bluuebunny/crossref_metadata_2025 huggingface dataset:
Surgical resection of ripple onset predicts outcome in pediatric epilepsy
Authors: Tamilia Eleonora , Park Eun‐Hyoung , Percivati Stefania , Bolton Jeffrey , Taffoni Fabrizio , Peters Jurriaan M. , Grant P. Ellen , Pearl Phillip L. , Madsen Joseph R. , Papadelis Christos
Published: July 2018

Objective

In patients with medically refractory epilepsy (MRE), interictal ripples (80–250Hz) are observed in large brain areas whose resection may be unnecessary for seizure freedom. This limits their utility as epilepsy biomarkers for surgery. We assessed the spatiotemporal propagation of interictal ripples on intracranial electroencephalography (iEEG) in children with MRE, compared it with the propagation of spikes, identified ripples that initiated propagation (onset‐ripples), and evaluated their clinical value as epilepsy biomarkers.

Methods

Twenty‐seven children who underwent epilepsy surgery were studied. We identified propagation sequences of ripples and spikes across multiple iEEG contacts and calculated each ripple or spike latency from the propagation onset. We classified ripples and spikes into categories (ie, onset, spread, and isolated) based on their spatiotemporal characteristics and correlated their mean rate inside and outside resection with outcome (good outcome, Engel 1 versus poor outcome, Engel≥2). We determined, as onset‐zone, spread‐zone, and isolated‐zone, the areas generating the corresponding ripple or spike category and evaluated the predictive value of their resection.

Results

We observed ripple propagation in all patients and spike propagation in 25 patients. Mean rate of onset‐ripples inside resection predicted the outcome (odds ratio = 5.37; p = 0.02) and correlated with Engel class (rho = −0.55; p = 0.003). Resection of the onset‐ripple‐zone was associated with good outcome (p = 0.047). No association was found for the spread‐ripple‐zone, isolated‐ripple‐zone, or any spike‐zone.

Interpretation

Interictal ripples propagate across iEEG contacts in children with MRE. The association between the onset‐ripple‐zone resection and good outcome indicates that onset‐ripples are promising epilepsy biomarkers, which estimate the epileptogenic tissue better than spread‐ripples or onset‐spikes. Ann Neurol 2018;84:331–346
Chiral N,N Ligands Enabling Palladium‐Catalyzed Enantioselective Intramolecular Heck–Matsuda Carbonylation Reactions by Sequential Migratory and CO Insertions
Authors: Carmona Rafaela C. , Köster Otto D. , Correia Carlos Roque Duarte
Published: July 2018

Unprecedented enantioselective intramolecular Heck carbonylation reactions of arenediazonium salts were enabled by a chiral N,N ligand. This reaction constitutes the first enantioselective Heck carbonylation that proceeds through migratory insertion followed by CO insertion. The enantioenriched functionalized dihydrobenzofurans were obtained in good to high yields and enantiomeric ratios of up to 98:2 under mild and operationally simple reaction conditions.
Tailored Cobalt‐Catalysts for Reductive Alkylation of Anilines with Carboxylic Acids under Mild Conditions
Authors: Liu Weiping , Sahoo Basudev , Spannenberg Anke , Junge Kathrin , Beller Matthias
Published: July 2018

The first cobalt‐catalyzed hydrogenative N‐methylation and alkylation of amines with readily available carboxylic acid feedstocks as alkylating agents and H2 as ideal reductant is described. Combination of tailor‐made triphos ligands with cobalt(II) tetrafluoroborate significantly improved the efficiency, thus promoting the reaction under milder conditions. This novel protocol allows for a broad substrate scope with good functional group tolerance, even in the presence of reducible alkenes, esters, and amides.
Direct N‐Alkylation and Kemp Elimination Reactions of 1‐Sulfonyl‐1H‐Indazoles
Authors: Tang Meng , Chu Bingjie , Chang Xiaowei
Published: July 2018

The reactions of 1‐sulfonyl‐1H‐indazoles under basic conditions are discussed, and the direct N‐alkylation and Kemp elimination reactions of these compounds are reported. A series of 2‐(p‐tosylamino)benzonitriles and N‐alkyl indazoles were prepared in good yields. Moreover, the 2‐(p‐tosylamino)benzonitriles could be transformed into a diverse range of important derivatives in a one‐pot reaction. This method was successfully applied to the total syntheses of quindolinone and cryptolepinone; quindolinone was prepared in a one‐pot reaction from 1‐sulfonyl‐1H‐indazole.
Self‐Assembly of Water‐Soluble Platinum(II)‐Based Metallacalixarenes and Tuning Their Conformational Interconversion via Synergistic Effects between Solvents and Anions
Authors: Deng Wei , Yu Zheng‐Su , Ma Hong‐Wei , Yu Shu‐Yan
Published: July 2018

The aqueous self‐assembly of the flexible ligand L bis(1H‐benz[d]imidazole‐1‐yl)methane and cis‐coordinated PtII precursors [(en)Pt2+, (tmeda)Pt2+, en=ethylenediamine, tmeda=N,N,N′,N′‐tetramethylethylenediamine)] led to the formation of the metallacalixarenes with full alternative conformations (e.g., two novel water‐soluble metallacalixarenes [M2L2]4+ and [M3L3]6+ with D2 and D3 symmetry, respectively). Their molecular structures were determined by single crystal X‐ray analyses in solid state. The two metallacalixarenes present different cavity sizes and the [M3L3]6+ cavity encapsulates one NO3−. NOESY NMR revealed that the conformational interconversion between 1,3‐alternate conformer in methanol and cone conformer in DMSO was tuned via the synergistic effect between solvent and anion. Guest encapsulation is also discussed.
Desymmetrization of Achiral Heterobicyclic Alkenes through Catalytic Asymmetric Hydrophosphination
Authors: Sadeer Abdul , Ong Yew Jin , Kojima Tadayuki , Foo Ce Qing , Li Yongxin , Pullarkat Sumod A. , Leung Pak‐Hing
Published: July 2018

Asymmetric addition of diarylphosphines to oxa‐ and azabicyclic alkenes proceeded in the presence of a chiral phosphapalladacycle catalyst and a mild acid at room temperature to give exclusively the enantioenriched addition products in excellent yields and good selectivities. Three new chiral carbon centers were generated stereoselectively by the catalytic hydrophosphination reaction.
Integrating theoretical and experimental permeability estimations for provisional biopharmaceutical classification: Application to the WHO essential medicines
Authors: Cabrera‐Pérez Miguel Ángel , Pham‐The Hai , Cervera Mirna Fernández , Hernández‐Armengol Rosario , Miranda‐Pérez de Alejo Claudia , Brito‐Ferrer Yudileidy
Published: July 2018

The accuracy of the provisional estimation of the Biopharmaceutics Classification System (BCS) is heavily influenced by the permeability measurement. In this study, several theoretical and experimental models currently employed for BCS permeability classification have been analysed. The experimental models included the in situ rat intestinal perfusion, the ex vivo rat intestinal tissue in an Ussing chamber, the MDCK and Caco‐2 cell monolayers, and the parallel artificial membrane (PAMPA). The theoretical models included the octanol–water partition coefficient and the QSPeR (Quantitative Structure‐Permeability Relationship) model recently developed. For model validation, a dataset of 43 compounds has been recompiled and analysed for the suitability for BCS permeability classification in comparison with the use of human intestinal absorption and oral bioavailability values. The application of the final model, based on a majority voting system showed a 95.3% accuracy for predicting human permeability. Finally, the present approach was applied to the 186 orally administered drugs in immediate‐release dosage forms of the WHO Model List of Essential Medicines. The percentages of the drugs that were provisionally classified as BCS Class I and Class III was 62.4%, suggesting that in vivo bioequivalence (BE) may potentially be assured with a less expensive and more easily implemented in vitro dissolution test, ensuring the efficiency and quality of pharmaceutical products. The results of the current study improve the accuracy of provisional BCS classification by combining different permeability models.
Chiral ligand‐induced photoluminescence intermittence difference of CdTe quantum dots
Authors: Yang Jie , Dong Chaoqing , Ren Jicun
Published: July 2018

Semiconductor quantum dots (QDs) are a new nano‐material, and their unique optical properties have become a focal point of research in both academia and industry. In this study, we studied photoluminescence (PL) intermittence (or ‘blinking’) behaviors of individual QDs prepared with different chiral ligands by using single molecule microscopy and single molecule fluorescence correlation spectroscopy (FCS). We found that the chirality of N‐isobutyryl‐d/l‐cysteine (D/L‐NIC) as surface stabilizers significantly influences PL blinking behaviors of cadmium telluride (CdTe) QDs synthesized in aqueous solution. The ‘on time’ distribution and the power‐law exponent analyses show that the D‐NIC more efficiently suppresses the blinking of QDs over L‐NIC. Ensemble spectroscopies verfied that the remarkably‐different blinking behaviors of QDs induced by ligand chirality were attributed to the different number of chiral ligands bound in the surface of QDs.
Virtual and augmented reality: Applications for the learning of technical historical heritage
Authors: Rojas‐Sola José I. , Aguilera‐García Ángel
Published: July 2018

This manuscript presents two applications developed for learning about the details and operation of Agustín de Betancourt́s machine for cutting cane and other aquatic plants in navigable channels and rivers, drawing on virtual reality for personal computers under Windows, and augmented reality for mobile devices based on Android, along with a 3D printing of the 3D model. Similarly, in the case of augmented reality, an algorithm for the selection of parts or systems has been developed that shows the technical information of each piece or system of this historical invention. Finally, the evaluation of these applications has been satisfactory according to the results of an anonymous survey with seven questions given to a group of 10 people because the values obtained from statistical variables such as the mean, median and standard deviation prove it.
Photosensitised Multiheme Cytochromes as Light‐Driven Molecular Wires and Resistors
Authors: van Wonderen Jessica H. , Li Daobo , Piper Samuel E. H. , Lau Cheuk Y. , Jenner Leon P. , Hall Christopher R. , Clarke Thomas A. , Watmough Nicholas J. , Butt Julea N.
Published: July 2018

Multiheme cytochromes possess closely packed redox‐active hemes arranged as chains spanning the tertiary structure. Here we describe five variants of a representative multiheme cytochrome engineered as biohybrid phototransducers for converting light into electricity. Each variant possesses a single Cys sulfhydryl group near a terminus of the heme chain, and this was efficiently labelled with a RuII(2,2′‐bipyridine)3 photosensitiser. When irradiated in the presence of a sacrificial electron donor (SED) the proteins exhibited different types of behaviour. Certain proteins were rapidly and fully reduced. Other proteins were rapidly semi‐reduced but resisted complete photoreduction. These findings reveal that photosensitised multiheme cytochromes can be engineered to act as resistors, with intrinsic regulation of light‐driven electron accumulation, and also as molecular wires with essentially unhindered photoreduction. It is proposed that the observed behaviour arises from interplay between the site of electron injection and the distribution of heme reduction potentials along the heme chain.
Impact and trends of intravascular imaging in diagnostic coronary angiography and percutaneous coronary intervention in inpatients in the United States
Authors: Smilowitz Nathaniel R. , Mohananey Divyanshu , Razzouk Louai , Weisz Giora , Slater James N.
Published: July 2018

Background

Intravascular imaging with intravascular ultrasound (IVUS) and optical coherence tomography (OCT) is an important adjunct to invasive coronary angiography.

Objectives

The primary objective was to examine the frequency of intravascular coronary imaging, trends in imaging use, and outcomes of patients undergoing angiography and/or percutaneous coronary intervention (PCI) in the United States.

Methods

Adult patients ≥18 years of age undergoing in‐hospital cardiac catheterization from January 2004 to December 2014 were identified from the National Inpatient Sample (NIS). International Classification of Diseases, Ninth Revision (ICD‐9) diagnosis and procedure codes were used to identify IVUS and OCT use during diagnostic angiography and PCI.

Results

Among 3,211,872 hospitalizations with coronary angiography, intracoronary imaging was performed in 88,775 cases (4.8% of PCI and 1.0% of diagnostic procedures), with IVUS in 98.9% and OCT in 1.1% of cases. Among patients undergoing PCI, the rate of intravascular coronary imaging increased from 2.1% in 2004–2005 to 6.6% in 2013–2014 (P < 0.001 for trend). Use of intravascular coronary imaging was associated with lower in‐hospital mortality in patients undergoing PCI (adjusted OR 0.77; 95% CI 0.71–0.83). There was marked variability in intravascular imaging by hospital, with 63% and 13% of facilities using intravascular imaging in <5% and >15% of PCIs, respectively.

Conclusions

In a large administrative database from the United States, intravascular imaging use was low, increased over time, and imaging was associated with reduced in‐hospital mortality. Substantial variation in the frequency of intravascular imaging by hospital was observed. Additional investigation to determine clinical benefits of IVUS and OCT are warranted.
Early collapse causing stenosis in a resorbable magnesium scaffold
Authors: Marynissen Thomas , McCutcheon Keir , Bennett Johan
Published: July 2018

We report a case of early in‐stent restenosis due to collapse of a Magmaris resorbable magnesium scaffold.
Initial clinical experience with the FlexPoint Steerable Transseptal Needle in left‐sided structural heart procedures
Authors: Rogers Jason H. , Stripe Benjamin R. , Singh Gagan D. , Boyd Walter D. , Fan Dali , Smith Thomas W.R.
Published: July 2018

Objectives

The purpose of this study is to describe the initial clinical experience with a steerable transseptal needle (STSN) for left‐sided structural heart procedures.

Background

Targeted transseptal (TS) puncture is required for many structural heart procedures, and the use of a steerable needle has not previously been described.

Methods

Consecutive patients undergoing structural heart interventions with targeted TS puncture under transesophageal echocardiographic (TEE) and fluoroscopic guidance were studied. The STSN was used in all patients with a standard commercial TS sheath. Deflection of the needle was performed “real time” to achieve localization of the TS puncture site.

Results

Twenty‐seven patients underwent STSN puncture of the interatrial septum. In all cases, the needle could be deflected in vivo to achieve optimal tenting and localization of the puncture site without having to remove or reshape the needle. The needle was deflected to match a wide range of right atrial diameters (width 4.3 ± 0.9 cm and length 6.0 ± 0.9 cm in the 4‐chamber view). In two patients with prior mitral valve surgery and a fibrotic septum, assisted crossing was achieved using the piercing stylet in one patient, and Bovie energy in the other. There were no procedural complications, and all patients had successful completion of the intended structural heart procedure.

Conclusions

The STSN needle can be used to target the intended puncture location on the interatrial septum with real‐time adjustable deflection without the need to remove and reshape the needle. In all cases crossing was successful and there were no complications.
Enzymatic Synthesis of Therapeutic Nucleosides using a Highly Versatile Purine Nucleoside 2’‐DeoxyribosylTransferase from Trypanosoma brucei
Authors: Pérez Elena , Sánchez‐Murcia Pedro A. , Jordaan Justin , Blanco María Dolores , Mancheño José Miguel , Gago Federico , Fernández‐Lucas Jesús
Published: July 2018

The use of enzymes for the synthesis of nucleoside analogues offers several advantages over multistep chemical methods, including chemo‐, regio‐ and stereoselectivity as well as milder reaction conditions. Herein, the production, characterization and utilization of a purine nucleoside 2’‐deoxyribosyltransferase (PDT) from Trypanosoma brucei are reported. TbPDT is a dimer which displays not only excellent activity and stability over a broad range of temperatures (50–70 °C), pH (4–7) and ionic strength (0–500 mM NaCl) but also an unusual high stability under alkaline conditions (pH 8–10). TbPDT is shown to be proficient in the biosynthesis of numerous therapeutic nucleosides, including didanosine, vidarabine, cladribine, fludarabine and nelarabine. The structure‐guided replacement of Val11 with either Ala or Ser resulted in variants with 2.8‐fold greater activity. TbPDT was also covalently immobilized on glutaraldehyde‐activated magnetic microspheres. MTbPDT3 was selected as the best derivative (4200 IU/g, activity recovery of 22 %), and could be easily recaptured and recycled for >25 reactions with negligible loss of activity. Finally, MTbPDT3 was successfully employed in the expedient synthesis of several nucleoside analogues. Taken together, our results support the notion that TbPDT has good potential as an industrial biocatalyst for the synthesis of a wide range of therapeutic nucleosides through an efficient and environmentally friendly methodology.
Hydroaminocarbonylation of Alkynes to Produce Primary α,β‐Unsaturated Amides Using NH4HCO3 Dually as Ammonia Surrogate and Brønsted Acid Additive
Authors: Wang Dong‐Liang , Guo Wen‐Di , Zhou Qing , Liu Lei , Lu Yong , Liu Ye
Published: July 2018

By using NH4HCO3 dually as ammonia surrogate and Brønsted acid additive, the production of primary α,β‐unsaturated amides via hydroaminocarbonylation of alkynes was accomplished efficiently. The advantages of using the solid and inexpensive NH4HCO3 included: (1) the facile and clean manipulation without presence of stinky gaseous NH3 or liquids organic amines, (2) the inhibition of the subsequent dehydration and hydrolysis of amides due to its weak basicity, and (3) the facilitated formation of Pd−H catalytic active species by the released H2CO3 serving as a weak Brønsted acid additive. In addition, the diphopshine of Dppp with the natural bite angle (βn) of 91° was found indispensable to spur the performance of the palladium catalyst for this reaction. Both terminal and internal phenylacetylene derivatives could be used as the substrates, affording the corresponding primary α,β‐unsaturated amides in good yields along with excellent regio‐selectivities to the branched ones.
Probing Nitrogen‐Doping Effects in the Core‐Shell Structured Catalysts for Bifunctional Electrocatalysis.
Authors: Li Qianru , Wan Gang , Zhao Wanpeng , Yang Ce , Peng Chunlei , Duan Zhengli , Chen Hangrong
Published: July 2018

The design of core‐shell structured catalysts has attracted wide interests due to their remarkable catalytic performances in many fields. Although the nitrogen doping is often integrated in such kind of catalysts, the main contribution is exclusively attributed to the metal sites or the core‐shell configuration. The role of nitrogen doping is often believed to be less important, which remains largely unexplored. Here, in an effort to probe the catalytic role of heterogeneous doping in such core‐shell structure, the effect of nitrogen doping on the activation of cobalt and iron carbide‐based materials for the electrocatalytic reduction of oxygen and the hydrogen evolution reaction is originally revealed. The nitrogen doping in the core‐shell structured biphasic interfaces is found to be of critical importance for triggering the electrocatalytic activity and selectivity. Therefore, this study shows the neglected but critical role of nitrogen doping and biphasic interactions in a core‐shell configuration, paving a new pathway towards the performance enhancement.
Temperature Effects on Concentration Polarization Thickness in Thin‐Film Composite Reverse Osmosis Membranes
Authors: Baghdadi Yasmine N. , Alnouri Sabla Y. , Matsuura Takeshi , Tarboush Belal J. Abu
Published: July 2018

Continuous research and development of reverse osmosis (RO) technologies has led to the production of membranes that are very effective with high salt rejection abilities. As temperature is one of the factors that affects salt rejection capabilities in membranes, this paper investigates the effect of temperature on the thickness of the concentration polarization layer (CPL) deposited on thin‐film composite seawater RO membranes. Two types of membranes were studied: those with ex situ macromolecules and those with in situ macromolecules. FilmTec's reverse osmosis system analysis design software was used to predict the variation of salt rejection and permeate flow rate with temperature. The impact of these variations on the thickness of the CPL was analyzed for different polyamide concentrations in the membrane.
Spatially Resolved Characterization of the Gas Propagator in Monolithic Structured Catalysts Using NMR Diffusiometry
Authors: Mirdrikvand Mojtaba , Ilsemann Jan , Thöming Jorg , Dreher Wolfgang
Published: July 2018

Gas diffusivity measurements in opaque porous media were performed using nuclear magnetic resonance. An optimized pulsed‐field gradient stimulated echo method with free volume selection was used to investigate the propagator of thermally polarized methane gas within commercial monolithic catalyst supports. Since signal losses due to T2 relaxation were minimized by using a short echo time, diffusion processes could be characterized by the measured propagator functions and effective diffusion coefficients were determined for a broad range of observation times and in different spatial directions. The study of this noninvasive characterization of gas diffusion found a clear effect of the monolith type and its pore size and coating on the effective gas diffusion coefficient and the apparent tortuosity for a given observation time.
Synthesis and Characterization of Self‐Assembled Chiral FeII2L3 Cages
Authors: Sun Bin , Nurttila Sandra S. , Reek Joost N. H.
Published: July 2018

We present here the synthesis of chiral BINOL‐derived (BINOL=1,1′‐bi‐2‐naphthol) bisamine and bispyridine‐aldehyde building blocks that can be used for the self‐assembly of novel chiral FeII2L3 cages when mixed with an iron(II) precursor. The properties of a series of chiral cages were studied by NMR and circular dichroism (CD) spectroscopy, cold‐spray ionization MS, and molecular modeling. Upon formation of the M2L3 cages, the iron corners can adopt various isomeric forms: mer, fac‐Δ, or fac‐Λ. We found that the coordination geometry around the metal centers in R‐Cages 1 and 2 were influenced by the chiral BINOL backbone only to a limited extent, as a mixture of cages was formed with fac and mer configurations at the iron corners. However, single cage species (fac‐RR‐Cage and fac‐RS‐Cage) that are enantiopure and highly symmetric were obtained by generating these chiral M2L3 cages by using the bispyridine‐aldehyde building blocks in combination with chiral amine moieties to form pyridylimine ligands for coordination to iron. Next to consistent NMR spectra, the CD spectra confirm the configurations fac‐(Λ,Λ) and fac‐(Δ,Δ) corresponding to RR‐ and RS‐Cage, respectively.
Synthesis of Lipid‐Carbohydrate‐Peptidyl‐RNA Conjugates to Explore the Limits Imposed by the Substrate Specificity of Cell Wall Enzymes on the Acquisition of Drug Resistance
Authors: Fonvielle Matthieu , Bouhss Ahmed , Hoareau Coralie , Patin Delphine , Mengin‐Lecreulx Dominique , Iannazzo Laura , Sakkas Nicolas , El Sagheer Affaf , Brown Tom , Ethève‐Quelquejeu Mélanie , Arthur Michel
Published: July 2018

Conjugation of RNA with multiple partners to obtain mimics of complex biomolecules is limited by the identification of orthogonal reactions. Here, lipid‐carbohydrate‐peptidyl‐RNA conjugates were obtained by post‐functionalization reactions, solid‐phase synthesis, and enzymatic steps, to generate molecules mimicking the substrates of FmhB, an essential peptidoglycan synthesis enzyme of Staphylococcus aureus. Mimics of Gly‐tRNAGly and lipid intermediate II (undecaprenyl‐diphospho‐disaccharide‐pentapeptide) were combined in a single “bi‐substrate” inhibitor (IC50=56 nm). The synthetic route was exploited to generate substrates and inhibitors containing d‐lactate residue (d‐Lac) instead of d‐Ala at the C‐terminus of the pentapeptide stem, a modification responsible for vancomycin resistance in the enterococci. The substitution impaired recognition of peptidoglycan precursors by FmhB. The associated fitness cost may account for limited dissemination of vancomycin resistance genes in S. aureus.
Mechanochromic Switching between Delayed Fluorescence and Phosphorescence of Luminescent Coordination Polymers Composed of Dinuclear Copper(I) Iodide Rhombic Cores
Authors: Kobayashi Atsushi , Yoshida Yuya , Yoshida Masaki , Kato Masako
Published: July 2018

The synthesis and photophysical properties of two luminescent CuI coordination polymers, [Cu2I2(PPh3)2(3‐tpyb)]n and [Cu2I2(PPh3)2(4‐tpyb)]n (Cu‐3‐tpyb and Cu‐4‐tpyb; PPh3=triphenylphosphine, m‐tpyb=1,3,5‐tris(m‐pyridyl)benzene (m=3, 4)), are described. X‐ray structural analysis indicated that one‐dimensional coordination chains comprising rhombic {Cu2I2(PPh3)2} cores and m‐tpyb bridging ligands were formed. Both Cu‐3‐tpyb and Cu‐4‐tpyb exhibited blue‐to‐yellow thermally activated delayed fluorescence (TADF) that originated from mixing of the metal‐to‐ligand and halide‐to‐ligand charge‐transfer excited states and moderate emission quantum yields of 0.29 and 0.27, respectively, at 298 K. Further, mechanochromic luminescence was observed for both complexes. The emission lifetimes indicated that the origin of emission switched from TADF to phosphorescence, which was derived from the triplet cluster‐centered (3CC) emissive state generated by grinding‐induced amorphization.
Fluorooxoborates: Ushering in a New Era of Deep Ultraviolet Nonlinear Optical Materials
Authors: Han Guopeng , Wang Ying , Zhang Bingbing , Pan Shilie
Published: July 2018

Borates are one of the most important classes of functional materials, and several hundreds of artificial borates have been synthesized. The substitution of oxygen by fluorine leads to manifold classes of borates. Fluorooxoborates (also known as fluoroborates), in which the F atoms covalently connect with the B atoms, show additional compositional and structural diversity compared to classic borates. Recently, owing to the large polarizability anisotropy, large HOMO–LUMO gaps, and high hyperpolarizability of the oxyfluoride BOxF4−x building blocks, fluorooxoborates have received unprecedented attention in the search for new ultraviolet (UV) and deep‐UV (DUV) nonlinear optical (NLO) materials. Specifically, some compounds have excellent NLO properties that are comparable or superior to KBe2BO3F2, which is the only usable crystal that generates coherent light below 200 nm through a direct second harmonic generation (SHG) process. This Minireview illustrates recent progress on the synthesis, crystal structures, structure‐properties relationships and applications of fluorooxoborates. This paper concludes by highlighting the outstanding opportunities offered by NLO fluorooxoborate crystals as an innovative avenue for DUV all solid‐state coherent light generation.
Isolated Collagen Mimetic Peptide Assemblies Have Stable Triple‐Helix Structures
Authors: Lalande Mathieu , Comby‐Zerbino Clothilde , Bouakil Mathilde , Dugourd Philippe , Chirot Fabien , Poully Jean‐Christophe
Published: July 2018

The origin of the triple‐helix structure and high stability of collagen has been debated for many years. As models of the triple helix and building blocks for new biomaterials, collagen mimetic peptide (CMP) assemblies have been deeply studied in the condensed phase. In particular, it was found that hydroxylation of proline, an abundant post‐translational modification in collagen, increases its stability. Two main hypotheses emerged to account for this behavior: 1) intra‐helix stereoelectronic effects, and 2) the role of water molecules H‐bound to hydroxyproline side‐chains. However, in condensed‐phase investigations, the influence of water cannot be fully removed. Therefore, we employed a combination of tandem ion mobility and mass spectrometries to assess the structure and stability of CMP assemblies in the gas phase. These results show a conservation of the structure and stability properties of triple helix models in the absence of solvent, supporting an important role of stereoelectronic effects. Moreover, evidence that small triple helix assemblies with controlled stoichiometry can be studied in the gas phase is given, which opens new perspectives in the understanding of the first steps of collagen fiber growth.
Extremely Long Lived Localized Singlet Diradicals in a Macrocyclic Structure: A Case Study on the Stretch Effect
Authors: Harada Yuta , Wang Zhe , Kumashiro Shunsuke , Hatano Sayaka , Abe Manabu
Published: July 2018

Localized singlet diradicals have attracted much attention, not only in the field of bond‐homolysis chemistry, but also in nonlinear optical materials. In this study, an extremely long lived localized singlet diradical was obtained by using a new molecular design strategy in which it is kinetically stabilized by means of a macrocycle that increases the molecular strain of the corresponding σ‐bonded compound. Notably, the lifetime of this diradical (14 μs) is two orders of magnitude longer than that of a standard singlet diradical without a macrocyclic structure (≈0.2 μs) at 293 K. The species is persistent below a temperature of 100 K. In addition to the kinetic stabilization of the singlet diradical, the spontaneous oxidation of its corresponding ring‐closed compound at 298 K produced oxygenated products under atmospheric conditions. Apparently, the “stretch effect” induced by the macrocyclic structure plays a crucial role in extending the lifetime of localized singlet diradicals and increasing the reactivity of their corresponding σ‐bonded compounds.
Alkyl Radical Generation by an Intramolecular Homolytic Substitution Reaction between Iron(II) and Trialkylsulfonium Groups
Authors: Jungen Stefan , Chen Peter
Published: July 2018

Invited for the cover of this issue are Peter Chen and Stefan Jungen at the Eidgenössische Technische Hochschule (ETH) in Zürich. The image depicts a table‐top firework with the tip of an ion guide used in mass spectrometers that spits out the products of a homolitic substitution reaction between iron(II) and trialkylsulfonium species. Read the full text of the article at 10.1002/chem.201801952.
A Visible‐Light‐Induced Strategy To Construct Osmanaphthalynes, Osmaanthracyne, and Osmaphenanthryne
Authors: Zhang Ming‐Xing , Xu Zhiqiang , Lu Tao , Yin Jun , Liu Sheng Hua
Published: July 2018

Herein, we describe a novel, green, and efficient synthesis of a series of different substituted osmanaphthalynes (including ‐H, ‐Br, ‐I, ‐CH3 and ‐CF3) and the first examples of the preparation of α‐osmaanthracyne and α‐osmaphenanthryne by means of a visible light‐induced intramolecular cyclization reaction of their corresponding osmium hydrido alkenylcarbyne complexes. This visible‐light‐driven method provides an efficient and straightforward approach to afford the desired fused metal heterocyclic complexes constructed with an Os atom as the metal center in high yield under mild conditions.
Decarboxylative Organocatalytic Allylic Amination of Morita–Baylis–Hillman Carbamates
Authors: Dočekal Vojtěch , Šimek Michal , Dračínský Martin , Veselý Jan
Published: July 2018

The present study reports the organocatalytic enantioselective allylic amination of Morita–Baylis–Hillman carbamates efficiently catalyzed by a chiral amine in the presence of a Brønsted acid. Chiral allylic amines were produced in high yields (up to 98 %) and enantioselectivities (up to 97 % ee). This method provides an efficient and easily performed route to prepare α‐methylene‐β‐lactams, and other optically active β‐lactams, such as the cholesterol‐lowering drug Ezetimibe.
Self‐Assembled Supramolecular Nanoparticles for Targeted Delivery and Combination Chemotherapy
Authors: Li Bingjie , Feng Zhenzhen , He Leiliang , Li Wenshan , Wang Qing , Liu Jianbo , Huang Jin , Zheng Yan , Ma Yanyun , Yang Xiaohai , Wang Kemin
Published: July 2018

It is challenging but imperative to merge imaging agents and small molecule therapeutics into one nanoentity for diagnosis and treatment. Herein, we constructed polymeric nanoparticles for targeted delivery and combination chemotherapy, which formed through host–guest interactions among three elements: 1) β‐cyclodextrin polymer (poly‐β‐CD), as the backbone of nanoparticles; 2) two antitumor drugs—doxorubicin (DOX) and docetaxel (DTX); and 3) aptamers labeled with adamantane and fluorescein (Ad‐aptamer‐FAM), as recognition elements. First, polymeric nanoparticles, termed self‐assembled supramolecular nanoparticles (SSNPs), were formulated by combining hydrophobic DTX and DOX with poly‐β‐CD via host–guest interactions. Then, the surface of SSNPs modified the aptamer to acquire targeting ability; such nanoparticles were termed targeted self‐assembled supramolecular nanoparticles (T‐SSNPs). As evidenced by MTS assay data, T‐SSNPs exhibited significant selective cytotoxicity toward target cells. The results also indicated that combination drugs achieved a good synergistic effect with a combination index of 0.43. Thus, an effective and simple drug delivery system was constructed for targeted delivery and combination chemotherapy.
Emotionally aligned: Preliminary results on the effects of a mindfulness‐based intervention for depression on congruence between implicit and explicit mood
Authors: Remmers Carina , Zimmermann Johannes , Buxton Alice , Unger Hans‐Peter , Koole Sander L. , Knaevelsrud Christine , Michalak Johannes
Published: July 2018

Background

Mindfulness‐based interventions (MBIs) are effective in treating major depression. Because mindfulness involves monitoring and accepting current experiences, it may lead people resolve incongruencies between emotional responses that would otherwise remain unnoticed. Mindfulness may thus foster congruence between implicit and explicit emotions. The current randomized controlled trial tested this notion.

Methods

N = 39 patients with an acute depressive episode were randomly assigned to an 8‐week MBI (n = 24) or a psychopharmacological consultation condition (n = 15). Explicit and implicit mood and depressive symptoms were assessed before treatment and at the end of treatment.

Results

Compared with the control condition, patients receiving MBI demonstrated higher congruence between implicit and explicit negative mood after treatment. There was no such difference in congruence of implicit and explicit positive mood. Additional analyses showed that only within the MBI group, individual differences in explicit mood became less stable. In contrast, individual differences in implicit mood remained stable in both groups.

Limitations

There was no control group including an active psychological intervention, the sample was small, and emotional congruence was not assessed within persons.

Conclusions

These findings correspond with the idea that mindfulness reduces incongruencies between implicit and explicit emotional responses. We found preliminary evidence for this effect for negative emotional responses. There was suggestive evidence that congruence arose from the alignment of explicit responses (which became less stable) to implicit responses (which remained stable). Studying the interplay between implicit and explicit processes may shed light on the working mechanisms of clinical‐psychological interventions.
Sequential Preparation of Dual‐Layer Fluorine‐Doped Tin Oxide Films for Highly Efficient Perovskite Solar Cells
Authors: Lee Kun‐Mu , Hou Min‐Yao , Suryanarayanan Vembu , Wu Ming‐Chung
Published: July 2018

A dual‐layer fluorine‐doped tin oxide (FTO) film has been fabricated by means of sequential spray pyrolysis for high‐efficiency perovskite solar cells (PSCs). The H‐FTO/L‐FTO dual layer film consists of a H‐FTO layer prepared at high deposition temperature (≈450 °C) and a L‐FTO layer, fabricated at low deposition temperature (≈150 °C), which is used to replace the traditional compact TiO2/FTO layer. The effects of F/Sn molar ratio, precursor solution concentration, and deposition temperature on the electrical, optical, surface morphological, and grain structural characteristics of H‐FTO layers have been studied systematically. With an increase in precursor solution concentration, the mobility and carrier concentration of H‐FTO increases; however, the grain size and sheet resistance decreases as the precursor solution concentration increases. A high deposition temperature results in a large grain size and enhanced haze value. The L‐FTO layer expresses compact layer growth, inconsistent with the H‐FTO surface structure, and possesses excellent electron collection and transport efficiency. The effect of the hole‐blocking characteristics of L‐FTO on the PSC performance is studied. This study provides a novel dual‐layer FTO film to replace the traditional compact TiO2/FTO layer, which is usually prepared by coating TiO2 precursor on FTO following calcination at 450 °C. The H‐FTO/L‐FTO dual‐layer film can simplify the fabrication process and maintain a high power conversion efficiency (PCE); this results in more efficient electron transportation and blocking of holes. The champion device of PSCs with H‐FTO/L‐FTO shows the highest PCE of 17.37 % under the illumination of 100 mW cm−2 (AM1.5G).
The Phosphodiesterase 9 Inhibitor PF‐04449613 Promotes Dendritic Spine Formation and Performance Improvement after Motor Learning
Authors: Lai Baoling , Li Miao , Hu Wanling , Li Wei , Gan Wen‐Biao
Published: July 2018

The cyclic nucleotide cGMP is an intracellular second messenger with important roles in neuronal functions and animals' behaviors. The phosphodiesterases (PDEs) are a family of enzymes that hydrolyze the second messengers cGMP and cAMP. Inhibition of phosphodiesterase 9 (PDE9), a main isoform of PDEs hydrolyzing cGMP, has been shown to improve learning and memory as well as cognitive function in rodents. However, the role of PDE9 in regulating neuronal structure and function in vivo remains unclear. Here we used in vivo two‐photon microscopy to investigate the effect of a selective PDE9 inhibitor PF‐04449613 on the activity and plasticity of dendritic spines of layer V pyramidal neurons in the mouse primary motor cortex. We found that administration of PF‐04449613 increased calcium activity of dendrites and dendritic spines of layer V pyramidal neurons in mice under resting and running conditions. Chronic treatment of PF‐04449613 over weeks increased dendritic spine formation and elimination under basal conditions. Furthermore, PF‐04449613 treatment over 1–7 days increased the formation and survival of new spines as well as performance improvement after rotarod motor training. Taken together, our studies suggest that elevating the level of cGMP with the PDE9 inhibitor PF‐04449613 increases synaptic calcium activity and learning‐dependent synaptic plasticity, thereby contributing to performance improvement after learning. © 2018 Wiley Periodicals, Inc. Develop Neurobiol 00: 000–000, 2018
The Molecular Interplay between Axon Degeneration and Regeneration
Authors: Girouard Marie‐Pier , Bueno Mardja , Julian Victoria , Drake Sienna , Byrne Alexandra B. , Fournier Alyson E.
Published: July 2018

Neurons face a series of morphological and molecular changes following trauma and in the progression of neurodegenerative disease. In neurons capable of mounting a spontaneous regenerative response, including invertebrate neurons and mammalian neurons of the peripheral nervous system (PNS), axons regenerate from the proximal side of the injury and degenerate on the distal side. Studies of Wallerian degeneration slow (WldS/Ola) mice have revealed that a level of coordination between the processes of axon regeneration and degeneration occurs during successful repair. Here, we explore how shared cellular and molecular pathways that regulate both axon regeneration and degeneration coordinate the two distinct outcomes in the proximal and distal axon segments. © 2018 Wiley Periodicals, Inc. Develop Neurobiol 00: 000–000, 2018
Asymmetric Synthesis of Diastereo‐ and Enantiopure Bioxahelicene 2,2′‐Bipyridines
Authors: Klívar Jiří , Šámal Michal , Jančařík Andrej , Vacek Jaroslav , Bednárová Lucie , Buděšínský Miloš , Fiedler Pavel , Starý Ivo , Stará Irena G.
Published: July 2018

A versatile asymmetric synthesis of five C2 symmetric enantio‐ and diastereopure bioxa[5]‐ and bioxa[6]helicene 2,2′‐bipyridines was developed. It relied either on a double intramolecular [2+2+2] cycloisomerization of dicyanotetrayne (forming simultaneously the 2,2′‐bipyridine unit and biazaoxahelicene backbone) or one‐pot/sequential intramolecular [2+2+2] cycloisomerization of triyne accompanied by an intermolecular haloazaoxahelicene reductive homocoupling. We reached an effective central‐to‐helical‐to‐axial chirality transfer that was controlled by the 1,3‐allylic‐type strain and sterically constricted atropoisomerization of the embedded 2,2′‐bipyridine unit. The chiroptical properties of the bioxahelicene 2,2′‐bipyridines were studied along with their fluorescence properties.
Hierarchically Assembled Two‐dimensional Hybrid Nanointerfaces: A Platform for Bioelectronic Applications
Authors: Kumari Renu , Osikoya Adeniyi Olugbenga , Anku William Wilson , Shukla Sudheesh Kumar , Govender Penny Poomani
Published: July 2018

We introduce a hybrid two‐dimensional nanointerface structure for bioelectronic systems. We fabricated smart hierarchically self‐assembled 2D electrobiocatalytic interface system based on the combination of gold nanoparticles doped graphene oxide (GO)‐molybdenum disulfide (MoS2) layered nanohybrid, conjugated with poly (N‐isopropylacrylamide, PNIPAAm) resulting in GO/AuNPs/MoS2/PNIPAAm interface. Horseradish peroxidase (HRP) was subsequently immobilized on the GO/AuNPs/MoS2/PNIPAAm interface through electrostatic interactions giving GO/AuNPs/MoS2/PNIPAAm/Peroxidase electrobiocatalytic interface system as a platform for electrobiocatalysis reactions for biosensing and bioelectronic applications. The electrobiocatalytic activity of the nanohybrid interface structure was studied using hydrogen peroxide (H2O2) as a model analyte. Cyclic Voltammetry showed diffusion controlled electron transfer properties at the interface. The fabricated bioelectrode exhibits a wide linear response to the detection of H2O2 from 1.57 to 11.33 mM, with a detection limit of 3.34 mM (S/N=3) and a capacitance of 8.6 F/cm2.
Multiphase periodic pressure difference boundary condition enhanced by a proportional‐integral‐derivative controller for the lattice Boltzmann method
Authors: Leclaire Sébastien , Latt Jonas , Vidal David , Bertrand François
Published: July 2018

A new pressure difference boundary condition between a pair of inlet and outlet boundaries in an immiscible multiphase periodic flow is introduced. This boundary condition is globally mass conservative and makes use of a simple proportional‐integral‐derivative controller to accurately control the pressure difference. For a droplet/bubble that crosses the outlet to reenter at the inlet of a periodic slit flow, the stability and accuracy of the boundary condition are numerically studied for a wide range of flow conditions. A visualization of a droplet crossing the outlet boundary provides qualitative evidence that the boundary condition works effectively. More importantly, quantitative results also confirm that the targeted average pressure difference is adequately set and that the total momentum in the pressure drop direction is nearly constant (which is what is expected from a perfect multiphase periodic pressure difference boundary condition). This new type of multiphase boundary condition is expected to open up new avenues to simulate complex interfacial multiphase systems using the lattice Boltzmann method.
An improved penalty immersed boundary method for multiphase flow simulation
Authors: Huang Wei‐Xi , Guo Wei
Published: July 2018

An improved version of the penalty immersed boundary method is proposed for simulating multiphase flows with nonuniform density and moving interface. The background fluid with a uniform density is solved on the fixed Eulerian grid, while the excessive mass is modelled by the Lagrangian points. Both the positive and negative density differences are taken into account, and the surface tension is included in the formulation. For validation of the present method, the Rayleigh‐Taylor instability problem and deformation of a droplet in a simple shear flow are computed. The numerical results are compared with the previous studies and the spatial accuracy is between the first and second order. Convergence of the computational results as the penalty coefficient increases is obtained. Furthermore, interaction of the fluid‐fluid interface with the rigid surface is also considered. To improve the numerical stability, the reinitialization operation is introduced to guarantee the quality of the Lagrangian mesh. As a demonstrating example, a droplet bypassing an obstacle in a channel flow is tested.
Impact of falls on depressive symptoms among the oldest old: Results from the AgeQualiDe study
Authors: Hajek André , Brettschneider Christian , van den Bussche Hendrik , Lühmann Dagmar , Oey Anke , Wiese Birgitt , Weyerer Siegfried , Werle Jochen , Fuchs Angela , Pentzek Michael , Stein Janine , Luck Tobias , Bickel Horst , Mösch Edelgard , Heser Kathrin , Wagner Michael , Scherer Martin , Maier Wolfgang , Riedel‐Heller Steffi G. , König Hans‐Helmut ,   for the AgeCoDe & AgeQualiDe Study Groups
Published: July 2018

Objective

The purpose of this study was to examine the impact of falls on depressive symptoms among the oldest old in Germany longitudinally.

Methods

Data were used from 2 waves of the multicenter prospective cohort “Study on needs, health service use, costs and health‐related quality of life in a large sample of oldest‐old primary care patients (85+)” (AgeQualiDe). This study covers primary care patients ≥85 years (at baseline: n = 547, average age of 88.9 ± 3.0 years; ranging from 85 to 100 years). General practitioner‐diagnosed falls were used as explanatory variable. The Geriatric Depression Scale was used as outcome measure.

Results

Linear fixed effects regressions showed that the occurrence of falls is associated with an increase in depressive symptoms (β = .60,P = .02), whereas changes in marital status, ageing, social support, functional decline (instrumental activity of daily living), cognitive impairment, and an increase in chronic diseases did not affect depressive symptoms. In sensitivity analysis, an increase in depressive symptoms was associated with functional impairment (basic activities of daily living; Barthel index;β = −.04,P = .005).

Conclusions

Based on a large, population‐based longitudinal study, this study underlined the impact of falls on depressive symptoms and consequently extended previous knowledge about an association between falls and depressive symptoms in the oldest old. Developing strategies to prevent falls might also help to prevent depressive symptoms.