bluuebunny/crossref_metadata_2025 huggingface dataset:
Unlocking Few‐Layered Ternary Chalcogenides for High‐Performance Potassium‐Ion Storage
Authors: Tian Huajun , Yu Xuechao , Shao Hezhu , Dong Liubing , Chen Yi , Fang Xiaqin , Wang Chengyin , Han Weiqiang , Wang Guoxiu
Published: June 2019

Potassium‐ion batteries (KIBs) have attracted increasing attention for grid‐scale energy storage due to the abundance of potassium resources, low cost, and competitive energy density. The key challenge for KIBs is to develop high‐performance electrode materials. However, the exploration of high‐capacity and ultrastable electrodes for KIBs remains challenging because of the sluggish diffusion kinetics of K+ ions during the charging/discharging processes. This study reports for the first time a facile ion‐intercalation‐mediated exfoliation method with Mg2+ cations and NO3– anions as ion assistants for the fabrication of expanded few‐layered ternary Ta2NiSe5 (EF‐TNS) flakes with interlayer spacing up to 1.1 nm and abundant Se sites (NiSe4 tetrahedra/TaSe6 octahedra clusters) for superior potassium‐ion storage. The EF‐TNS deliver a high capacity of 315 mAh g–1, excellent rate capability (121 mAh g–1 at a current density of 1000 mA g–1), and ultrastable cycling performance (81.4% capacity retention after 1100 cycles). Detailed theoretical analysis via first‐principles calculations and experimental results elucidate that K+ ions intercalate through the expanded interlayers effectively and prefer to transport along zigzag pathways in layered Ta2NiSe5. This work provides a new avenue for designing novel ternary intercalation/pseudocapacitance‐type KIBs with high capacity, excellent rate capability, and superior long‐term cycling performance.
Intrinsic Effects of Ruddlesden‐Popper‐Based Bifunctional Catalysts for High‐Temperature Oxygen Reduction and Evolution
Authors: Huan Yu , Chen Shouxiao , Zeng Rui , Wei Tao , Dong Dehua , Hu Xun , Huang Yunhui
Published: June 2019

Unveiling the intrinsic effects of Ruddlesden‐Popper (RP) series An+1BnO3n+1 (A = La, B = Ni, Co, Mn, Cu, n = 1, 2 and 3) catalysts is essential in order to optimize the activity of oxygen reduction reaction (ORR) and evolution reaction (OER). Here, it is demonstrated that the oxygen vacancy is not the key point for RP to realize high ORR and OER activity at high temperature. Instead, interstitial O2− with high concentration and fast migration, and lattice oxygen with high activity are favorable for the high‐temperature catalytic activity. Aliovalent cation doping is an effective strategy to modify the catalytic activity. For the RP catalysts, low‐valence ion doping does not introduce oxygen vacancies, which suppresses the activity of lattice oxygen and decreases the interstitial O2− concentration; whereas high‐valence ion doping enhances the interstitial O2– concentration and the lattice oxygen activity. The evaluations of six RP series (La2NiO4, La2CoO4, La3Co2O7, La4Ni3O10, La2MnO4, and La2CuO4 based) and twenty samples as oxygen electrodes for solid oxide fuel cells (SOFCs) and solid oxide electrolysis cells (SOECs) demonstrate that this finding is applicable to all the selected RP series.
Similarities in pelvic dimorphisms across populations
Authors: DelPrete Hillary
Published: June 2019

Objectives

The shape and size of the pelves of males and females differ, due in part, to the differing constraints of the sexes. Previous research has demonstrated that many factors impact pelvic morphology, thereby it is not surprising that there is pelvic variation within and across populations. Because of this variation, pelvic measures that are sexually dimorphic also differ by population. However, measures that are critical for reproduction should remain sexually dimorphic, regardless of circumstance. This study examines pelvic dimorphisms across six samples to determine if they are consistent.

Methods

Twenty‐three pelvic measurements were collected from 668 individuals from six skeletal populations. Multiple t‐tests were run within samples to determine which traits were dimorphic. Further, an index value was computed for each variable to examine and to classify level of dimorphism; values were classified as high, moderate, or low. All results were compared across samples.

Results

Ten measures remained dimorphic across every population; females were consistently larger for posterior spaces of the inlet, midplane, and outlet, bi‐spinous diameter, transverse diameter of the outlet, and circumference of the midplane. Males were consistently larger for anterior space of the outlet, pelvic breadth, iliac length, and pelvic depth. Index values varied across populations; however, level of dimorphism remained consistent.

Conclusions

These findings suggest that some measures of the pelvic canal have a higher selection intensity than others. Further, variability in index values suggests that while maintaining the statistically significant presence of dimorphism, there is a degree of flexibility in the degree of dimorphism.
Molybdenum‐Catalyzed Oxidative Cleavage of Raw Poplar Sawdust into Mono‐Aromatics and Organic Acid Esters
Authors: Ma Yangyang , Ma Jiping , Xia Fei , Lu Fang , Du Zhongtian , Xu Jie
Published: June 2019

Conversion of non‐edible lignocellulosic biomass into value‐added chemicals is of great significance and also particularly attractive. However, owing to the complexity and inertness, valorization of native lignocellulose remains to be quite challenging. Herein, catalytic oxidative cleavage of raw poplar sawdust was studied, mono‐aromatics and organic acid esters with 34.8 wt% and 27.4 wt% yield respectively were achieved over MoO2(acac)2 with molecular oxygen, which was suggested to be attributed to a prior cleavage of the carbohydrate fractions. This catalytic oxidation approach demonstrates the feasibility of transformation of raw woody biomass into valuable chemicals.
On the Mechanism of Palladium‐Catalyzed Unsaturated Bond Transformations: A Review of Theoretical Studies
Authors: Xiong Qin , Chen Haohua , Zhang Tao , Shan Chunhui , Bai Ruopeng , Lan Yu
Published: June 2019

Palladium‐catalyzed transformation reactions of unsaturated molecules have considerable importance because of their versatility and wide range of applications. Over the past decades, various experimental studies on palladium‐catalyzed unsaturated bond transformation have been reported, and mechanistic and computational studies have also progressed considerably. With the development of computing methods and power, theoretical calculation has become a powerful tool for mechanistic study of transition‐metal catalysis. In this review, we summarize the literature on mechanistic studies of palladium‐catalyzed transformations of unsaturated molecules, including hydrogenation, alkylation, arylation, silylation, vinylation, cyclization and esterification. Mechanistically, most of these reactions undergo a redox pathway, involving either oxidative addition, insertion, transmetalation, β‐H elimination or reductive elimination. Some instead undergo a non‐redox pathway, mainly involving insertion or β‐H elimination.
Direct Z‐Scheme Hetero‐phase Junction of Black/Red Phosphorus for Photocatalytic Water Splitting
Authors: Liu Fulai , Shi Rui , Wang Zhuan , Weng Yuxiang , Che Chi‐Ming , Chen Yong
Published: June 2019

Black phosphorus (BP) has recently drawn attention in photocatalysis for its optical properties. However, limited by the rapid recombination of photogenerated carriers, the use of BP for photocatalytic water splitting still remains a huge challenge. Herein, we prepare a black/red phosphorus (BP/RP) hetero‐phase junction photocatalyst by a wet‐chemistry method to promote the interfacial charge separation and thus achieve Z‐scheme photocatalytic water splitting without using sacrificial agents. The Z‐scheme mechanism was confirmed by time‐resolved transient absorption spectroscopy. This work provides a novel insight into the interface design of hetero‐phase junction with atomic precision.
Expanding APEX2 Substrates for Proximity‐Dependent Labeling of Nucleic Acids and Proteins in Living Cells
Authors: Zhou Ying , Wang Gang , Wang Pengchong , Li Zeyao , Yue Tieqiang , Wang Jianbin , Zou Peng
Published: June 2019

The subcellular organization of biomolecules such as proteins and nucleic acids is intimately linked to their biological functions. APEX2, an engineered ascorbate peroxidase that enables proximity‐dependent labeling of proteins in living cells, has emerged as a powerful tool for deciphering the molecular architecture of various subcellular structures. However, only phenolic compounds have thus far been employed as APEX2 substrates, and the resulting phenoxyl radicals preferentially react with electron‐rich amino acid residues. This narrow scope of substrates could potentially limit the application of APEX2. In this study, we screened a panel of aromatic compounds and identified biotin‐conjugated arylamines as novel probes with significantly higher reactivity towards nucleic acids. As a demonstration of the spatial specificity and depth of coverage in mammalian cells, we applied APEX2 labeling with biotin‐aniline (Btn‐An) in the mitochondrial matrix, capturing all 13 mitochondrial messenger RNAs and none of the cytoplasmic RNAs. APEX2‐mediated Btn‐An labeling of RNA is thus a promising method for mapping the subcellular transcriptome, which could shed light on its functions in cell physiology.
Synthesis, characterization of Schiff base metal complexes and their biological investigation
Authors: El‐Sonbati A.Z. , Mahmoud W.H. , Mohamed Gehad G. , Diab M.A. , Morgan Sh.M. , Abbas S.Y.
Published: June 2019

A new Schiff base ligand named (E)‐2‐(((3‐aminophenyl)imino)methyl)phenol (HL) was prepared through condensation reaction of m‐phenylenediamine and 2‐hydroxybenzaldehyde in 1:1 molar ratio. The new ligand was characterized by elemental analysis and spectral techniques. The coordination behavior of a series of transition metal ions named Cr (III), Mn (II), Fe (III), Co (II), Ni (II), Cu (II), Zn (II) and Cd (II) with the newly prepared Schiff base ligand (HL) is reported. The nature of bonding and the stereochemistry of the complexes have been deduced from elemental analyses, IR, UV–Vis, 1H NMR, mass, electronic spectra, magnetic susceptibility and conductivity measurements and further their thermal stability was confirmed by thermogravimetric analysis (TG). From IR spectra, it was observed that the ligand is a neutral tridentate ligand coordinates to the metal ions through protonated phenolic oxygen, azomethine nitrogen and nitrogen atom of NH2 group. The existence, the number and the position of the water molecules was studied by thermal analysis. The molecular structures of the Schiff base ligand (HL) and its metal complexes were optimized theoretically and the quantum chemical parameters were calculated. The synthesized ligand and its complexes were screened for antimicrobial activities against bacterial species (Staphylococcus aureus and Bacillis subtilis, (gram positive bacteria)), (Salmonella SP., Escherichia coli and Pseudomonas aeruginosa, (gram negative bacteria)) and fungi (Aspergillus fumigatus and Candida albicans). The complexes were found to possess high biological activities against different organisms. Molecular docking was used to predict the efficiency of binding between Schiff base ligand (HL) and both receptors of Escherichia coli (3 T88) and Staphylococcus aureus (3Q8U). The receptor of Escherichia coli (3 T88) showed best interaction with Schiff base ligand (HL) compared to receptor of Staphylococcus aureu (3Q8U).
Toughening of semi‐IPN structured epoxy using a new PEEK‐type polymer via in situ azide–alkyne click polymerization
Authors: Lee Jin Seo , Ko Na Yeong , Kwak Nho Hoon , Ying Wu Bin , Lee Bumjae
Published: June 2019

A new poly(ether ether ketone)‐type polymer prepared from 1,4‐bis(azidomethyl)benzene (p‐BAB), 4,4′‐bis(2‐propynyloxy)benzophenone (PBP) or 4,4′‐sulfonylbis(propynyloxy)‐benzene (SBP) via azide–alkyne click polymerization was used as a toughening agent to improve the fracture toughness, thermal stability of the toughened epoxy and reduce its viscosity during processing. The epoxy was toughened by the polymer [poly(p‐BAB/PBP)] via in situ polymerization during the curing process, which largely decreased viscosity during the epoxy mixing process compared to that of a neat epoxy. The fracture toughness of 5 wt % poly(p‐BAB/PBP) toughened epoxy is two times higher than that of the neat epoxy, and even higher than that of the polyethersulfone‐type [poly(p‐BAB/SBP)] toughened epoxy using the same amount of toughening agents. In addition, the T
g of this toughened epoxy is higher than that of engineering plastic, which could be regarded as the evidence for the excellent thermal resistance. These phenomena might be attributed to the formation of semi‐interpenetrating polymer networks composed by the epoxy network and the linear poly(p‐BAB/PBP). In situ poly(p‐BAB/PBP) has unique advantages such as decreased viscosity and improved thermal stability in comparison with in situ poly(p‐BAB/SBP). These features are significant for the development of carbon‐fiber‐reinforced plastics as alternate materials to metals. Therefore, in situ poly(p‐BAB/PBP) is a promising toughener for epoxy systems. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 48178.
Hydrogel increases diclofenac skin permeation and absorption
Authors: Haltner‐Ukomadu Eleonore , Sacha Manuel , Richter Andrea , Hussein Khaled
Published: June 2019

Purpose

Topical nonsteroidal anti‐inflammatory drug formulations are used commonly to treat musculoskeletal pain and inflammation. Drug properties and formulation composition are the primary determinants of the transdermal drug delivery rate. The ex vivo transdermal flux through human skin of three topical diclofenac formulations was compared.

Methods

The formulations tested were hydrogel 1% diclofenac sodium and two emulsion gels (1.16%/2.32% diclofenac diethylamine, equivalent to 1%/2% diclofenac sodium). Human abdominal skin obtained during unrelated surgical procedures was stored at −20 °C until use. Skin specimens were thawed, prepared and placed in Franz diffusion cells (stratum corneum facing donor cell). The test formulation (~200 mg) was applied to the donor cell skin surface, and the receptor compartment was periodically sampled over 48 hours. The drug concentration in the receptor medium was determined by a validated HPLC method. Raman spectral imaging was performed to visualize the location and distribution of diclofenac.

Results

After 5 hours, the cumulative amount of hydrogel diclofenac transiting the skin was about 10 times that of the emulsion gel 1.16% (P=0.0004) and about twice that of the emulsion gel 2.32% (P=0.022). Similar results were seen after 9 hours. Raman spectroscopy showed that the hydrogel formulation was a homogeneous mixture of its various components, including diclofenac. The emulsion gels were non‐homogeneous, with diclofenac in close proximity to the lipophilic (paraffin) phase.

Conclusions

The transdermal transit of diclofenac from the hydrogel demonstrated a faster onset and a greater absorption rate than either emulsion gel formulation, suggesting that the hydrogel formulation may have a faster onset of action in underlying tissues vs. the emulsion gel products.
Metabolomics analysis of Pulsatilla decoction on treatment of wetness‐heat‐induced diarrhea in rats based on UPLC–Q/TOF–MS/MS
Authors: Hua Yong‐li , Ma Qi , Li Wei , Zhang Xiao‐song , Cheng Xiao‐hua , Jia Ya‐qian , Peng Xiao‐ting , Yao Wan‐ling , Ji Peng , Hu Jun‐jie , Wei Yan‐ming
Published: June 2019

Pulsatilla decoction (PD) is a classical prescription in traditional Chinese medicine that has therapeutic effects on wetness‐heat‐induced diarrhea (WHD). To investigate the therapeutic effects of PD in the treatment of WHD and elucidate the potential mechanism, we used a metabolomics strategy on the base of ultraperformance liquid chromatography coupled with quadrupole time‐of‐flight/mass spectrometry (UPLC–Q/TOF–MS/MS) and analyzed the serum samples of 32 rats to identify differential metabolites and pathways associated with the PD treatment of WHD. With variable importance for projection >1.0 in the Orthogonal partial least‐squares discriminant analysis (OPLS‐DA ) models and FC ≥1.2 or ≤0.8, 67 differential metabolites in the model and control groups and 33 differential metabolites in the model and PD groups were screened. A total of 23 differential metabolites were selected based on Venny analysis. Functional analysis showed that the differential metabolites identified were primarily involved in pentose and glucuronate interconversions, glycerophospholipid metabolism, tryptophan metabolism, starch and sucrose metabolism, and glycerolipid metabolism. This study suggested that PD exerts inhibitory effects on WHD. In particular, the significant roles of PD for treating WHD lie in regulating perturbed energy metabolism, glycerophospholipid metabolism and glycerolipid metabolism, and promoting lysoPC production restoring the function of intestinal tract.
Clinical practice guidelines for the diagnosis and treatment of adult diffuse glioma‐related epilepsy
Authors: Liang Shuli , Fan Xing , Zhao Ming , Shan Xia , Li Wenling , Ding Ping , You Gan , Hong Zhen , Yang Xuejun , Luan Guoming , Ma Wenbin , Yang Hui , You Yongpin , Yang Tianming , Li Liang , Liao Weiping , Wang Lei , Wu Xun , Yu Xinguang , Zhang Jianguo , Mao Qing , Wang Yuping , Li Wenbin , Wang Xuefeng , Jiang Chuanlu , Liu Xiaoyan , Qi Songtao , Liu Xingzhou , Qu Yan , Xu Jiwen , Wang Weimin , Song Zhi , Wu Jinsong , Liu Zhixiong , Chen Ling , Lin Yuanxiang , Zhou Jian , Liu Xianzeng , Zhang Wei , Li Shichuo , Jiang Tao
Published: June 2019

Background

Glioma‐related epilepsy (GRE) is defined as symptomatic epileptic seizures secondary to gliomas, it brings both heavy financial and psychosocial burdens to patients with diffuse glioma and significantly decreases their quality of life. To date, there have been no clinical guidelines that provide recommendations for the optimal diagnostic and therapeutic procedures for GRE patients.

Methods

In March 2017, the Joint Task Force for GRE of China Association Against Epilepsy and Society for Neuro‐Oncology of China launched the guideline committee for the diagnosis and treatment of GRE. The guideline committee conducted a comprehensive review of relevant domestic and international literatures that were evaluated and graded based on the Oxford Centre for Evidence‐Based Medicine Levels of Evidence, and then held three consensus meetings to discuss relevant recommendations. The recommendations were eventually given according to those relevant literatures, together with the experiences in the diagnosis and treatment of over 3000 GRE cases from 24 tertiary level hospitals that specialize in clinical research of epilepsy, glioma, and GRE in China.

Results

The manuscript presented the current standard recommendations for the diagnostic and therapeutic procedures of GRE.

Conclusions

The current work will provide a framework and assurance for the diagnosis and treatment strategy of GRE to reduce complications and costs caused by unnecessary treatment. Additionally, it can serve as a reference for all professionals involved in the management of patients with GRE.
Palladium Single‐Atom Catalysts Supported on C@C3N4 for Electrochemical Reactions
Authors: Kim Hee‐Eun , Lee In Hyuk , Cho Jinwon , Shin Sangyong , Ham Hyung Chul , Kim Jin Young , Lee Hyunjoo
Published: June 2019

Single atom catalysts (SACs) maximize the utilization of noble metal whereas nanoparticle catalysts have inner metal atoms unavailable. In this study, various electrocatalytic reactions were investigated for Pd and Pt SACs. The single atoms were immobilized on thin layers of graphitic carbon nitride with carbon black (for simplicity, C@C3N4) to produce an electrochemically efficient and stable SACs. Single atomic structure was confirmed by high‐angle annular dark field scanning transmission electron microscopy (HAADF‐STEM) and extended X‐ray absorption fine structure (EXAFS) analyses. Oxygen reduction reaction (ORR) and CO stripping experiments were conducted, and the results were compared with the corresponding nanoparticle catalysts. Lack of ensemble sites in the SACs resulted in two‐electron pathway for ORR; single atomic Pd on C@C3N4 (C@C3N4−Pd1) showed high activity and selectivity for H2O2 formation. DFT calculations showed that C@C3N4−Pd1 follows a downhill path for H2O2 formation unlike single atomic Pt on C@C3N4 (C@C3N4‐Pt1), resulting in enhanced H2O2 selectivity. Weaker adsorption of oxygen intermediates on C@C3N4−Pd1 resulted in enhanced ORR activity. The SACs showed no interaction with CO as confirmed by no CO stripping peak. This resulted in no activity for formic acid oxidation following indirect pathway or methanol oxidation, which necessitates COads as reaction intermediates. SACs can be efficient electrocatalysts with high activity and unique selectivity.
Establishing Communication Between Artificial Cells
Authors: Aufinger Lukas , Simmel Friedrich C.
Published: June 2019

Communication between artificial cells is essential for the realization of complex dynamical behaviors at the multi‐cell level. It is also an important prerequisite for modular systems design, because it determines how spatially separated functional modules can coordinate their actions. Among others, molecular communication is required for artificial cell signaling, synchronization of cellular behaviors, computation, group‐level decision‐making processes and pattern formation in artificial tissues. In this review, an overview of various recent approaches to create communicating artificial cellular systems is provided. In this context, important physicochemical boundary conditions that have to be considered for the design of the communicating cells are also described, and a survey of the most striking emergent behaviors that may be achieved in such systems is given.
Thermomorphic Multiphase Systems: Switchable Solvent Mixtures for the Recovery of Homogeneous Catalysts in Batch and Flow Processes
Authors: Bianga Jonas , Künnemann Kai U. , Gaide Tom , Vorholt Andreas J. , Seidensticker Thomas , Dreimann Jens M. , Vogt Dieter
Published: June 2019

Over the past 20 years, thermomorphic multiphase systems (TMS) have been used as a versatile and elegant strategy for the recovery and recycling of homogeneous transition‐metal catalysts, in both batch‐scale experiments and continuously operated processes. TMS ensure a homogeneous reaction in a monophasic reaction mixture at reaction temperature and the recovery of the homogeneous transition‐metal catalyst through liquid–liquid separation at a lower separation temperature. This is achieved by using at least two solvents, which have a highly temperature‐sensitive miscibility gap. The suitability of commercially available solvents makes this approach highly interesting from an industrial point of view. For the first time, herein, all studies in the area of TMS are reviewed, with the aim of providing a concise and integral representation of this approach for homogeneous catalyst recovery. In addition to the discussion of examples from the literature, the thermodynamic fundamentals of the temperature‐dependent miscibility of solvents are also presented. This review also gives key indicators to compare different TMS approaches, for instance. In this way, new solvent combinations and in‐depth research, as well as improvements to existing approaches, can be addressed and promoted.
Vibrational circular dichroism as a probe of solid‐state organisation of derivatives of cyclic β‐amino acids: Cis‐ and trans‐2‐aminocyclobutane‐1‐carboxylic acid
Authors: Declerck Valérie , Pérez‐Mellor Ariel , Guillot Régis , Aitken David J. , Mons Michel , Zehnacker Anne
Published: June 2019

Peptide models built from cis‐ and trans‐2‐aminocyclobutane‐1‐carboxylic acids (ACBCs) are studied in the solid phase by combining Fourier‐transform infrared spectroscopy (FTIR) absorption spectroscopy, vibrational circular dichroism (VCD), and quantum chemical calculations using density functional theory (DFT). The studied systems are N‐tert‐butyloxycarbonyl (Boc) derivatives of 2‐aminocyclobutanecarboxylic acid (ACBC) benzylamides, namely Boc−(cis‐ACBC)−NH−Bn and Boc−(trans‐ACBC)−NH−Bn. These two diastereomers show very different VCD signatures and intensities, which of the trans‐ACBC derivative being one order of magnitude larger in the region of the ν (CO) stretch. The spectral signature of the cis‐ACBC derivative is satisfactorily reproduced by that of the monomer extracted from the solid‐state geometry of related ACBC derivatives, which shows that no long‐range effects are implicated for this system. In terms of hydrogen bonds, the geometry of this monomer is intermediate between the C6 and C8 structures (exhibiting a 6‐ or 8‐membered cyclic NH⋯O hydrogen bond) previously evidenced in the gas phase. The benzyl group must be in an extended geometry to reproduce satisfactorily the shape of the VCD spectrum in the ν (CO) range, which qualifies VCD as a potential probe of dispersion interaction. In contrast, reproducing the IR and VCD spectrum of the trans‐ACBC derivative requires clusters larger than four units, exhibiting strong intermolecular H‐bonding patterns. A qualitative agreement is obtained for a tetramer, although the intensity enhancement is not reproduced. These results underline the sensitivity of VCD to the long‐range organisation in the crystal.
Product color emotional design adaptive to product shape feature variation
Authors: Ding Man , Bai Zhonghang
Published: June 2019

When a user selects a product, he/she considers the emotional experience induced by the product color. However, when affected by product shape feature, the color image perception space of a user becomes more complex and dynamic. To address this problem, a product color emotional design method adaptive to product shape feature variation is proposed in this article. Based on psychological means, factor analysis and semantic differential methods are used to elucidate the mechanism for the formation of a color image perception space of a user influenced by product shape feature. Using support vector regression, a product color image evaluation model adaptive to product shape feature variation is constructed, and is then optimized via a genetic algorithm. A corresponding design system is constructed based on the method proposed in this article. A case study involving the design of a thermos for children is presented to demonstrate the operational procedure involved in the proposed method and to verify its performance. The results of the verification experiments confirm that the design scheme from system recommendation essentially meets the anticipated image target and assists the designer effectively. The method and system proposed in this study can generate a product color design scheme, which is unconstrained by shape feature and can satisfy user emotional preferences and needs, and have a certain applicability and practicability.
Trinuclear Lanthanide Coordination Clusters: Single‐Molecule‐Magnet Behavior and Catalytic Activity in the Friedel‐Crafts Alkylation Reaction
Authors: Sarkar Arijit , Gómez‐García Carlos J. , Benmansour Samia , Nayek Hari Pada
Published: June 2019

A new multidentate ligand (H3L) was synthesized by the condensation reaction of 4‐tert‐butyl‐2,6‐diformylphenol and 2‐amino‐4‐nitrophenol. The reaction of the ligand with hydrated lanthanide nitrate produced two isostructural trinuclear coordination clusters: [DyLn3L3(DMF)3(H2O)2] ⋅ 3.8DMFLn=Dy (1) and Nd (2) (DMF=N, N‐dimethylformamide). Single‐crystal X‐ray diffraction analysis revealed that there are three lanthanide ions arranged in an almost perfect linear fashion in both complexes. Magnetic studies show single‐molecule‐magnet (SMM) behavior in the Dy derivative with τ0=1.7×10−6 s and a thermal energy barrier of 7.0 cm−1. Both complexes were used as catalysts towards the Friedel‐Crafts alkylation reaction of indole with different aldehydes with yields varying from 59–98 %. Complex 1 showed better catalytic efficiency than complex 2. This is the first report of using trinuclear lanthanide coordination clusters as catalysts for the Friedel‐Crafts alkylation reaction.
Cognitive fusion and depressive symptoms in women with chronic pain: A longitudinal growth curve modelling study over 12 months
Authors: Carvalho Sérgio A. , Trindade Inês A. , Gillanders David , Pinto‐Gouveia José , Castilho Paula
Published: June 2019

This study aims to (a) explore individual differences in women with chronic pain (CP) in regard to pain intensity, functional impairment, cognitive fusion, and depressive symptoms and (b) longitudinally test whether cognitive fusion is a significant predictor of depression symptoms, while controlling for pain intensity and functional impairment, over a 12‐month period. This study follows a longitudinal design and was conducted in a sample of 86 women with CP who responded to an online battery of questionnaires in three equally spaced assessment moments. In order to explore the growth trajectory of variables of interest, latent growth curve models were examined. Also, correlation analyses were conducted between demographic and illness‐related variables and depressive symptoms, as well as between all variables in all assessment moments. Cognitive fusion and functional impairment (but not pain intensity) were significantly associated with baseline levels of depressive symptoms. Cognitive fusion significantly predicted the growth trajectory of depressive symptoms, whereas pain intensity and functional impairment did not. No demographic (age, marital status, education, socio‐economic) nor illness‐related variables (number of CP diagnoses, duration of CP, taking medication) were associated with depressive symptoms at any point. These results suggest that the trajectory of depressive symptoms in women with CP is not predicted by the intensity of pain nor pain‐related functional impairment, but rather by the tendency to get entangled with internal experiences (e.g., thoughts, emotions, and physical sensations), which may or may not be related to pain‐specific contents. Clinical implications are discussed.
Drivers and spatial structure of abiotic and biotic properties of lakes, wetlands, and streams at the national scale
Authors: King Katelyn , Cheruvelil Kendra Spence , Pollard Amina
Published: June 2019

Broad‐scale studies have improved our ability to make predictions about how freshwater biotic and abiotic properties will respond to changes in climate and land use intensification. Further, fine‐scaled studies of lakes, wetlands, or streams have documented the important role of hydrologic connections for understanding many freshwater biotic and abiotic processes. However, lakes, wetlands, and streams are typically studied in isolation of one another at both fine and broad scales. Therefore, it is not known whether these three freshwater types (lakes, wetlands, and streams) respond similarly to ecosystem and watershed drivers nor how they may respond to future global stresses. In this study, we asked, do lake, wetland, and stream biotic and abiotic properties respond to similar ecosystem and watershed drivers and have similar spatial structure at the national scale? We answered this question with three U.S. conterminous data sets of freshwater ecosystems. We used random forest (RF) analysis to quantify the multi‐scaled drivers related to variation in nutrients and biota in lakes, wetlands, and streams simultaneously; we used semivariogram analysis to quantify the spatial structure of biotic and abiotic properties and to infer possible mechanisms controlling the ecosystem properties of these freshwater types. We found that abiotic properties responded to similar drivers, had large ranges of spatial autocorrelation, and exhibited multi‐scale spatial structure, regardless of freshwater type. However, the dominant drivers of variation in biotic properties depended on freshwater type and had smaller ranges of spatial autocorrelation. Our study is the first to document that drivers and spatial structure differ more between biotic and abiotic variables than across freshwater types, suggesting that some properties of freshwater ecosystems may respond similarly to future global changes.
Prescribed fire and partial overstory removal alter an acorn–rodent conditional mutualism
Authors: Greenler Skye M. , Estrada Laura A. , Kellner Kenneth F. , Saunders Michael R. , Swihart Robert K.
Published: June 2019

In eastern North America, oak (Quercus) regeneration failure has spurred management using silvicultural approaches better aligned with the autecology of oaks. In particular, shelterwood harvests can create favorable intermediate light conditions for oak establishment and prescribed fire is predicted (by the oak–fire hypothesis) to favor oak regeneration. These approaches substantially modify forest structure and may affect crucial trophic interactions including the conditional mutualism between oaks and granivorous rodents that scatterhoard acorns, which shifts along a continuum from antagonistic to mutualistic depending on external factors. We investigated how overwinter survival and dispersal of northern red oak (Quercus rubra) acorns were influenced by location within or outside of group shelterwood harvests (small canopy gaps created throughout an intact forest stand) with and without prescribed fire. We conducted two concurrent experiments to test (1) dispersal and survival of acorns presented on the forest floor and (2) acorn pilferage rates from caches that mimic squirrel scatterhoards in shelterwood gap/group interiors, edges, and the uncut forest matrix in burned and unburned forest stands. In both experiments, acorn survival was generally higher in burned than unburned stands. Acorn survival from forest floor presentations was higher in the unharvested forest matrix than harvest gap interiors; however, there was no effect of proximity to harvest gaps on survival of cached acorns. Survival of cached acorns was associated with understory vegetative cover (−), coarse woody debris cover (−), and distance to nearest tree (+), but uncorrelated with canopy cover above the cache. Our results suggest that reduced understory cover following prescribed fire may increase perceived habitat riskiness for granivores resulting in higher acorn survival up to 2 yr post‐fire. These findings unify the oak–fire and oak–granivore conditional mutualism hypotheses, and suggest that the environmental conditions following prescribed fire and group shelterwood harvests may shift the oak–granivore conditional mutualism in a direction beneficial for oak regeneration.
The potential of satellite greenness to predict plant diversity among wetland types, ecoregions, and disturbance levels
Authors: Taddeo Sophie , Dronova Iryna , Harris Kendall
Published: June 2019

The unprecedented global biodiversity loss has massive implications for the capacity of ecosystems to maintain functions critical to human well‐being, urgently calling for rapid, scalable, and reproducible strategies for biodiversity monitoring, particularly in threatened ecosystems with difficult field access such as wetlands. Remote sensing indicators of spectral variability and greenness may predict the diversity of plant communities based on their optical diversity; however, most evidence is based on narrowband spectral data or terrestrial ecosystems. We investigate how spectral greenness and heterogeneity from publicly available broadband multi‐spectral Landsat satellite imagery explain variation in vegetation diversity across different wetland types, ecoregions, and disturbance levels using 1,138 sites surveyed by U.S. EPA's National Wetland Condition Assessment. We found positive correlations of plant species richness and diversity with indicators of annual maximum spectral greenness and its spatial heterogeneity, explaining up to 43% variation within the global sample, 48% within wetland types or ecoregions, and up to 61% with abiotic covariates. The combined effect of spectral greenness and heterogeneity was stronger than the best‐performing model using climatic, topographic, and edaphic factors alone. When compared among major U.S. watersheds and individual states, the fit of diversity‐greenness models increased when more wetland types were included within the corresponding region's boundaries, up to 61% at the watershed and 77% at the state level, respectively, for diversity models and up to 73% and 80%, respectively, for richness models. Model outliers were characterized by a significantly greater diversity of nonnative species (P < 0.0001), suggesting that changes in model performance and greenness distributions could be used as indicators of shifts in plant community composition, particularly in tidal wetlands making the majority of outliers with significantly lower than predicted diversity. This study represents a first‐time national‐scale effort to use publicly available remote sensing, climatic, and topographic data to predict plant diversity in wetlands, which tend to be understudied compared to terrestrial ecosystems despite being among the most stressed ecosystems on Earth. Our study suggests that multi‐temporal broadband satellite imagery could provide a low‐cost assessment of regional and national wetland biodiversity for prioritization of conservation efforts and early detection of biodiversity loss.
Eye‐tracking study on the effects of happiness and sadness on body dissatisfaction and selective visual attention during mirror exposure in bulimia nervosa
Authors: Naumann Eva , Biehl Stefanie , Svaldi Jennifer
Published: June 2019

Objective

Abundant research points to the central role of body image disturbances in the occurrence of eating disorders (ED). While emotional arousal has been identified as a trigger for binge eating in bulimia nervosa (BN), empirical knowledge on the influence of emotions on body image in individuals with BN is scarce. The present study sought to experimentally examine effects of a positive and negative emotion induction on body dissatisfaction and selective attention towards negatively valenced body parts among people with BN.

Method

In a randomized‐controlled cross‐over design, happiness and sadness were induced by film clips one‐week apart in women with BN (n= 23) and non‐ED controls (n= 26). After the emotion induction, participants looked at their body in a full‐length mirror, while their attentional allocation was recorded with the help of a mobile eye tracker. Participants repeatedly rated their momentary body dissatisfaction.

Results

Induction of happiness led to a significant decrease in self‐reported body dissatisfaction. Furthermore, attentional bias (higher gaze duration and frequency) towards the most disliked body part relative to the most liked body part was significantly greater in the sadness than happiness condition in BN. No significant effects of emotion induction on gaze duration and gaze frequency during mirror exposure were found for controls.

Discussion

In line with assumptions of current models on ED, findings support the notion that emotional state influences the body image of patients with BN.
Transition Metal Substituted Polyoxometalates as α‐Glucosidase Inhibitors
Authors: Hu Jing‐Jing , Wang Li , Chen Bing‐Nian , Chi Guo‐Xiang , Zhao Mei‐Juan , Li Yue
Published: June 2019

α‐Glucosidase inhibitors slow the digestion of carbohydrates and reduce blood sugar levels after meals. Recently, our experimental team found that phosphomolybdic acid with a Dawson‐type structure can effectively inhibit the activity of α‐glucosidase. Dawson‐type phosphomolybdic acid {H6(P2Mo18O62), H8[P2Mo17Fe(OH2)O61], H8[P2Mo17Co(OH2)O61] and H8[P2Mo17Ni(OH2)O61] abbreviated as P2Mo18, P2Mo17Fe, P2Mo17Co and P2Mo17Ni} were synthesized, and their inhibitory potential for α‐glucosidase was evaluated by enzyme kinetic analysis and molecular docking techniques. The results of kinetic analysis showed that P2Mo18, P2Mo17Fe, P2Mo17Co and P2Mo17Ni had a good inhibitory effect on α‐glucosidase, and the inhibitor concentration values of 50 % reduction in activity were 0.174 ± 0.0146 µm, 0.504 ± 0.00507 mm, 0.402 ± 0.00381 mm, 0.293 ± 0.0137 mm, respectively. Among them, P2Mo18, P2Mo17Co and P2Mo17Ni showed reversible mixed inhibition on α‐glucosidase, and P2Mo17Fe showed reversible competitive inhibition on α‐glucosidase. In addition, the four compounds separately form non‐covalent interactions with the enzyme molecule, including hydrogen bonds formed, wan der vaals interactions. This result is consistent with the mechanism study of enzyme kinetics. Overall, our results indicate that Dawson‐type parent P2Mo18 and three transition‐metal‐substituted phosphomolybdic acids P2Mo17Fe, P2Mo17Co and P2Mo17Ni are very promising as α‐glucosidase inhibitors for the treatment of diabetes.
Behavior of Organotin Sulfide Clusters towards Zinc Compounds
Authors: Dornsiepen Eike , Dehnen Stefanie
Published: June 2019

The reactivity of the organotin sulfide clusters [(R1Sn)3S4Cl] (A, R1 = CMe2CH2COMe) and [(R1Sn)4S6] (B) towards different zinc chloride phosphane complexes [ZnCl2(PR3)2] as well as diphenylzinc ZnPh2 was investigated. A diversity of different reaction products was obtained. In reactions starting from A, the tin sulfide cluster core was retained as a cation upon release of the chloride ligand, but side reactions occurred that yielded various chlorostannate or chlorozincate anions to crystallize along with the cations in the salts [(R2Sn)3S4][SnCl3] (1, R2 = CMe2CH2C(NNH2)Me), [(R3Sn)3S4]2[dppe(ZnCl3)2] (2, R3 = CMe2CH2(NNHPh)Me), and [(R2Sn)3S4]2[ZnCl4] (3). In one case, transfer of the organic substituent R3 from tin to phosphorus was observed, resulting in the phosphonium salt [R3PMe3][HPMe3][ZnCl4] (4). When reacting cluster compound B with different zinc species, no zinc‐containing compounds were isolated. Instead, in one case we observed hydrolysis of B and subsequent formation of the adamantane‐type mixed oxide/sulfide cluster [(R2Sn)4S5O] (5), as a consequence of the Lewis acidity of ZnCl2. In the reaction of B with ZnPh2, rearrangement of the cluster was observed under transmetallation of the phenyl substituent, yielding the dinuclear complex [(R2PhSn)2S2] (6).
Amino Acid Functionalized Organotin Trichlorides and Their Tin Sulfide Clusters
Authors: Engel Annikka , Dehnen Stefanie
Published: June 2019

We present a new synthesis of functionalized tin sulfide clusters via organotin trichlorides with boc‐protected amino acids (RAAcSnCl3). In this work we used non‐polar (alanine, valine, leucine, phenylalanine and methionine), polar/neutral (serine and tyrosine) and basic (histidine) amino acids. We obtained single crystals from a Boc‐protected valine derivative of the originally used organotin trichloride R1SnCl3 [R1 = CMe2CH2C(O)Me] and determined its structure by means of X‐ray diffraction. A subsequent reaction with sulfide sources led to a variety of respective cluster structures. By using either (Me3Si)2S or Na2S, the reaction product turns out to be the defect‐heterocubane cluster [(RAAcSn)3S4Cl] or the “doppeldecker”‐type cluster [(RAAcSn)4S6], respectively, according to 119Sn NMR spectroscopy.
Synthesis, Characterization, and Spectroscopic Properties of Allylic Ruthenium(II) Complexes of a Highly Conjugated Perinone
Authors: Nuñez Bahena Erick , Fernández Gijón César Augusto , Fomine Sergei , Alexandrova Larissa , Le Lagadec Ronan
Published: June 2019

Highly conjugated perinones were evaluated as proligands with [Ru(η6‐arene)Cl2]2 precursors (arene = p‐cymene or benzene). None of them, except itaco‐perinone (IP) bearing one exocyclic methylene group, were able to form coordination compounds. Expected η1‐coordination through the lone pair of the nitrogen or oxygen atoms of the perinone did not occur. Instead a deprotonation reaction involving the exocyclic methylene was observed and the corresponding [Ru(η6‐arene)(η3‐IP)Cl] complex was isolated in moderate yields. Mechanistic studies revealed that the base‐promoted isomerization of itaco‐perinone to citraco‐perinone prevented higher yields in the synthesis of the allylic complexes. Additionally, it was observed that IP can dimerize through the exocyclic methylene group, indicating high reactivity of this carbon–carbon double bond. Electronic absorption and emission properties of the perinones and organometallic compounds were studied.
Synthesis and Derivatization of Julolidine: A Powerful Heterocyclic Structure
Authors: Varejão Jodieh Oliveira Santana , Varejão Eduardo Vinícius Vieira , Fernandes Sergio Antonio
Published: June 2019

Julolidines constitute a class of N‐heterocycle compounds which have in common the 2,3,6,7‐tetrahydro‐1H,5H‐benzo[1,2]quinolizine ring. Due mainly to its fluorescence properties, such structures have shown potential application in a range of scientific and technological areas and have attracted attention of a great variety of research groups. For example, julolidines have been used for detection of ions and volatile compounds in environmental and biological samples, to the construction of dye‐sensitized solar cells, photoconductive materials and as fluorescent sensors for bioimaging. This review summarizes the strategies reported to the synthesis of the julolidine ring and the principal modifications for obtaining more complex julolidine derivatives with improved fluorescence properties of these compounds. In this context, aldol condensation, olefination, imine synthesis, and cross‐coupling reactions have been extensively explored and discussed. Examples of applications, which illustrate the great potential of such structures, will also be briefly presented.
SO2F2‐Activated Efficient Beckmann Rearrangement of Ketoximes for Accessing Amides and Lactams
Authors: Zhang Guofu , Zhao Yiyong , Xuan Lidi , Ding Chengrong
Published: June 2019

A novel, mild and practical protocol for the efficient activation of the Beckmann rearrangement utilizing the readily available and economical sulfuryl fluoride (SO2F2 gas) has been developed. The substrate scope of the operationally simple methodology has been demonstrated by 37 examples with good to nearly quantitative isolated yields (over 90 % yield in most cases) in a short time, including B(OH)2, COOH, NH2, and OH substituted substrates. A tentative mechanism was proposed involving formation and elimination of key intermediate, sulfonyl ester.