет в лаборатории аналитических и физико-химических методов исследования ИППУ СО РАН. Представленные результаты выполнены с использованием метода моделирования рентгенограмм для одномерно (1D) разупорядоченных кристаллов. Установлены изменения типа дефектов структуры в зависимости от температуры прокаливания, в том числе в условиях in situ рентгенографии. Предложен структурный механизм образования дегидратированной фазы при Т=200 °С. Представлены новые модели структур MgAl и NiAl оксидов. Установлены структуры фаз, входящих в состав продуктов гидратации оксидов. Объяснено различие в поведении оксидов при гидратации.
Современные катализаторы и способы неокислительного превращения метана
Authors: Golinsky D. , Vinichenko N. , Zatolokina E. , Pashkov V. , Paukshtis E. , Gulyaeva T. , Pavluchenko P. , Krol O. , Beliy A.
Published: February 2019

В работе проведено обобщение имеющихся данных по современным способам неокислительной конверсии метана и катализаторам для представленных процессов. Рассмотрены закономерности превращения молекулы на цеолитных и металлоксидных системах (двустадийные процессы). Также представлены результаты исследований по совместному превращению метана и н-пентана. Показано влияние природы металла, типа носителя, а также условий проведения процесса на особенности хемосорбции метана и степень его дегидрирования. Изучена реакционная способность образующихся углеводородных фрагментов в реакции образования ароматических углеводородов с н-пентаном.
ЗАКОНОМЕРНОСТИ ФОРМИРОВАНИЯ АКТИВНОЙ ПОВЕРХНОСТИ ВОЛЬФРАМАТСОДЕРЖАЩЕГО ДИОКСИДА ЦИРКОНИЯ, КАК КАТАЛИЗАТОРА ИЗОМЕРИЗАЦИИ С7-АЛКАНОВ
Authors: Smolikov M.D. , Shkurenok V.A. , Yablokova S.S. , Kir’yanov D.I. , Belyi A.S.
Published: February 2019

Изомеризация парафиновых углеводородов является одним из важнейших процессов нефтеперерабатывающей промышленности, направленный на получение высокооктановых экологичных компонентов современных бензинов. Актуальным направлением в изомеризации является переработка фракции, содержащей С7-алканы. Обзор посвящен современным представлениям о закономерностях формирования активной поверхности вольфраматсодержащего диоксида циркония, который представляет собой высокоактивную каталитическую систему для реакции изомеризации гептанов. В обзоре рассматриваются вопросы по влиянию способа синтеза вольфраматсодержащего диоксида циркония, его химического состава, фазового строения и кислотных свойств на формирование активной поверхности систем WO3/ZrO2 и их каталитическую активность. Рассмотрена роль платины в каталитических системах WO3/ZrO2 для реакции изомеризации С7-алканов.
Co-expression of HIF-1α, MDR1 and LAPTM4B in peripheral blood of solid tumors
Authors: Rehman Zaira , Fahim Ammad , Bhatti Attya , Sadia Hajra , John Peter
Published: February 2019

The hypoxic tumor microenvironment is the major contributor of chemotherapy resistance in solid tumors. One of the key regulators of hypoxic responses within the cell is the hypoxia inducible factor-1α (HIF-1α) that is involved in transcription of genes promoting cell survival and chemotherapy resistance. Multidrug resistance gene-1 (MDR1) and Lysosome-associated protein transmembrane 4B-35 (LAPTM4B-35) are among those notable players which augment their responses to cellular hypoxia. MDR1 is the hypoxia responsive gene involved in multidrug resistance phenotype while LAPTM4B-35 is involved in chemotherapy resistance by stabilizing HIF-1α and overexpressing MDR1. Overexpression of HIF-1α, MDR1 and LAPTM4B has been associated with poor disease outcome in many cancers when studied individually at tissue level. However, accessibility of the tissues following the course of chemotherapy for ascertaining chemotherapy resistance is difficult and sometimes not clinically feasible. Therefore, indication of hypoxic biomarkers in patient’s blood can significantly alter the clinical outcome. Hence there is a need to identify a blood based marker to understand the disease progression. In the current study the expression of hypoxia associated chemotherapy resistance genes were studied in the peripheral blood lymphocytes of solid tumor patients and any potential correlation with disease progression were explored. The expression of HIF-1α, MDR1 and LAPTM4B was studied in blood of 72 breast, 42 ovarian, 32 colon and 21 prostate cancer patients through real time PCR analysis using delta cycle threshold method. The statistical scrutiny was executed through Fisher’s Exact test and the Spearman correlation method. There was 12–13 fold increased in expression of HIF-1α, two fold increased in MDR1 and 13–14 fold increased in LAPTM4B mRNA level in peripheral blood of breast, ovarian, prostate and colon cancer patients. In the current study there was an association of HIF-1α, MDR1 and LAPTM4B expression with advanced tumor stage, metastasis and chemotherapy treated group in breast, ovarian, prostate and colon cancer patients. The Spearman analysis also revealed a positive linear association among HIF-1α, MDR1 and LAPTM4B in all the studied cancer patients. The elevated expression of HIF-1α, MDR1 and LAPTM4B in peripheral blood of solid tumor patients can be a predictor of metastasis, disease progression and treatment response in these cancers. However, larger studies are needed to further strengthen their role as a potential biomarker for cancer prognosis.
Splitting on categorical predictors in random forests
Authors: Wright Marvin N. , König Inke R.
Published: February 2019

One reason for the widespread success of random forests (RFs) is their ability to analyze most datasets without preprocessing. For example, in contrast to many other statistical methods and machine learning approaches, no recoding such as dummy coding is required to handle ordinal and nominal predictors. The standard approach for nominal predictors is to consider all 2k − 1 − 1 2-partitions of the k predictor categories. However, this exponential relationship produces a large number of potential splits to be evaluated, increasing computational complexity and restricting the possible number of categories in most implementations. For binary classification and regression, it was shown that ordering the predictor categories in each split leads to exactly the same splits as the standard approach. This reduces computational complexity because only k − 1 splits have to be considered for a nominal predictor with k categories. For multiclass classification and survival prediction no ordering method producing equivalent splits exists. We therefore propose to use a heuristic which orders the categories according to the first principal component of the weighted covariance matrix in multiclass classification and by log-rank scores in survival prediction. This ordering of categories can be done either in every split or a priori, that is, just once before growing the forest. With this approach, the nominal predictor can be treated as ordinal in the entire RF procedure, speeding up the computation and avoiding category limits. We compare the proposed methods with the standard approach, dummy coding and simply ignoring the nominal nature of the predictors in several simulation settings and on real data in terms of prediction performance and computational efficiency. We show that ordering the categories a priori is at least as good as the standard approach of considering all 2-partitions in all datasets considered, while being computationally faster. We recommend to use this approach as the default in RFs.
Intrauterine growth and the maturation process of adrenal function
Authors: Iwata Sachiko , Kinoshita Masahiro , Okamura Hisayoshi , Tsuda Kennosuke , Saikusa Mamoru , Harada Eimei , Saitoh Shinji , Iwata Osuke
Published: February 2019

Backgrounds

Environmental factors during early life alter the hypothalamus-pituitary-adrenal (HPA) axis regulation and increase the risk of diseases in later life. However, adrenal function at each developmental stage has not fully been investigated in relation to pathological antenatal conditions. Cortisol levels of newborns with intrauterine growth restriction (IUGR) are elevated during the neonatal period; however, when studied during early childhood, cortisol levels are reduced compared with their peers, suggesting that the HPA axis regulation might be altered from activation to suppression, the timing of which remains uncertain.

Aim

The aim of this study was to assess the presence of an interaction between intrauterine growth and postnatal age on cortisol levels in newborns hospitalised at a neonatal intensive care unit.

Methods

We performed a secondary analysis using a dataset from saliva samples of 62 newborns collected between 30 and 40 weeks corrected age. Interactions between postnatal age and clinical variables with regard to cortisol levels were assessed.

Results

The z-score of the birth weight and IUGR showed significant interactions with postnatal age on cortisol levels; cortisol levels were higher ≤5 days of birth and lower >14 days of birth than those in their peers without IUGR.

Conclusion

The adrenal function of newborns with IUGR might be altered from activation to suppression within the first several weeks of life. Longitudinal studies need to address when/how IUGR alters adrenal functions, and how these responses are associated with diseases during adulthood.
“We're not gonna be friends anymore”: Associations between viewing relational aggression on television and relational aggression in text messaging during adolescence
Authors: Coyne Sarah M. , Ehrenreich Samuel E. , Holmgren Hailey G. , Underwood Marion K.
Published: February 2019

A number of studies suggest that adolescents who view relational aggression on television are more likely to engage in higher levels of subsequent relational aggression in social interactions. This study examined longitudinal associations between viewing relational aggression on television and relationally aggressive behavior in text messaging over a 1‐year period during adolescence. Participants were 197 adolescents who completed a number of questionnaires regarding media use and aggression. Adolescents were each given a BlackBerry device and a sample of text messages was coded for aggressive behavior. Results revealed that exposure to relational aggression on television was associated with higher levels of relational aggression in texting one year later, but only for girls. Results are discussed with reference to the General Aggression Model.
A likely pathogenic variant in the SLC20A2 gene presenting with progressive myoclonus
Authors: Lamquet Simon , Ramos Eliana M. , Legati Andrea , Coppola Giovanni , Hemelsoet Dimitri , Vanakker Olivier M.
Published: February 2019

A 60‐year‐old man is presented with progressive involuntary muscle movements and neuropsychiatric symptoms who developed a variety of additional complaints over 2 years. Brain imaging revealed bilateral basal ganglia calcifications suggesting primary familial brain calcification. Analysis of the SLC20A2 gene revealed a missense mutation (c.541C>T, p.(Arg181Trp)), in silico predicted to be deleterious and not found in available databases. Segregation analysis confirmed his asymptomatic father to harbor the same mutation, though on brain imaging basal ganglia calcifications were found. This report illustrates the intrafamilial variability of the phenotype and generalized myoclonus as the presenting symptom.
Cortical activation during sleep predicts dream experience in narcolepsy
Authors: D'Atri Aurora , Scarpelli Serena , Schiappa Cinzia , Pizza Fabio , Vandi Stefano , Ferrara Michele , Cipolli Carlo , Plazzi Giuseppe , De Gennaro Luigi
Published: February 2019

Objective

Narcolepsy type 1 widely affects the architecture of sleep with frequent fast transition to REM sleep at both nighttime and daytime sleep onset. The occurrence of repeated sleep onset REM periods over the Multiple Sleep Latency Test offers a unique opportunity to identify EEG patterns predictive of successful dream recall after short periods composed of only REM or NREM sleep. It also permits to disentangle state‐ from trait‐like differences in dream recall, by using a within‐subjects design.

Methods

A consecutive series of 115 first‐diagnosed drug‐free adult narcolepsy‐type 1 patients underwent Multiple Sleep Latency Tests and were asked after each nap opportunity if they had or had not a dream experience. Scalp EEG power and a specific index of cortical activation (delta/beta power ratio), obtained from naps of 43 patients with both presence and absence of dream recall in the same sleep stage, were compared separately for REM and NREM sleep.

Results

Successful dream recall was associated with an increased EEG desynchronization in both REM and NREM over partially overlapping cortical areas. Compared to unsuccessful recall, it showed (1) lower delta power over centro‐parietal areas during both stages, (2) higher beta power in the same cortical areas during NREM, and (3) lower values in the delta/beta ratio during NREM in most scalp locations.

Interpretation

A more activated electrophysiological milieu in both REM and NREM sleep promotes dream recall, strengthening the notion that the parietal areas are crucial not only in generating dream experience, as shown in brain‐damaged patients, but also in the memory processing leading to recall.
I Would Never Take Preventive Medication! Perspectives and Information Needs of People Who Underwent Predictive Tests for Rheumatoid Arthritis
Authors: Mosor Erika , Stoffer‐Marx Michaela , Steiner Günter , Raza Karim , Stack Rebecca J. , Simons Gwenda , Falahee Marie , Skingle Diana , Dobrin Mircia , Schett Georg , Englbrecht Matthias , Smolen Josef S. , Kjeken Ingvild , Hueber Axel J. , Stamm Tanja A.
Published: February 2019

Objective

Little is known about the experiences, values, and needs of people without arthritis who undergo predictive biomarker testing for the development of rheumatoid arthritis (RA). Our study aimed to explore the perspectives of these individuals and describe their information needs.

Methods

A qualitative, multicenter interview study with a thematic analysis was conducted in Austria, Germany and the UK. Individuals were interviewed who underwent predictive biomarker testing for RA and had a positive test result but no diagnosis of any inflammatory joint disease. Participants included patients with arthralgia and asymptomatic individuals. Information and education needs were developed from the qualitative codes and themes using the Arthritis Educational Needs Assessment Tool as a frame of reference.

Results

Thematic saturation was reached in 34 individuals (76% female, 24 [71%] with arthralgia, and 10 [29%] asymptomatic individuals). Thirty‐seven codes were summarized into 4 themes: 1) decision‐making around whether to undergo initial predictive testing, 2) willingness to consider further predictive tests, and/or 3) preventive interventions, including medication, and 4) varying reactions after receiving a positive test result. Individuals with arthralgia were more likely to be willing to take preventive action, undergo further testing, and experience psychological distress than asymptomatic individuals. All participants expressed the need for tailored, patient‐understandable information.

Conclusion

Individuals at risk of RA are currently the subjects of research aimed at developing better predictive strategies and preventive approaches. Their perceptions and needs should be addressed to inform the future development of interventions combined with education.
Enantioselective Organocatalytic Enamine C−H Oxidation/Diels‐ Alder Reaction
Authors: Džambaski Zdravko , Tzaras Dimitrios‐Ioannis , Lee Sunggi , Kokotos Christoforos G. , Bondzic Bojan P.
Published: February 2019

α,β‐unsaturated aldehydes have been traditionally used in LUMO lowering asymmetric aminocatalysis (iminium catalysis), while the use of saturated aldehydes as substrates in this type of catalysis has been elusive, until recently. Herein, we demonstrate that organic, single‐electron oxidants in the presence of diarylprolinol silylether type catalysts serve as effective tools for the transformation of electron rich enamines to iminium ions which partake in a subsequent Diels‐Alder reaction. This enantioselective one‐pot transformation represents the first example of saturated aldehydes being used in domino Diels‐Alder reaction processes and demonstrates the power of this protocol for construction of stereo‐defined chiral compounds and building blocks.

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Catenary Electromagnetics for Ultra‐Broadband Lightweight Absorbers and Large‐Scale Flat Antennas
Authors: Huang Yijia , Luo Jun , Pu Mingbo , Guo Yinghui , Zhao Zeyu , Ma Xiaoliang , Li Xiong , Luo Xiangang
Published: February 2019

Catenary functions are exciting and fundamental building blocks in constructing various kinds of waves in subwavelength structures. Here, a simple yet powerful approach inspired by catenary optics is proposed to realize efficient manipulation of electromagnetic waves in terms of both amplitude and phase. By properly engineering the catenary electromagnetic fields and frequency dispersion, lightweight metafilm‐based broadband absorbers with polarization‐independent bandwidth covering 0.65–6.2 GHz are experimentally achieved, and the bandwidth is further broadened to 0.9–40 GHz. With the same approach, a large‐scale flat antenna based on generalized reflection is demonstrated in the satellite communication system. To enable the batch manufacturing, a flexible substrate–based microfabrication process is developed with a minimum feature size of down to sub‐micrometer and total size up to almost 1 m. These results may provide important guidance for the design of metasurface‐based devices.
Quantifying between‐cohort and between‐sex genetic heterogeneity in major depressive disorder
Authors: Trzaskowski Maciej , Mehta Divya , Peyrot Wouter J. , Hawkes David , Davies Daniel , Howard David M. , Kemper Kathryn E. , Sidorenko Julia , Maier Robert , Ripke Stephan , Mattheisen Manuel , Baune Bernhard T. , Grabe Hans J. , Heath Andrew C. , Jones Lisa , Jones Ian , Madden Pamela A.F. , McIntosh Andrew M. , Breen Gerome , Lewis Cathryn M. , Børglum Anders D. , Sullivan Patrick F. , Martin Nicholas G. , Kendler Kenneth S. , Levinson Douglas F. , Wray Naomi R. ,   Major Depressive Disorder Working Group of the Psychiatric Genomics Consortium
Published: February 2019

Major depressive disorder (MDD) is clinically heterogeneous with prevalence rates twice as high in women as in men. There are many possible sources of heterogeneity in MDD most of which are not measured in a sufficiently comparable way across study samples. Here, we assess genetic heterogeneity based on two fundamental measures, between‐cohort and between‐sex heterogeneity. First, we used genome‐wide association study (GWAS) summary statistics to investigate between‐cohort genetic heterogeneity using the 29 research cohorts of the Psychiatric Genomics Consortium (PGC; N cases = 16,823, N controls = 25,632) and found that some of the cohort heterogeneity can be attributed to ascertainment differences (such as recruitment of cases from hospital vs. community sources). Second, we evaluated between‐sex genetic heterogeneity using GWAS summary statistics from the PGC, Kaiser Permanente GERA, UK Biobank, and the Danish iPSYCH studies but did not find convincing evidence for genetic differences between the sexes. We conclude that there is no evidence that the heterogeneity between MDD data sets and between sexes reflects genetic heterogeneity. Larger sample sizes with detailed phenotypic records and genomic data remain the key to overcome heterogeneity inherent in assessment of MDD.
The genetic and environmental structure of fear and anxiety in juvenile twins
Authors: Sawyers Chelsea , Ollendick Thomas , Brotman Melissa A. , Pine Daniel S. , Leibenluft Ellen , Carney Dever M. , Roberson‐Nay Roxann , Hettema John M.
Published: February 2019

Fear and anxiety are conceptualized as responses to acute or potential threat, respectively. Adult twin studies found substantial interplay between genetic and environmental factors influencing fear disorders (phobias) and anxiety disorders. Research in children, however, has largely examined these factors independently. Thus, there exists a substantial knowledge gap regarding the underlying etiologic structure of these closely‐related constructs during development. Symptom counts for five fear (criticism, the unknown, death, animal, medical) and four anxiety (generalized, panic, separation, social) dimensions were obtained for 373 twin pairs ages 9–14. Multivariate twin modeling was performed to elucidate the genetic and environmental influences distributed amongst these dimensions. The best fitting model contained one genetic, two familial environmental, and two unique environmental factors shared between fear and anxiety symptoms plus dimension‐specific genetic and unique environmental factors. Although several environmental factors were shared between fear and anxiety dimensions, one latent factor accounted for genetic influences across both domains. While adult studies find somewhat distinct etiological differences between anxiety and phobic disorders, the current results suggest that their relative genetic and environmental influences are not as clearly demarcated in children. These etiological distinctions are more nuanced, likely contributing to the highly diffuse symptom patterns seen during development.
Slope‐Dominated Carbon Anode with High Specific Capacity and Superior Rate Capability for High Safety Na‐Ion Batteries
Authors: Qi Yuruo , Lu Yaxiang , Ding Feixiang , Zhang Qiangqiang , Li Hong , Huang Xuejie , Chen Liquan , Hu Yong‐Sheng
Published: February 2019

The comprehensive performance of carbon anodes for Na‐ion batteries (NIBs) is largely restricted by their inferior rate capability and safety issues. Herein, a slope‐dominated carbon anode is achieved at a low temperature of 800 °C, which delivers a high reversible capacity of 263 mA h g−1 at 0.15C with an impressive initial Coulombic efficiency (ICE) of 80 %. When paired with the NaNi1/3Fe1/3Mn1/3O2 cathode, the reversible capacity at 6C is still 75 % of that at 0.15C, and 73 % of the capacity is retained after 1000 cycles at 3C. The enhanced Na storage performance could be attributed to the unique microstructure with randomly oriented short carbon layers and the relatively higher defect concentration. Given its robustness, such a low‐temperature carbonization strategy could also be applicable to other precursors and provide a new opportunity to design slope‐dominated carbon anodes for high safety, low‐cost NIBs with excellent ICE and superior rate capability.
Metastatic mixed adenoneuroendocrine carcinoma of the liver successfully resected by hepatic trisectionectomy following chemotherapy: A case report
Authors: Sato Osamu , Tsuchikawa Takahiro , Yamada Toru , Sato Daisuke , Nakanishi Yoshitsugu , Asano Toshimichi , Noji Takehiro , Yo Kurashima , Ebihara Yuma , Murakami Soichi , Nakamura Toru , Okamura Keisuke , Shichinohe Toshiaki , Mitsuhashi Tomoko , Hirano Satoshi
Published: February 2019

Key Clinical Message

The chemotherapy guidelines for mixed adenoneuroendocrine carcinoma (MANEC) remain poorly defined, and prognosis remains dismal. In this case, we successfully performed resection after FOLFOX for unresectable metastatic MANEC of the liver. Thus, chemotherapy for adenocarcinoma may be effective for MANEC.
Ti‐Doped Ultra‐Small CoO Nanoparticles Embedded in an Octahedral Carbon Matrix with Enhanced Lithium and Sodium Storage
Authors: Li Junkai , Wang Dong , Zhou Junshuang , Hou Li , Gao Faming
Published: February 2019

Herein, we demonstrate the synthesis of ultra‐small Ti‐doped CoO nanoparticles, embedded in an octahedral carbon matrix, (Ti‐doped‐CoO@C) by pyrolyzing a Co−Ti‐bimetallic metal‐organic framework (MOF). The results reveal that optimal pyrolysis resulted in the uniform distribution of the CoO nanoparticles (∼10 nm) in an octahedral carbon matrix. Ti‐doping enhanced the specific surface area of the as‐synthesized Ti‐doped‐CoO@C nanocomposite. Owing to the octahedral carbon matrix and Ti‐doping, the nanocomposite exhibits excellent electrical conductivity and abundant accessible active sites. It is worth noting that the carbon matrix sustains the volumetric changes and the homogenous mesoporous structure facilitates rapid mass transport and electron transfer during the charge/discharge process. Therefore, the as‐synthesized Ti‐doped‐CoO@C nanocomposites exhibited excellent charge storage properties as an anode material in Li‐ and Na‐ion batteries. In Li‐ion batteries, the as‐synthesized Ti‐doped‐CoO@C nanocomposites delivered a specific capacity of 1108 mAh g−1 after 150 cycles at a current density of 200 mAg−1 and total capacitive contribution reached up to 86.6 %, at the scan rate of 0.5 mV s−1. In Na ion batteries, the Ti‐doped‐CoO@C nanocomposites demonstrated a stable specific capacity of 285 mAh g−1 after 100 cycles, at a current density of 100 mAg−1 and total capacitive contribution reached up to 78.4 %, at the scan rate of 0.5 mV s−1. Furthermore, excellent rate performance and efficient charge transfer behavior have been exhibited by the Ti‐doped‐CoO@C nanocomposites. The present study provides a generic approach to synthesize MOF‐derived heteroatom‐doped metal‐oxide/carbon nanocomposites for a wide range of applications.
Defects Promote Ultrafast Charge Separation in Graphitic Carbon Nitride for Enhanced Visible‐Light‐Driven CO2 Reduction Activity
Authors: Shi Hainan , Long Saran , Hou Jungang , Ye Lu , Sun Yanwei , Ni Wenjun , Song Chunshan , Li Keyan , Gurzadyan Gagik G. , Guo Xinwen
Published: February 2019

Fundamental photocatalytic limitations of solar CO2 reduction remain due to low efficiency, serious charge recombination, and short lifetime of catalysts. Herein, two‐dimensional graphitic carbon nitride nanosheets with nitrogen vacancies (g‐C3Nx) located at both three‐coordinate N atoms and uncondensed terminal NHx species were prepared by one‐step tartaric acid‐assistant thermal polymerization of dicyandiamide. Transient absorption spectra revealed that the defects in g‐C3N4 act as trapped states of charges to result in prolonged lifetimes of photoexcited charge carriers. Time‐resolved photoluminescence spectroscopy revealed that the faster decay of charges is due to the decreased interlayer stacking distance in g‐C3Nx in favor of hopping transition and mobility of charge carriers to the surface of the material. Owing to the synergic virtues of strong visible‐light absorption, large surface area, and efficient charge separation, the g‐C3Nx nanosheets with negligible loss after 15 h of photocatalysis exhibited a CO evolution rate of 56.9 μmol g−1 h−1 under visible‐light irradiation, which is roughly eight times higher than that of pristine g‐C3N4. This work presents the role of defects in modulating light absorption and charge separation, which opens an avenue to robust solar‐energy conversion performance.
Inorganic Molecular Electride Mg4O3: Structure, Bonding, and Nonlinear Optical Properties
Authors: Kulichenko Maksim , Fedik Nikita , Bozhenko Konstatin V. , Boldyrev Alexander I.
Published: February 2019

Growing demands of material science and, in particular, in the field of nonlinear optics (NLO) encourage us to look for stable highly polarizable molecules with excess diffuse electrons. An unusual class of compounds called electrides comply with these requirements. Many attempts have been made, yet only few electrides have been synthesized as solids and none of them as molecular species. In this paper, a new theoretically designed molecular species with electride characteristics is reported. The idea of this molecular electride comes from the formation of electride‐like features in the MgO crystal with defect F‐centers. The geometry of the investigated molecule can be described as a Mg4O4cube with one oxygen atom removed. In Mg4O3, two 3s electrons are pushed out from the inner area of the molecule forming a diffuse electride multicentered bond. Our calculations show that this electride‐like cluster possesses a noticeably large first hyperpolarizabilityβ=5733 au. At the same time, a complete cube Mg4O4and Mg4O32+without electride electron pair have much smallerβ: 0 au and 741 au, respectively. This fact indicates the decisive role of the electride electron pair in NLO properties. Additionally, vertical detachment energies of isomers (VDE), excitation energies ΔE, polarizabilitiesα, and IR spectra were calculated. These properties, includingβ, are supposed to be observable experimentally and can serve as indirect evidence of the stable molecular electride formation.
Ultralong Ternary PtRuTe Mesoporous Nanotubes Fabricated by Micelle Assembly with a Self‐Sacrificial Template
Authors: Yin Shuli , Wang Hongjing , Deng Kai , Dai Zechuan , Wang Ziqiang , Xu You , Li Xiaonian , Xue Hairong , Wang Liang
Published: February 2019

High surface area and fast mass transport rate are important to enhance the activity and stability of catalysts. In this work, tellurium nanowires and F127 triblock copolymer are used as self‐sacrificial and soft templates, respectively, to synthesize PtRuTe mesoporous nanotubes (MNTs). The designed PtRuTe MNTs show uniformly distributed mesopores and an internally hollow structure, which can effectively improve Pt utilization, the catalytic activity and durability, and CO tolerance for the methanol oxidation reaction. Very different from previous 1D metallic catalysts with solid interiors and smooth surfaces, PtRuTe MNTs are unique, with a mesoporous exterior and hollow interior. The facile route presented herein is very feasible for fabricating 1D mesoporous metallic catalysts.
Gas‐Phase Synthesis of Triphenylene (C18H12)
Authors: Zhao Long , Xu Bo , Ablikim Utuq , Lu Wenchao , Ahmed Musahid , Evseev Mikhail M. , Bashkirov Eugene K. , Azyazov Valeriy N. , Howlader A. Hasan , Wnuk Stanislaw F. , Mebel Alexander M. , Kaiser Ralf I.
Published: February 2019

For the last decades, the hydrogen‐abstraction−acetylene‐addition (HACA) mechanism has been widely invoked to rationalize the high‐temperature synthesis of PAHs as detected in carbonaceous meteorites (CM) and proposed to exist in the interstellar medium (ISM). By unravelling the chemistry of the 9‐phenanthrenyl radical ([C14H9].) with vinylacetylene (C4H4), we present the first compelling evidence of a barrier‐less pathway leading to a prototype tetracyclic PAH – triphenylene (C18H12) – via an unconventional hydrogen abstraction–vinylacetylene addition (HAVA) mechanism operational at temperatures as low as 10 K. The barrier‐less, exoergic nature of the reaction reveals HAVA as a versatile reaction mechanism that may drive molecular mass growth processes to PAHs and even two‐dimensional, graphene‐type nanostructures in cold environments in deep space thus leading to a better understanding of the carbon chemistry in our universe through the untangling of elementary reactions on the most fundamental level.
Fluorine‐Enriched Graphdiyne as an Efficient Anode in Lithium‐Ion Capacitors
Authors: Shen Xiangyan , He Jianjiang , Wang Kun , Li Xiaodong , Wang Xin , Yang Ze , Wang Ning , Zhang Yanliang , Huang Changshui
Published: February 2019

Lithium‐ion capacitors (LICs) have shown extraordinary promise for electrochemical energy storage but are usually limited to electrodes with low energy density or power density owing to the lack of active storage sites and ion diffusion limitation. In this study, fluorine‐enriched graphdiyne (F‐GDY) is prepared by a solvothermal reaction. Owing to the 42‐C hexagonal porous structure, abundant sp and sp2 hybrid carbon atoms, and even distribution of fluorine, F‐GDY has enormous potential as an anode for lithium‐ion storage. The outstanding rate performance (1825.9 mAh g−1 at 0.1 A g−1, 979.2 mAh g−1 at 5 A g−1) and stable cycling stability of F‐GDY in the lithium‐ion battery inspire the assembly of a LIC with F‐GDY as an anode and activated carbon (AC) as a cathode. When the AC/F‐GDY mass ratio is 7:1, the LIC gives the largest energy density of 200.2 Wh kg−1, corresponding to a power density of 131.17 W kg−1. This LIC also shows excellent long‐term cycling stability with a retention of approximately 80 % after 5000 cycles at 2 A g−1 and a retention of more than 80 % after 6000 cycles at 5 A g−1.
Ecological consequences of anomalies in atmospheric moisture and snowpack
Authors: Johnston Aaron N. , Bruggeman Jason E. , Beers Aidan T. , Beever Erik A. , Christophersen Roger G. , Ransom Jason I.
Published: February 2019

Although increased frequency of extreme‐weather events is one of the most secure predictions associated with contemporary climate change, effects of such events on distribution and abundance of climate‐sensitive species remain poorly understood. Montane ecosystems may be especially sensitive to extreme weather because of complex abiotic and biotic interactions that propagate from climate‐driven reductions in snowpack. Snowpack not only protects subnivean biotas from extreme cold, but also influences forage availability through timing of melt‐off and water availability. We related relative abundances of an alpine mammal, the American pika (Ochotona princeps), to measures of weather and snowpack dynamics over an 8‐yr period that included before and after a year of record‐low snowpack in Washington, USA. We sought to (1) quantify any change in pika abundance associated with the snowpack anomaly and (2) identify aspects of weather and snowpack that influenced abundance of pikas. Pikas showed a 1‐yr lag response to the snowpack anomaly and exhibited marked declines in abundance at elevations below 1,400 m simultaneous with increased abundances at higher elevations. Atmospheric moisture, indexed by vapor pressure deficit (VPD), was especially important, evidenced by strong support for the top‐ranked model that included the interaction of VPD with snowpack duration. Notably, our novel application of VPD from gridded climate data for analyses of animal abundances shows strong potential for improving species distribution models because VPD represents an important aspect of weather that influences the physiology and habitat of biota. Pikas were apparently affected by cold stress without snowpack at mid elevations, whereas changes to forage associated with snowpack and VPD were influential at high and low elevations. Our results reveal context dependency in pika responses to weather and illustrate how snow drought can lead to rapid change in the abundance of subnivean animals.
Asynchrony in individual and subpopulation fecundity stabilizes reproductive output of an alpine plant population
Authors: Waddle Ellen , Piedrahita Lucas R. , Hall Elijah S. , Kendziorski Grace , Morris William F. , DeMarche Megan L. , Doak Daniel F.
Published: February 2019

Population‐wide outcomes such as abundance, reproductive output, or mean survival can be stabilized by non‐synchronous variation in the performance of individuals or subpopulations. Such “portfolio effects” have been increasingly documented at the scale of subpopulations and are thought to play an important role in generating stability of population phenomena in the face of environmental variation. However, few studies quantify the strength and origin of portfolio effects at the finer scale of individuals. We used 16 yr of fruit production and climate data for an alpine plant to dissect the scale of portfolio effects in reproduction, as well as the contribution of individual traits including size and flowering time in driving reproductive output. Asynchrony in reproductive success substantially reduces variation in population‐level reproductive output, with approximately one‐fourth of this stabilizing effect arising from individual differences, mostly not those characterized by measured traits, and approximately three‐fourths from asynchrony across subpopulations. These results emphasize the different scales and causes of portfolio effects. The decomposition for portfolio effects we provide can facilitate similar breakdowns of the strength and causes of these effects in other systems.
Mixed‐Valence Vanadium (IV/V) Glycolates and Lactates with N‐Heterocycle Ligands: Localized Structures and Catalytic Oxidation of Thioanisole
Authors: Jin Wan‐Ting , Weng Wei‐Zheng , Zhou Zhao‐Hui
Published: February 2019

Dimeric mixed‐valence vanadium (IV/V) glycolates and lactates with N‐heterocycle ligands, [V2O3(phen)3(glyc)]Cl·7H2O (1), [V2O3(phen)3(S‐lact)]Cl·5.5H2O (2), (NH4)2[V2O3(bpy)2(glyc)2]Cl·4H2O (3), (NH4)[V2O3(bpy)2(S‐lact)2]·7H2O (4) and (NH4)2[V2O3(bpy)2(R,S‐lact)2]Cl·H2O (5), have been isolated in a wide pH range from weak acidic to alkaline solutions (H2glyc = glycolic acid, H2lact = lactic acid, phen = 1,10‐phenanthroline, bpy = 2,2′‐bipyridine). The glycolates and lactates in 1 and 2 chelate to VV whereas in 3–5 chelate to VIV and VV with α‐alkoxy and α‐carboxy groups. These complexes feature interesting localized O=VIV–O–VV=O bridging structures, which are supported by structural analyses, bond valance calculations, UV/Vis, EPR experiments and exhibit different electrochemical behaviors. These complexes were further used for the selective oxidation of thioanisole to methyl phenyl sulfoxide.
Omega‐3 Polyunsaturated Fatty Acids as an Adjunct to Non‐Surgical Treatment of Periodontitis
Authors: Stańdo Mirella , Lewkowicz Natalia
Published: February 2019

Recently, a growing interest in products containing omega‐3 polyunsaturated fatty acids (PUFAs) docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA) has emerged. It turned out that omega‐3 PUFAs have therapeutic, anti‐inflammatory, and protective properties in the patients with rheumatoid arthritis, ulcerative colitis, asthma, cardiovascular and periodontal diseases. Omega‐3 PUFAs inhibit the synthesis of pro‐inflammatory factors such as cytokines and eicosanoids. Moreover, omega‐3 PUFAs are enzymatically transformed into lipid mediators, i.a. resolvins and protectins possessing the properties to soothe the ongoing inflammatory process and minimize tissue damage as well as to increase tissue protection in acute inflammation. The use of omega‐3 PUFAs in the treatment of periodontitis may be beneficial due to controlling an inflammatory response against subgingival biofilm, reducing the level of pro‐inflammatory cytokines and inhibiting osteoclast function. This, in turn, improves clinical parameters of periodontitis, such as bleeding on probing (BOP), periodontal probing depth (PD), and connective tissue attachment level (CAL). In this paper, the most important information about the mechanisms of omega‐3 PUFAs EPA and DHA action, and their sources in the daily diet are discussed. The recent literature regarding the effects of using omega‐3 PUFAs as a complementary and supportive element in the non‐surgical treatment of periodontitis are also reviewed.

Practical Applications: Studies in humans and animals have suggested a beneficial therapeutic effect of omega‐3 fatty acids in the control of inflammation and periodontal tissue protection in periodontitis.

The multidirectional action of omega‐3 polyunsaturated fatty acids (PUFAs) and their role in periodontal inflammation are reviewed here.
Antioxidant Activity of Spent Coffee Ground Extracts Toward Soybean Oil and Fish Oil
Authors: Hwang Hong‐Sik , Winkler‐Moser Jill K. , Kim Youngmok , Liu Sean X.
Published: February 2019

Although studies have shown that spent coffee ground (SCG) extracts have antioxidant activity, no systematic study has been reported under actual storage conditions. The purpose of this study is to estimate the feasibility of practical application of SCG extracts as natural antioxidants for soybean oil and fish oil. An ethanol extract (EE), an acetone extract (AE), and polar compounds isolated from oil (PCO) are prepared and their activity is compared to a synthetic antioxidant, butylated hydroxytoluene (BHT). EE shows the strongest radical scavenging activity for 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) radicals and the highest total phenolic content (TPC) followed by AE and then PCO. However, during storage of soybean oil and fish oil at 35 and 50 °C, AE has the strongest antioxidant activity as determined by peroxide value, conjugated diene value, p‐anisidine value, and headspace volatile analyses. In soybean oil, 0.25% AE has antioxidant activity that is equal to or better than 0.02% BHT. In fish oil, the antioxidant activity of 0.25% AE is inferior to that of 0.02% BHT. However, increased concentrations of AE show improved antioxidant activity. This study shows that SCG extracts can be practically used as natural antioxidants for vegetable oils and omega‐3 oils.

Practical Application: Due to lack of information about the antioxidant activity of spent coffee ground (SCG) extracts, this study is specifically aimed and designed to provide information on their activity toward soybean oil and fish oil during actual storage. This study shows that 0.25% acetone extract has equal or better protective effects than BHT in soybean oil at 35 and 50 °C. The activity is further improved with increasing concentration. The activity of the acetone extract in fish oil is not as strong as in soybean oil, but higher concentrations further improve the antioxidant activity. In this study, it is clearly demonstrated that the SCG extracts can have practical use as natural antioxidants for vegetable oils and oils with high concentration of omega‐3 fatty acids.

Among spent coffee ground (SCG) extracts, the acetone extract (AE) has the strongest antioxidant activity. In soybean oil, 0.25% AE has antioxidant activity that is equal to or better than 0.02% butylated hydroxytoluene (BHT). This study shows that SCG extracts can be practically used as natural antioxidants for edible oils.
Development of a 450 nm Laser Irradiation Desorption Method for Fast Headspace Solid‐Phase Microextraction of Volatiles from Krill Oil (Euphausia superba)
Authors: Song Gongshuai , Zhang Mengna , Zhang Yanping , Wang Honghai , Chen Kang , Dai Zhiyuan , Shen Qing
Published: February 2019

A laser irradiation desorption (LID) method is developed using a 450 nm blue semiconductor laser and gas chromatography mass spectrometry (GC/MS) for analyzing the flavor of Antarctic krill oil (Euphausia superba). The experimental parameters of LID are optimized by response surface methodology (RSM), and the optima are obtained as follows; laser power (10 W), irradiation time (5 min), and sample volume (3 g). The results show that a total of 41 volatile molecular species are detected, including six alcohols, 10 aldehydes, five ketones, 14 hydrocarbons, and six other compounds. Compared with the conventional heating assisted desorption technique, the LID can release volatile molecular species with higher abundance in a considerably reduced extraction time from 30 to 5 min. Finally, the proposed method is validated in terms of sensitivity, precision, linearity, and recovery, which demonstrate its advantages of high efficiency and simplified procedure.

Practical Applications: An LID method is developed using a 450 nm blue semiconductor laser for analyzing the flavor of Antarctic krill oil (E. superba). Compared with the conventional heating assisted desorption technique, the LID can release more volatile molecular species with higher abundance in a considerably shorter extraction time, and the intensive laser power does not induce the autoxidation of polyunsaturated fatty acids. It shows the advantages of a highly efficient, and simplified procedure.

A laser irradiation desorption (LID) method is developed using a 450 nm blue semiconductor laser for analyzing the flavor of Antarctic krill oil (Euphausia superba).
Recent studies of docking and molecular dynamics simulation for liquid‐phase enantioseparations
Authors: Peluso Paola , Dessì Alessandro , Dallocchio Roberto , Mamane Victor , Cossu Sergio
Published: February 2019

Liquid‐phase enantioseparations have been fruitfully applied in several fields of science. Various applications along with technical and theoretical advancements contributed to increase significantly the knowledge in this area. Nowadays, chromatographic techniques, in particular HPLC on chiral stationary phase, are considered as mature technologies. In the last thirty years, CE has been also recognized as one of the most versatile technique for analytical scale separation of enantiomers. Despite the huge number of papers published in these fields, understanding mechanistic details of the stereoselective interaction between selector and selectand is still an open issue, in particular for high‐molecular weight chiral selectors like polysaccharide derivatives. With the ever growing improvement of computer facilities, hardware and software, computational techniques have become a basic tool in enantioseparation science. In this field, molecular docking and dynamics simulations proved to be extremely adaptable to model and visualize at molecular level the spatial proximity of interacting molecules in order to predict retention, selectivity, enantiomer elution order, and profile noncovalent interaction patterns underlying the recognition process. On this basis, topics and trends in using docking and molecular dynamics as theoretical complement of experimental LC and CE chiral separations are described herein. The basic concepts of these computational strategies and seminal studies performed over time are presented, with a specific focus on literature published between 2015 and November 2018. A systematic compilation of all published literature has not been attempted.
Information Disclosure by the European Union as a Tool to Improve Implementation? A Comparative Analysis of the Perception of Domestic Regulators
Authors: Versluis Esther , Polak Josine
Published: February 2019

The implementation of European Union law is not without problems, and there are many potential solutions to address this situation. This article analyzes the impact of information disclosure by the European Union (EU) on the application ofEUpolicy in the member states according to domestic regulators. By comparatively analyzingEUdirectives on air safety and pollution prevention in the Netherlands, Poland, and Portugal, this study illustrates that domestic street‐level actors hold mixed perceptions about the utilization of information.EU‐level disclosure is only perceived to be effective when the information is collected by a trusted external actor, and when it is discussed confidentially among stakeholders.