bluuebunny/crossref_metadata_2025 huggingface dataset:
Tuning Intramolecular Förster Resonance Energy Transfer and Activating Intramolecular Singlet Fission
Authors: Lavarda Giulia , Zirzlmeier Johannes , Gruber Marco , Rami Parisa R. , Tykwinski Rik R. , Torres Tomás , Guldi Dirk M.
Published: September 2018

The synergy of panchromatic absorption throughout most of the visible range of the solar spectrum and intramolecular singlet fission (SF) has been realized in a series of conjugates featuring different light‐harvesting subphthalocyanines (SubPcs) and an energy accepting pentacene dimer (Pnc2). At the focal point was a modular SubPc approach, which was based on decorating the SubPc core with different peripheral substituents to tailor and fine‐tune their optical properties. Transient absorption measurements assisted in corroborating that the SubPcs act as energy‐transfer antennas by means of unidirectional and quantitative intramolecular Förster resonance energy transfer (FRET) to the Pnc2, where an intramolecular SF affords triplet quantum yields reaching unity.
Mechanical properties of linear low‐density polyethylene fire‐retarded with melamine polyphosphate
Authors: Zaghloul Moustafa Mahmoud Yousry Mahmoud
Published: September 2018

The ecologically friendly flame retardant melamine polyphosphate (MPP) was prepared and incorporated into linear low‐density polyethylene (LLDPE). The impacts of this halogen‐free flame retardant on the mechanical characteristics of LLDPE were investigated in this research. The flame‐retardant properties were evaluated, and the mechanical properties, including flexural, tensile, compressive, fracture toughness, and shear behaviors, were tested. The weight fraction of the filler material ranges from 5% to 30%. The influence of filler weight content of the produced composites was evaluated by means of a universal testing machine in order to identify their behavior. The flammability of composites was highly improved with the addition of MPP. It was observed that the Young's modulus and flexural modulus increased almost linearly; similarly, the tensile fracture strength and tensile yield strength increased with the increase in MPP weight fraction. The tensile elongation at break decreased sharply between zero and 10% weight fraction, followed by a slight decrease up to 30% weight fraction. The flexural strength peaked with the increase in MPP weight fraction. The compressive strength and shear strength of the specimens were directly proportional to MPP content up to 15% and 30%, respectively. The novelty in the optimization of MPP content as well as the preparation method reveal a wide range of applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 134, 46770
Molecular interactions arising in polyethylene‐bentonite nanocomposites
Authors: Bonilla‐Blancas A. E. , Romero‐Ibarra I. C. , Vazquez‐Arenas J. , Sanchez‐Solis A. , Manero O. , Alvarez‐Ramirez J.
Published: September 2018

High density polyethylene (HDPE), linear low density polyethylene (LLDPE) and low density polyethylene (LDPE) are blended, and compared against a similar mixture but functionalized LDPE with maleic anhydride (MAh), HDPE‐LLDPE‐LDPE‐g‐MAh. In order to obtain nanocomposites from these polymer blends, a modified bentonite was added by incorporating l‐lysine into the bentonite galleries by melt extrusion. The resulting nanocomposites presented improved mechanical properties linked to strong polymer‐bentonite interactions and exfoliated structures as verified by transmission electron microscopy and rheometry. A detailed analysis of the feasible polymer‐bentonite interactions was conducted, of particular concern between the polar MAh groups and the intercalated l‐lysine. To gain further insights into the type of molecular interactions (i.e. polymer‐bentonite), a model nanocomposite was synthesized in solution to carry out further assessments through NMR, infrared spectroscopy and rheology analysis. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 46920.
Changes in the spatial–temporal patterns of droughts in the Brazilian Northeast
Authors: Cunha Ana Paula M. A. , Tomasella Javier , Ribeiro‐Neto Germano G. , Brown Matthew , Garcia Samia R. , Brito Sheila B. , Carvalho Magog A.
Published: September 2018

In Northeast Brazil (NEB), severe droughts have high socioeconomic impacts. In this study, the spatial–temporal characteristics of drought were evaluated based on a new drought index at 4‐km spatial resolution, derived from regional empirical relationships between a remote sensing‐based index and rain‐gauge‐based standardized precipitation index (SPI), a well‐known drought meteorological index. This index was used to compare the spatial pattern of severe drought events (1982–1983, 1992–1993, 1997–1998, and 2012–2013) of the last 30 years. Strong El Niño related droughts were found to be generally spatially limited, affecting around 30% of NEB and concentrated in the northern part of the region, while 2012 drought, which was not El Niño related, was widespread, reaching 46% of NEB. These results stressed the importance of analyzing droughts at the subregion scale using data with higher spatial resolution. Statistically significant trends (p < 0.05) toward drier conditions detected in the SPI time‐series were linked to the tropical Atlantic Ocean warming trend, which result in an increased drought risk and social vulnerability in the region.
Clinical epidemiology of congenital heart disease in Nigerian children, 2012–2017
Authors: Ekure Ekanem N. , Kalu Nnenna , Sokunbi Ogochukwu J. , Kruszka Paul , Olusegun‐Joseph Akinsanya D. , Ikebudu Desmond , Bala David , Muenke Maximilian , Adeyemo Adebowale
Published: September 2018

Background

Congenital heart diseases (CHDs) affect ~1% of newborns and are a significant cause of morbidity and mortality in children. We present the clinical epidemiology of CHD as seen in a large university medical center in Nigeria.

Methods

Participants were 767 children with echocardiographically confirmed CHD seen over a 5‐year period at the Lagos University Teaching Hospital, Nigeria.

Results

Clinical presentation was often late with just over half (58.1%) presenting in infancy. The male:female distribution was 1:1. The predominant types of cardiac lesion seen were septal defects (43%), conotruncal defects (23.7%), atrioventricular septal defects (9.8%), and right ventricular outflow tract obstruction (7.3%). Cyanotic CHD was seen in 28.4% of cases and the single most common cyanotic CHD was Tetralogy of Fallot (13.4%). Children with cyanotic CHD were older (p = .002), had more severe lesions (p < .0001) and were more likely to have cardiac intervention (p < .0001). Extracardiac malformations were present in nearly one‐third of the children. Syndromes associated with CHD were identified in 15.5% of the children and included Down syndrome (11.9%), congenital rubella syndrome (1.0%), and Marfan syndrome (0.7%).

Conclusions

This study is a large case series of CHD from a single site in sub‐Saharan Africa utilizing clinical, epidemiological, and developmental considerations. It provides a rich and up‐to‐date description of the clinical epidemiology of CHD in Nigerian children while yielding data that could be useful for designing genetic, molecular, and biomarker studies.
Emotional intelligence (EI) and self‐directed learning: Examining their relation and contribution to better student learning outcomes in higher education
Authors: Zhoc Karen C. H. , Chung Tony S. H. , King Ronnel B.
Published: September 2018

Self‐directed learning is recognised as a key goal of higher education. To facilitate self‐directed learning, emotional intelligence (EI), which encompasses the ability to regulate one's own emotions and to generate positive emotions, is important. The present study aimed to examine the effects ofEIon self‐directed learning and howEIand self‐directed learning contribute to key learning outcomes in higher education, including grade point average (GPA), generic learning outcomes (including social, cognitive and self‐growth outcomes) and students’ satisfaction with their university experience. The study adopted a prospective longitudinal design with 560 first‐year undergraduate students completing different measures at the beginning and end of the academic year. Results of the structural equation modelling showed thatEIhad a strong effect on self‐directed learning, which in turn was positively associated withGPAand various generic learning outcomes that are related to students’ satisfaction with the university experience. To better delineate the relationship betweenEIand self‐directed learning, multiple regression was performed. Results indicated that three key emotional abilities—emotional regulation of the self (ERS), appraisal of emotions in the self (AES) and emotional regulation of others (ERO)—were positively associated with self‐directed learning. This study provided empirical evidence that students who are more emotionally intelligent are more self‐directed, leading to higher achievement in both academic and generic development, which in turn results in higher university satisfaction. Implications of the findings are discussed.
Power of the Wilcoxon–Mann–Whitney test for non‐inferiority in the presence of death‐censored observations
Authors: Schmidtmann Irene , Konstantinides Stavros , Binder Harald
Published: September 2018

In clinical trials with patients in a critical state, death may preclude measurement of a quantitative endpoint of interest, and even early measurements, for example for intention‐to‐treat analysis, may not be available. For example, a non‐negligible proportion of patients with acute pulmonary embolism will die before 30 day measurements on the efficacy of thrombolysis can be obtained. As excluding such patients may introduce bias, alternative analyses, and corresponding means for sample size calculation are needed. We specifically consider power analysis in a randomized clinical trial setting in which the goal is to demonstrate noninferiority of a new treatment as compared to a reference treatment. Also, a nonparametric approach may be needed due to the distribution of the quantitative endpoint of interest. While some approaches have been developed in a composite endpoint setting, our focus is on the continuous endpoint affected by death‐related censoring, for which no approach for noninferiority is available. We propose a solution based on ranking the quantitative outcome and assigning worst rank scores to the patients without quantitative outcome because of death. Based on this, we derive power formulae for a noninferiority test in the presence of death‐censored observations, considering settings with and without ties. The approach is illustrated for an exemplary clinical trial in pulmonary embolism. The results there show a substantial effect of death on power, also depending on differential effects in the two trial arms. Therefore, use of the proposed formulae is advisable whenever there is death to be expected before measurement of a quantitative primary outcome of interest.
Synthetic repetitive extragenic palindromic (REP) sequence as an efficient mRNA stabilizer for protein production and metabolic engineering in prokaryotic cells
Authors: Deng Chen , Lv Xueqin , Li Jianghua , Liu Yanfeng , Du Guocheng , Amaro Rodrigo Ledesma , Liu Long
Published: September 2018

In prokaryotic cells, 3′–5′ exonucleases can attenuate messenger RNA (mRNA) directionally from the direction of the 3′–5′ untranslated region (UTR), and thus improving the stability of mRNAs without influencing normal cell growth and metabolism is a key challenge for protein production and metabolic engineering. Herein, we significantly improved mRNA stability by using synthetic repetitive extragenic palindromic (REP) sequences as an effective mRNA stabilizer in two typical prokaryotic microbes, namely, Escherichia coli for the production of cyclodextrin glucosyltransferase (CGTase) and
Corynebacterium glutamicum for the production of
N‐acetylglucosamine (GlcNAc). First, we performed a high‐throughput screen to select 4 out of 380 REP sequences generated by randomizing 6 nonconservative bases in the REP sequence designed as the degenerate base “N.” Secondly, the REP sequence was inserted at several different positions after the stop codon of the CGTase‐encoding gene. We found that mRNA stability was improved only when the space between the REP sequence and stop codon was longer than 12 base pairs (bp). Then, by reconstructing the spacer sequence and secondary structure of the REP sequence, a REP sequence with 8 bp in a stem‐loop was obtained, and the CGTase activity increased from 210.6 to 291.5 U/ml. Furthermore, when this REP sequence was added to the 3′‐UTR of glucosamine‐6‐phosphate
N‐acetyltransferase 1 (
GNA1), which is a gene encoding a key enzyme GNA1 in the GlcNAc synthesis pathway, the GNA1 activity was increased from 524.8 to 890.7 U/mg, and the GlcNAc titer was increased from 4.1 to 6.0 g/L in
C.
glutamicum. These findings suggest that the REP sequence plays an important function as an mRNA stabilizer in prokaryotic cells to stabilize its 3′‐terminus of the mRNA by blocking the processing action of the 3′–5′ exonuclease. Overall, this study provides new insight for the high‐efficiency overexpression of target genes and pathway fine‐tuning in bacteria.
Chemical Composition, Security and Bioactivity of the Red Pigment from Penicillium purpurogenum Li‐3
Authors: Jin Hong‐Jie , Zhang Xin , Cao Hong , Niu Yu‐Jing , Li Chun , Liu Hong
Published: September 2018

The chemical composition, security and bioactivity of pigments from Penicillium purpurogenum Li‐3 strain screened by our group were firstly studied in this work. DPPH and the filter disc diffusion method were used to determine the biological activities of the red pigments. The pigment was characterized by UV/VIS, FT‐IR, NMR and UPLC‐Q‐TOF‐MS. HPLC/MS was used to detect mycotoxins (citrinin) in fermentation broth. An acute toxicity was detected in the embryos of zebrafish. As a consequence, the crude red pigment from the AcOEt fraction showed better DPPH scavenge capacity and antibacterial activity. Spectroscopic (UV, FT‐IR, 13C‐NMR) and UPLC‐Q‐TOF‐MS analysis revealed that the Penicillium purpurogenum Li‐3 red pigment (RPs) was monascus‐like pigment and its molecular weight was 439.1997. Moreover, the red pigment was shown to be weak cytotoxic against the zebrafish embryos. The yield of the red pigment increased 69 % under optimized culture conditions. These outstanding properties will enlarge the application of RPs for natural food additives, new antioxidant and antibacterial drug development.
Onyx is the new black
Authors: Belardi Jorge A. , Albertal Mariano
Published: September 2018

Key Points

Ultrathin drug‐eluting stent (DES) constitute the workhorse stent for routine percutaneous coronary interventions.

The Resolute Onyx is a novel radiopaque, ultrathin DES with very low crossing profile.

In the present prospective, single arm study, Resolute (R) Onyx was non‐inferior and superior to a prior R iteration, in terms of late loss at 8 months follow‐up.

Data are only preliminary due to sample size and length of follow‐up.
Radial hemostasis: Harder, better, faster, stronger?
Authors: Seto Arnold H. , Kern Morton J.
Published: September 2018

Key Points

Hemostasis protocols after transradial catheterization are highly variable.

Hemostatic patches potentially speed hemostasis at the arteriotomy site, improving efficiency and throughput.

Larger trials of hemostatic patches are needed to demonstrate their superiority to conventional approaches.
Construction of NiCo2S4@NiMoO4 Core‐Shell Nanosheet Arrays with Superior Electrochemical Performance for Asymmetric Supercapacitors
Authors: Chen Sanming , Zhang Zhipeng , Zeng Weijia , Chen Jiaxiang , Deng Libo
Published: September 2018

In this work, we develop hierarchical NiCo2S4@NiMoO4 nanosheet arrays directly anchored on nickel foam by a hydrothermal method. The self‐supported core‐shell architecture take advantage of high electroactive surface area, rapid channels for ion diffusion and electron transport, and the synergistic contributions from both the NiCo2S4 core and NiMoO4 shell. Remarkably, the NiCo2S4@NiMoO4 electrode showed high specific capacitance of 1487.6 F g−1 at a current density of 1 A g−1 and superior cycling stability (89.7 % capacitance retention after 8000 charge‐discharge cycles). An asymmetric supercapacitor (ASC) with an optimized cell voltage of 1.6 V was assembled by using activated carbon (AC) as the negative electrode and NiCo2S4@NiMoO4 electrode as the positive electrode, achieving an extraordinary energy density of 53.2 Wh kg−1 at a power density of 560 W kg−1, and remained 34.8 Wh kg−1 at a maximum power density of 11.2 kW kg−1. The outstanding electrochemical behavior indicate that the NiCo2S4@NiMoO4 nanosheet arrays hold great promise for high‐performance energy storage devices.
Flexible and Tailorable Na−CO2 Batteries Based on an All‐Solid‐State Polymer Electrolyte
Authors: Wang Xingchao , Zhang Xuejing , Lu Yong , Yan Zhenhua , Tao Zhanliang , Jia Dianzeng , Chen Jun
Published: September 2018

Rechargeable Na< C‐>CO2 batteries coupling Na anodes with the greenhouse gas CO2 cathode are promising energy‐storage devices due to the high energy density, environmental friendliness and cost‐effectiveness. However, major challenges impeding the application of Na−CO2 batteries are safety concern regarding the leakage of flammable liquid electrolytes and the instability of the Na anodes. Herein, we construct all‐solid‐state flexible Na−CO2 batteries by designing an integrated structure built of a Na anode, poly(ethylene oxide)/NaClO4/SiO2 electrolyte and multiwall carbon nanotubes cathode. The batteries exhibit much improved safety and good cyclability (240 cycles with an overpotential increase of ∼0.4 V). Remarkably, we fabricated lab scale‐up integrated batteries (8×16 cm2), which display large capacity (450 mAh) and high energy density (173 Wh kg−1). Moreover, the integrated batteries show excellent bendability (≥1,000 times), foldability in individual shapes, as well as stable operation time (80 h) at bending states of 0° to 360°. Our work demonstrates a way to exploit flexible and safe solid‐state Na−CO2 batteries.
Household financial planning strategies for managing longevity risk
Authors: Bajtelsmit Vickie L. , Wang Tianyang
Published: September 2018

This study examines how longevity risk, in conjunction with other postretirement risks, impacts retirement consumption decisions and retirement wealth needs. We develop a theoretical model that directly examines the relationship between longevity risk and consumption/savings, and empirically test these theoretical implications by simulating retirement outcomes for representative households, including longevity, inflation, investment, health, and long‐term care risks. Our study shows that the top third of households by longevity need approximately 20% more retirement wealth than those households who live only an average life span. Investigations of various risk mitigation strategies suggest that combination strategies, particularly those that include delayed retirement, can significantly reduce the retirement wealth target. This research provides valuable new insights on household financial planning strategies for managing longevity risk.
Perspectives on mental accounting: An exploration of budgeting and investing
Authors: Zhang C. Yiwei , Sussman Abigail B.
Published: September 2018

This article provides an overview of recent advances in the literature on mental accounting within the context of consumer financial decision‐making. We first discuss the categorization process that underlies mental accounting and the methods people use to categorize funds. We then highlight some of the notable work that examines how mental accounting influences budgeting, spending, and investment decisions. The article concludes by proposing an agenda for future research, focusing on current gaps in our knowledge and promising areas to explore.
Designing Eco‐Sustainable Dye‐Sensitized Solar Cells by the Use of a Menthol‐Based Hydrophobic Eutectic Solvent as an Effective Electrolyte Medium
Authors: Boldrini Chiara Liliana , Manfredi Norberto , Perna Filippo Maria , Capriati Vito , Abbotto Alessandro
Published: September 2018

The use of a hydrophobic eutectic solvent based on dl‐menthol and a naturally occurring acid such as acetic acid has been tested as an eco‐friendly electrolyte medium in dye‐sensitized solar cells. In the presence of a de‐aggregating agent and a representative hydrophobic organic photosensitizer, the corresponding devices displayed relatively good power conversion efficiencies in very thin active layers. In particular, the higher cell photovoltage detected in comparison to devices based on toxic and volatile organic compounds may stem from a more efficient interface interaction, as suggested by electrochemical impedance spectroscopy studies showing greater charge recombination resistance and electron lifetime.
A Universal Geochemical Scenario for Formamide Condensation and Prebiotic Chemistry
Authors: Saladino Raffaele , Di Mauro Ernesto , García‐Ruiz Juan Manuel
Published: September 2018

The condensation of formamide has been shown to be a robust chemical pathway affording molecules necessary for the origin of life. It has been experimentally demonstrated that condensation reactions of formamide are catalyzed by a number of minerals, including silicates, phosphates, sulfides, zirconia, and borates, and by cosmic dusts and meteorites. However, a critical discussion of the catalytic power of the tested minerals, and the geochemical conditions under which the condensation would occur, is still missing. We show here that mineral self‐assembled structures forming under alkaline silica‐rich solutions are excellent catalysts for the condensation of formamide with respect to other minerals. We also propose that these structures were likely forming as early as 4.4 billion years ago when the whole earth surface was a reactor, a global scale factory, releasing large amounts of organic compounds. Our experimental results suggest that the conditions required for the synthesis of the molecular bricks from which life self‐assembles, rather than being local and bizarre, appears to be universal and geologically rather conventional.
Improving the Halogen–Magnesium Exchange by using New Turbo‐Grignard Reagents
Authors: Ziegler Dorothée S. , Wei Baosheng , Knochel Paul
Published: September 2018

This Minireview describes the scope of the halogen–magnesium exchange. It shows that the use of the turbo‐Grignard reagent (iPrMgCl⋅LiCl) greatly enhances the rate of the Br– and I–Mg exchange. Furthermore, this magnesium reagent allows the performance of a fast sulfoxide–magnesium exchange. Also, the use of sBuMgOR⋅LiOR (R=2‐ethylhexyl) enables a Br–Mg exchange in toluene leading to various Grignard reagents in toluene. Additionally, the new exchange reagent sBu2Mg⋅2 LiOR (R=2‐ethylhexyl) further increases the rate of the halogen–magnesium exchange allowing one to perform a chlorine–magnesium exchange for aromatic chlorides bearing an ortho‐methoxy substituent in toluene.
Biofunctionalization of Nano Channels by Direct In‐Pore Solid‐Phase Peptide Synthesis
Authors: Brodrecht Martin , Breitzke Hergen , Gutmann Torsten , Buntkowsky Gerd
Published: September 2018

Diatom biosilica are highly complex inorganic/organic hybrid materials. To get deeper insights on their structure at a molecular level, model systems that mimic the complex natural compounds were synthesized and characterized. A simple and efficient peptide immobilization strategy was developed, which uses a well‐ordered porous silica material as a support and commercially available Fmoc‐amino acids, similar to the known solid‐phase peptide synthesis. As an example, Fmoc‐glycine and Fmoc‐phenylalanine are immobilized on the silica support. The success of functionalization was investigated by 13C CP MAS and 29Si CP MAS solid‐state NMR. Thermogravimetric analysis (TGA) and elemental analysis (EA) were performed to quantify the functionalization. Changes of the specific surface area, pore volume, and pore diameters in all modification steps were studied by Brunauer–Emmett–Teller based nitrogen adsorption–desorption measurements (BET). The combination of the analytical methods provided high grafting densities of 2.1±0.2 molecules/nm2 on the surface. Furthermore, they allowed for monitoring chemical changes on the pore surface and changes of the pore properties of the material during the different functionalization steps. This universal approach is suitable for the selective synthesis of pores with tunable surface‐peptide functionalization, with applications to the synthesis of a big variety of silica–peptide model systems, which in the future may lead to a deeper understanding of complex biological systems.
Li2BaSc(BO3)2F and LiBa2Pb(BO3)2F with Layered Structures featuring Special Li−O/F Configurations
Authors: Chen Yanna , Zhang Min , Hu Cong , Wu Hongping , Yang Zhihua , Pan Shilie
Published: September 2018

Two new borate fluorides, Li2BaSc(BO3)2F and LiBa2Pb(BO3)2F, with layered structures featuring special Li−O/F configurations have been successfully prepared by the high‐temperature solution method. Li2BaSc(BO3)2F contains the first reported 2∞[Li2(BO3)2F] double layers that are evolved from 2∞[Be2BO3F2] single layers in KBe2BO3F2 through substituting BeO4 with the LiO3F tetrahedra. The adjacent double layers are tightly connected by strong Sc−O bonds, generating the strongest interlayer bond and smallest interlayer distance among KBe2BO3F2 derivatives with double‐layered structures. LiBa2Pb(BO3)2F features 2∞[Li(BO3)2F] single layers built up of special LiO4F2 octahedra and the BO3 triangles. To our best knowledge, the LiO4F2 octahedron is observed for the first time in borates. Besides, the LiO4F2 octahedra construct unique 1∞[LiO4F] straight chains through sharing apical F atoms, which is different from the configurations of the similar six‐coordinated LiO6 octahedra in other borates.
Reduced Graphene Oxide Chemically Modified with Aggregation‐Induced Emission Polymer for Solid‐State Optical Limiter
Authors: Liu Zhiwei , Dong Ningning , Jiang Peng , Wang Kexin , Wang Jun , Chen Yu
Published: September 2018

Aggregation‐induced emission (AIE) materials are usually not suitable for constructing solid nonlinear optical (NLO) devices because strong solid‐state aggregation behavior would shorten the excited‐state lifetime, add relaxation pathways, and thereby reduce effective NLO absorption. To address this problem a newly synthesized AIE material, poly{[9,9‐bis(6‐azidohexyl)‐9H‐fluorene]‐alt‐(1,1,2,2‐tetraphenylethene)} (PAHFTP), was treated with reduced graphene oxide (RGO) to give the soluble derivative of poly[(9,9‐dihexyl‐9H‐fluorene)‐alt‐(1,1,2,2‐tetraphenylethene)] (PFTP) covalently grafted onto RGO (PFTP‐RGO). Upon covalent grafting of PAHFTP onto the RGO surface, about 91.89 % of the fluorescence intensity of the PAHFTP film was quenched due to electron transfer from PFTP to RGO, which yielded PFTP.+–RGO.− radical‐ion pairs. The as‐prepared PFTP‐RGO was embedded into a non‐optically active poly(methyl methacrylate) (PMMA) matrix to produce the PFTP‐RGO/PMMA film with good optical quality. As expected, the PAHFTP/PMMA film did not show any NLO response. In contrast to the PFTP‐RGO/PMMA and RGO/PMMA films, the annealed PFTP‐RGO/PMMA exhibited superior OL performance, with low OL thresholds of 0.24 GW cm−2 (1.44 J cm−2) at 532 nm and 0.18 GW cm−2 (1.08 J cm−2) at 1064 nm. The damage thresholds of the annealed PFTP‐RGO/PMMA film are around 33.88 J cm−2 at 900 μJ at 532 nm and 37.32 J cm−2 at 1000 μJ at 1064 nm, respectively.
How Do Substrates Bind to a Bifunctional Thiourea Catalyst? A Vibrational CD Study on Carboxylic Acid Binding
Authors: Kreienborg Nora M. , Merten Christian
Published: September 2018

Knowledge about the active conformation of an asymmetric catalyst is highly valuable in order to understand its stereoinductive power, but spectroscopic access to these structures is often limited. For the example of Takemoto's bifunctional thiourea, we demonstrate the capability of VCD spectroscopy to characterize the conformational preferences of the catalyst with and without having a reactant bound to it. In particular we show that the binding orientation of carboxylic acids can easily be derived from a computationally guided analysis of the spectra. Moreover, we identify characteristic marker bands, which are only visible in the VCD spectra of the catalyst/acid mixtures but not in the corresponding IR spectra. Lastly, we also discuss the problem that the popular DFT functional M06‐2X, which we found to perform exceptionally well in the calculations of vibrational frequencies for fluorinated molecules, predicts incorrect structures of the molecular clusters. We relate this poor performance in predicting the structure of the binding topologies to an overestimation of dispersive CH–π and π–π interactions, which occur due to a neglect of the solvent molecules in the clusters. VCD spectroscopy is thus shown to be a powerful tool to identify and subsequently correct such mispredictions of solution‐phase structures.
Multipurpose Energetic Materials by Shuffling Nitro Groups on a 3,3′‐Bipyrazole Moiety
Authors: Kumar Dheeraj , Tang Yongxing , He Chunlin , Imler Gregory H. , Parrish Damon A. , Shreeve Jean'ne M.
Published: September 2018

A family of 3,3′‐bipyrazole‐based energetic compounds having C‐NO2/N‐NO2 functionalities was synthesized by using various nitrating conditions. These nitro derivatives of bipyrazole are significantly more dense and energetic compared to the corresponding nitropyrazole analogues while maintaining the desired thermal stability and sensitivity. Depending on the number and nature of energetic nitro groups (C‐NO2/N‐NO2), different classes of energetic materials, such as green primary explosives, high‐performance secondary explosives and heat‐resistant explosives, were obtained. All the compounds were thoroughly characterized by IR, NMR [1H, 13C{1H}, 15N], elemental analysis, and differential scanning calorimetry (DSC). Four were also structurally characterized with single‐crystal X‐ray diffraction studies. Heats of formation and detonation performance were calculated using Gaussian 03 and EXPLO5 v6.01 programs, respectively.
Rare‐Earth Cyclobutadienyl Sandwich Complexes: Synthesis, Structure and Dynamic Magnetic Properties
Authors: Day Benjamin M. , Guo Fu‐Sheng , Giblin Sean R. , Sekiguchi Akira , Mansikkamäki Akseli , Layfield Richard A.
Published: September 2018

The potassium cyclobutadienyl [K2{η4‐C4(SiMe3)4}] (1) reacts with MCl3(THF)3.5 (M=Y, Dy) to give the first rare‐earth cyclobutadienyl complexes, that is, the complex anions [M{η4‐C4(SiMe3)4}{η4‐C4(SiMe3)3‐κ‐(CH2SiMe2}]2−, (2M), as their dipotassium salts. The tuck‐in alkyl ligand in 2M is thought to form through deprotonation of the “squarocene” complexes [M{η4‐C4(SiMe3)4}2]− by 1. Complex 2Dy is a single‐molecule magnet, but with prominent quantum tunneling. An anisotropy barrier of 323(22) cm−1 was determined for 2Dy in an applied field of 1 kOe, and magnetic hysteresis loops were observed up to 7 K.
The PRISM intervention for adolescents and young adults with cancer: Paying attention to the patient as a whole person
Authors: Mack Jennifer W.
Published: September 2018

The Promoting Resilience in Stress Management intervention brings welcome news to adolescents and young adults with cancer, with an increase in resilience, improved cancer‐related quality of life, and decreased overall distress among patients who participated in the intervention in comparison with controls. As the investigators think about their next steps, consideration of how best to expand this intervention to underserved populations should be a priority.

See also pages 3911‐20.
Non‐Perovskite Hybrid Material, Imidazolium Lead Iodide, with Enhanced Stability
Authors: Seth Charu , Khushalani Deepa
Published: September 2018

A systematic study of a new hybrid organic‐inorganic material where the cation has been replaced with imidazolium is presented. Imidazolium lead iodide (ImPI) shares the same stoichiometry of ABX3 as a perovskite, however, it has a hexagonal structure. This material shows a vastly improved thermal stability as compared to the more popular hybrid perovskite, methyl ammonium lead iodide (MAPI). ImPI also exhibits a dramatic phase stability as compared to MAPI as demonstrated by the variable temperature XRD data (both low temperature and high temperature). In addition to the enhanced thermal robustness, ImPI shows three times better stability than MAPI under ambient conditions. The stability can be attributed to better packing efficiency of the ImPI lattice which in turn depends on the symmetrical and bulkier organic cation, imidazolium. Optoelectronic measurements were also performed and specifically, unlike for MAPI, photoluminescence measurements of ImPI showcased a broad emission over a range of 500 nm to 900 nm which could be attributed to the presence of self‐trapped excitons and as such this broad emission holds promise for light emitting device applications.
Relative and Absolute Bioavailability Study of Emicizumab to Bridge Drug Products and Subcutaneous Injection Sites in Healthy Volunteers
Authors: Kotani Naoki , Yoneyama Koichiro , Kawakami Nobuhiko , Shimuta Tohru , Fukase Hiroyuki , Kawanishi Takehiko
Published: September 2018

Emicizumab (ACE910) is a bispecific antibody that is a novel, subcutaneously injectable treatment for patients with hemophilia A. This study assessed the relative bioavailability of emicizumab between old and new drug products (DPs) and among 3 commonly used subcutaneous injection sites (abdomen, upper arm, and thigh), together with its absolute bioavailability in healthy volunteers. Forty‐eight healthy volunteers were randomized into 4 groups to receive a single subcutaneous injection of 1 mg/kg with the old or new DP, and another 12 volunteers each received a single, 90‐minute, intravenous infusion of 0.25 mg/kg with the new DP. Similar pharmacokinetic profiles were observed between the DPs, with geometric mean ratios of 1.199 (90% confidence interval [CI] 1.060‐1.355) for the maximum plasma concentration and 1.083 (90% CI 0.920‐1.275) for area under the plasma concentration‐time curve extrapolated to infinity. The geometric mean ratios of maximum plasma concentration and area under the plasma concentration‐time curve extrapolated to infinity for upper arm versus abdomen were 0.823 (90% CI 0.718‐0.943) and 0.926 (90% CI 0.814‐1.053), respectively, and those for thigh versus abdomen were 1.168 (90% CI 1.030‐1.324) and 1.073 (90% CI 0.969‐1.189), respectively. Absolute bioavailability ranged from 80.4% to 93.1%. These results suggested that no emicizumab dose adjustment would be needed when switching the DPs or injecting to different sites interchangeably and that emicizumab injected subcutaneously is highly bioavailable.
Cover patches: A general feature extraction strategy for spoofing detection
Authors: Cai Guorong , Su Songzhi , Leng Chengcai , Wu Jipeng , Wu Yundong , Li Shaozi
Published: September 2018

Face anti‐spoofing has attracted many attentions in security applications, such as mobile payment and entrance guard. Until now, face anti‐spoofing technique is still a challenging task. Mainstream image‐based spoofing algorithms usually use global motion or texture information to distinguish whether an input face is live or fake. However, the performance of these methods are sensitive in light changes, or images acquired from different sensors. The main reason is that spoofed face image always has slight different texture in local areas, such as landmark or salient region of face. To this end, this paper proposes a novel multi‐patches feature extraction strategy to detect spoofing. First, a set of patches with specific combination scheme is selected to cover the face image. Second, features such as hand‐crafted Gray Level Co‐occurrence Matrix (GLCM), Local Binary Patterns (LBP), or deep features are extracted from these patches. Third, all features are combined as the global descriptor of the face image, then fed into an SVM classifier to verify the anti‐spoofing detection. Experimental results show that the proposed strategy can effectively enhance the performance, concerning with the accuracy of spoofed face detection in four widely used anti‐spoofing databases.
A relative privacy model for effective privacy preservation in transactional data
Authors: Bewong Michael , Liu Jixue , Liu Lin , Li Jiuyong , Choo Kim‐Kwang Raymond
Published: September 2018

Data publishing is pivotal to advances in knowledge discovery. Nonetheless, such publishing may suffer from privacy disclosures. This is especially the case in transactional data such as web search and point of sales logs. The reason is that the current potent privacy preserving mechanisms mainly focus on relational data. In this work, we propose a new privacy metric for transactional data to prevent inference attacks by ensuring that the adversary learns no more about an intended victim than what is publicly available. We then propose a publication mechanism Anony, which satisfies our privacy metric without excessive loss of utility. Finally, we present an empirical evaluation of our method on three benchmark datasets, and the results show the effectiveness of our method.
Predicting the results of molecular specific hybridization using boosted tree algorithm
Authors: Zhu Weijun , Han Yingjie , Wu Huanmei , Liu Yang , Nan Xiaofei , Zhou Qinglei
Published: September 2018

In the field of bioinformatics and DNA computing, simulated hybridization experiments can replace real molecular hybridization experiments to some extent, avoiding some disadvantages of the actual experimental design. However, the core techniques, which are employed by the popular DNA simulation software, are limited to the exponential computational complexity of the combinatorial problems. As a result, it is impossible to decide whether a specific hybridization among complex DNA molecules is effective or not within acceptable time. To address this common problem, we hereby introduce a new method based on the machine learning technique. First, a sample set is employed to train the boosted tree algorithm, which resulted in a corresponding machine learning model. Second, this model is applied to predict the classification results of molecular hybridization for a given group of DNA molecular coding. The experiment results showed that the new method had an average accuracy level of 94.2% and an average efficiency level 90 839 times higher than that of the existing representative approaches. Especially for the case study in this paper, the efficiency of the new method is 235 000, 250 000, and 990 000 times higher than that of the three existing methods, respectively. These experimental results indicate that our new approach can quickly and accurately determine the biological effectiveness of molecular hybridization for a given DNA design.
Interaction of Non‐polarizable Cations with Azaborine Isomers and Their Mono‐Substituted Derivatives: Position, Induction, and Non‐Classical Effects Matter
Authors: Yourdkhani Sirous , Chojecki Michał , Korona Tatiana
Published: September 2018

Progress in BN/CC isosterism has opened an overwhelming urge to find prospective applications of this class of materials. Herein, the interaction of three BN isosteres of benzene, i. e. 1,2‐, 1,3‐, 1,4‐azaborines and their mono‐substituted derivatives with Na+and Mg2+cations has been surveyed in light of symmetry‐adapted perturbation theory (SAPT) and interacting quantum atoms method (IQA). We have found that the orientation of the cations towards azaborines depends considerably on boron and nitrogen dispersion pattern. However, this tendency cannot be justified by electrostatics alone, without taking into account the induction as the major stabilizing factor, and Pauli repulsion, which effectively shapes the potential energy surface. Due to the significant role of induction, molecular electrostatic potentials (MEPs) can predict the interaction strength and anisotropy only if they are obtained from densities perturbed by the effective field of the cations.Through‐bondandthrough‐spaceeffects of the substituents strongly depend on their position in the ring, where the through‐bond effects are dominated by theinductivecontribution. The importance of the induction energy even at short distances, and of the non‐classical IQA component signify themulti‐center covalencycharacter of azaborine‐cation interactions. Therefore, a pure classical view on the interaction between the cation and compounds standing on the organic/inorganic border is to a large extent misleading.
Dimerization of Metallofullerenes to Obtain Materials with Enhanced Nonlinear Optical Properties
Authors: Jiang Yuhang , Wang Dongsheng , Xu Dan , Zhang Jinying , Wang Zhiyong
Published: September 2018

In this work, we theoretically designed a new class of fullerene derivatives, metallofullerene heterodimers, through cross dimerization of metallofullerene monomers Li@C60, Y@C82 and Y2@C80. The molecular structures, electronic structures, linear and nonlinear optical properties of the heterodimers were studied by using density functional theory calculations. We found that two fullerene cages are connected through a relatively weak carbon‐carbon single bond. Inter‐cage electron transfer takes place in the heterodimers because of the different electron accepting abilities of the metallofullerene moieties. The first hyperpolarizability of the metallofullerenes increases remarkably as a result of dimerization. Time‐dependent density functional theory calculations reveal that the enhanced first hyperpolarizability of the dimer is associated with charge‐transfer transitions. This study demonstrates that covalent dimerization is an efficient means to improve the nonlinear optical response of metallofullerenes.
Derealization and self‐harm strategies are used to regulate disgust, fear, and sadness in adult survivors of childhood sexual abuse
Authors: Bradley Aoife , Karatzias Thanos , Coyle Eimear
Published: September 2018

Emotion regulation (ER) difficulties have been identified as an important target for clinical intervention in the treatment of post‐traumatic stress disorder (PTSD) symptoms in survivors of childhood sexual abuse (CSA). However, there is limited research regarding the use of specific strategies to regulate specific emotions following exposure to traumatic events. The aim of the current study was to investigate the indirect effects of four trauma‐related emotions (anger, sadness, disgust, and fear) on PTSD severity via two mediators: derealization and self‐harm. In particular, we tested that if the two hypothetical mediators operate sequentially, derealization precedes self‐harm and/or self‐harm precedes derealization. A predominate female clinical sample (N = 109) of CSA survivors completed measures of experience of emotions, ER, and post‐traumatic stress. Bivariate and serial mediation analyses were conducted to test the direct and indirect effects of trauma‐related emotions on PTSD severity. Serial mediation analyses indicated that there were significant total effects of all trauma‐related emotions on PTSD severity. Three trauma‐related emotions (sadness, disgust, and fear) were indirectly associated to PTSD severity via derealization and self‐harm and via self‐harm and derealization. Results indicate that difficulties in regulating the emotions of sadness, disgust, and fear may result in more severe derealization and self‐harm as coping strategies, which in turn lead to greater PTSD severity. The sequence of mediators does not hold great importance in these pathways. Overall, our findings suggest that therapeutically targeting derealization and self‐harm might enable the reduction of PTSD among CSA survivors.
Estimating environmental suitability
Authors: Drake John M. , Richards Robert L.
Published: September 2018

Methods for modeling species’ distributions in nature are typically evaluated empirically with respect to data from observations of species occurrence and, occasionally, absence at surveyed locations. Such models are relatively “theory‐free.” In contrast, theories for explaining species’ distributions draw on concepts like fitness, niche, and environmental suitability. This paper proposes that environmental suitability be defined as the conditional probability of occurrence of a species given the state of the environment at a location. Any quantity that is proportional to this probability is a measure of relative suitability and the support of this probability is the niche. This formulation suggests new methods for presence‐background modeling of species distributions that unify statistical methodology with the conceptual framework of niche theory. One method, the plug‐and‐play approach, is introduced for the first time. Variations on the plug‐and‐play approach were studied with respect to their numerical performance on 106 species from an exhaustively sampled presence–absence survey of vegetation in the Canton of Vaud, Switzerland. Additionally, we looked at the robustness of these methods to the presence of irrelevant information and sample size. Although irrelevant variables eroded the predictive performance of all methods, these methods were found to be both numerically and statistically robust.
Synthesis, Crystal Structures and Magnetic Properties of Two Heterobridged µ‐Phenoxo‐µ1,1‐Azide/Isocyanate Dinickel(II) Compounds: Experimental and Theoretical Exploration
Authors: Mandal Shuvankar , Majumder Samit , Mondal Suraj , Mohanta Sasankasekhar
Published: September 2018

This investigation deals with the syntheses, crystal structures and experimental and density functional theoretical magnetic properties of two heterobridged and isomorphous µ‐phenoxo‐µ1,1‐azide/isocyanate dinickel(II) compounds of composition [NiII2(L)2(µ1,1‐N3)(CH3CN)(CH3OH)](ClO4)·CH3CN (1) and [NiII2(L)2(µ1,1‐NCO)(CH3CN)(CH3OH)](ClO4)·CH3CN (2), where HL is the 1:1 condensation product of 3‐ethoxysalicylaldehyde and 4‐(2‐aminoethyl)‐morpholine. The two compounds are isostructural as well, except that 1 contains end‐on azide and 2 contains end‐on isocyanate. One metal ion is surrounded by O(µ‐phenoxo), N(µ1,1‐azide/µ1,1‐isocyanate), N(imine), N(amine), O(ethoxy) and O(phenoxide, monodentate) atoms, while the second metal ion is surrounded by O(µ‐phenoxo), N(µ1,1‐azide/µ1,1‐isocyanate), N(imine), N(amine), O(methanol) and N(acetonitrile) atoms. Variable‐temperature (2–300 K) magnetic susceptibility and variable‐field (up to 5 T) magnetization data reveal ferromagnetic exchange interaction with J = 18.0 cm–1 for 1 and J = 11.4 cm–1 for 2. Broken symmetry density functional calculations of exchange interaction have been performed on both complexes and the DFT‐computed J values are nicely matched with the experimental J values [J(exp) = 18.0 cm–1 and J(DFT) = 17.2 cm–1 for 1; J(exp) = 11.4 cm–1 and J(DFT) = 8.9 cm–1 for 2]. The magnetic properties have been nicely rationalized in terms of spin density, magnetic orbitals and breakdown approach.