bluuebunny/crossref_metadata_2025 huggingface dataset:
Experience with Integrating Diagnostic Decision Support Software with Electronic
Health Records: Benefits versus Risks of Information Sharing
Authors: Segal Michael M. , Rahm Alanna K. , Hulse Nathan C. , Wood Grant , Williams Janet L. , Feldman Lynn , Moore Gregory J. , Gehrum David , Yefko Michelle , Mayernick Steven , Gildersleeve Roger , Sunderland Margie C. , Bleyl Steven B. , Haug Peter , Williams Marc S.
Published: December 2017

Introduction: Reducing misdiagnosis has long been a goal of medical informatics.
Current thinking has focused on achieving this goal by integrating diagnostic decision
support into electronic health records.Methods: A diagnostic decision support system
already in clinical use was integrated into electronic health record systems at two
large health systems, after clinician input on desired capabilities. The decision
support provided three outputs: editable text for use in a clinical note, a summary
including the suggested differential diagnosis with a graphical representation of
probability, and a list of pertinent positive and pertinent negative findings (with
onsets).Results: Structured interviews showed widespread agreement that the tool was
useful and that the integration improved workflow. There was disagreement among various
specialties over the risks versus benefits of documenting intermediate diagnostic
thinking. Benefits were most valued by specialists involved in diagnostic testing, who
were able to use the additional clinical context for richer interpretation of test
results. Risks were most cited by physicians making clinical diagnoses, who expressed
concern that a process that generated diagnostic possibilities exposed them to legal
liability.Discussion and Conclusion: Reconciling the preferences of the various groups
could include saving only the finding list as a patient-wide resource, saving
intermediate diagnostic thinking only temporarily, or adoption of professional
guidelines to clarify the role of decision support in diagnosis.
Health Information Exchange Use (1990-2015): A Systematic Review
Authors: Devine Emily Beth , Totten Annette M. , Gorman Paul , Eden Karen B. , Kassakian Steven , Woods Susan , Daeges Monica , Pappas Miranda , McDonagh Marian , Hersh William R.
Published: December 2017

Background: In June 2014, the Office of the National Coordinator for Health
Information Technology published a 10-year roadmap for the United States to achieve
interoperability of electronic health records (EHR) by 2024. A key component of this
strategy is the promotion of nationwide health information exchange (HIE). The 2009
Health Information Technology for Economic and Clinical Health (HITECH) Act provided
significant investments to achieve HIE.Objective: We conducted a systematic literature
review to describe the use of HIE through 2015.Methods: We searched MEDLINE, PsycINFO,
CINAHL, and Cochrane databases (1990 - 2015); reference lists; and tables of contents of
journals not indexed in the databases searched. We extracted data describing study
design, setting, geographic location, characteristics of HIE implementation, analysis,
follow-up, and results. Study quality was dual-rated using pre-specified criteria and
discrepancies resolved through consensus.Results: We identified 58 studies describing
either level of use or primary uses of HIE. These were a mix of surveys, retrospective
database analyses, descriptions of audit logs, and focus groups. Settings ranged from
community-wide to multinational. Results suggest that HIE use has risen substantially
over time, with 82% of non-federal hospitals exchanging information (2015), 38% of
physician practices (2013), and 17-23% of long-term care facilities (2013). Statewide
efforts, originally funded by HITECH, varied widely, with a small number of states
providing the bulk of the data. Characteristics of greater use include the presence of
an EHR, larger practice size, and larger market share of the health-system.Conclusions:
Use of HIE in the United States is growing but is still limited. Opportunities remain
for expansion. Characteristics of successful implementations may provide a path
forward.
Physical activity and breast cancer: Results of a focus group to devise novel exercise interventions for women with breast cancer
Authors: Smith-Turchyn Jenna , Richardson Julie , Tozer Richard , Thabane Lehana , McNeely Margaret
Published: December 2017

Objective: To determine, from the diverse perspective of vested members of the health care team, novel exercise intervention strategies to implement within the cancer care institution in order to overcome barriers to exercise participation and promotion for women with breast cancer (BC).Methods: Design: Qualitative descriptive study. Setting: Cancer care institution. Participants: Health care professionals (HCPs) who work with women with BC. Intervention: A focus group was used to answer the research question. A moderator guided the focus group using a semi-structured script. Measurements: The focus group was recorded and transcribed. The transcript was coded independently using topic and analytical coding.Results: Three main issues came forth during analysis. These included a lack of (1) exercise programming and equipment available within the cancer care institution (2) communication with rehabilitation professionals, and (3) effective exercise education strategies available for patients with BC. Specific strategies were suggested to overcome each issue. Limitations: As purposeful sampling was used for recruitment, it is possible that participants agreed to be in this study because they had positive views on the need to incorporate exercise more effectively into practice.Conclusions: To our knowledge this is the first study to include a multidisciplinary team to come to a consensus on a knowledge translation exercise strategy. Findings show that future exercise interventions should implement active interventions within the cancer institution, include rehabilitation professionals as part of the health care team, and use technology to educate patients.
MOISTURE REMOVAL ASSESSMENT USING DESICCANT LIQUIDS WITH A BUBBLE-AIR GENERATOR
Authors: GALLARDO SALAZAR JUAN MANUEL , ZUBIZARRETA JIMENEZ ROGELIO , HIJANO REYES ANTONIO
Published: December 2017

There are buildings where the latend load is very high and it is required to remove moisture from the air to achieve the confot conditions. The most extended method to reduce humidity are based on cooling coils, this system reduces the amount of water in the air stream through the condensation of water on the coil surface. Another approacch is based on desiccant materials, it aims at improving the process efficiency through the secuestration of water on this material surface. As it is surface phenomenom, as higher is the contact surface between air stream and desiccant, as much water will be removed. Solid desiccant have been broadly used for these applicatiosn, but the use of desiccant liquids is not extended, some of the reasons are related to the reduced contact surface between liquid and air. The evaluated approaches have focused on the application of liquid desiccant film or spray. This paper shows the assessment of an innovative approach based on the genearation of air bubbles into a desiccant liquid bath, this approach aims at improving mass transfer rate. This paper shows the evaluation of the dehumidification capacity of desiccant liquids and the technical feasibility of this technique.
The structural basis for dynamic DNA binding and bridging interactions which condense the bacterial centromere
Authors: Fisher Gemma LM , Pastrana César L , Higman Victoria A , Koh Alan , Taylor James A , Butterer Annika , Craggs Timothy , Sobott Frank , Murray Heath , Crump Matthew P , Moreno-Herrero Fernando , Dillingham Mark S
Published: December 2017

The ParB protein forms DNA bridging interactions around parS to condense DNA and earmark the bacterial chromosome for segregation. The molecular mechanism underlying the formation of these ParB networks is unclear. We show here that while the central DNA binding domain is essential for anchoring at parS, this interaction is not required for DNA condensation. Structural analysis of the C-terminal domain reveals a dimer with a lysine-rich surface that binds DNA non-specifically and is essential for DNA condensation in vitro. Mutation of either the dimerisation or the DNA binding interface eliminates ParB-GFP foci formation in vivo. Moreover, the free C-terminal domain can rapidly decondense ParB networks independently of its ability to bind DNA. Our work reveals a dual role for the C-terminal domain of ParB as both a DNA binding and bridging interface, and highlights the dynamic nature of ParB networks in Bacillus subtilis.
Dynamic modulation of activity in cerebellar nuclei neurons during pavlovian eyeblink conditioning in mice
Authors: ten Brinke Michiel M , Heiney Shane A , Wang Xiaolu , Proietti-Onori Martina , Boele Henk-Jan , Bakermans Jacob , Medina Javier F , Gao Zhenyu , De Zeeuw Chris I
Published: December 2017

While research on the cerebellar cortex is crystallizing our understanding of its function in learning behavior, many questions surrounding its downstream targets remain. Here, we evaluate the dynamics of cerebellar interpositus nucleus (IpN) neurons over the course of Pavlovian eyeblink conditioning. A diverse range of learning-induced neuronal responses was observed, including increases and decreases in activity during the generation of conditioned blinks. Trial-by-trial correlational analysis and optogenetic manipulation demonstrate that facilitation in the IpN drives the eyelid movements. Adaptive facilitatory responses are often preceded by acquired transient inhibition of IpN activity that, based on latency and effect, appear to be driven by complex spikes in cerebellar cortical Purkinje cells. Likewise, during reflexive blinks to periocular stimulation, IpN cells show excitation-suppression patterns that suggest a contribution of climbing fibers and their collaterals. These findings highlight the integrative properties of subcortical neurons at the cerebellar output stage mediating conditioned behavior.
CHILE: SENTENCIA TRIBUNAL CONSTITUCIONAL, ROL 3729-17 RESPECTO DEL PROYECTO DE LEY QUE REGULA LA DESPENALIZACIÓN DE LA INTERRUPCIÓN VOLUNTARIA DEL EMBARAZO EN TRES CAUSALES
Authors:   Pontificia Universidad Católica de Chile
Published: December 2017

Sentencia TC
Robust Free‐Standing Nano‐Thin SiC Membranes Enable Direct Photolithography for MEMS Sensing Applications
Authors: Phan Hoang‐Phuong , Nguyen Tuan‐Khoa , Dinh Toan , Iacopi Alan , Hold Leonie , Shiddiky Muhammad J. A. , Dao Dzung Viet , Nguyen Nam‐Trung
Published: December 2017

This work presents fabrication of micro structures on sub–100 nm SiC membranes with a large aspect ratio up to 1:3200. Unlike conventional processes, this approach starts with Si wet etching to form suspended SiC membranes, followed by micro‐machined processes to pattern free‐standing microstructures such as cantilevers and micro bridges. This technique eliminates the sticking or the under‐etching effects on free‐standing structures, enhancing mechanical performance which is favorable for MEMS applications. In addition, post‐Si‐etching photography also enables the formation of metal electrodes on free standing SiC membranes to develop electrically‐measurable devices. To proof this concept, the authors demonstrate a SiC pressure sensor by applying lithography and plasma etching on released ultrathin SiC films. The sensors exhibit excellent linear response to the applied pressure, as well as good repeatability. The proposed method opens a pathway for the development of self‐sensing free‐standing SiC sensors.
Controlling Spatiotemporal Mechanics of Supramolecular Hydrogel Networks with Highly Branched Cucurbit[8]uril Polyrotaxanes
Authors: Tan Cindy Soo Yun , Liu Ji , Groombridge Alexander S. , Barrow Steven J. , Dreiss Cécile A. , Scherman Oren A.
Published: December 2017

Attempts to rationally tune the macroscopic mechanical performance of supramolecular hydrogel networks through noncovalent molecular interactions have led to a wide variety of supramolecular materials with desirable functions. While the viscoelastic properties are dominated by temporal hierarchy (crosslinking kinetics), direct mechanistic studies on spatiotemporal control of supramolecular hydrogel networks, based on host–guest chemistry, have not yet been established. Here, supramolecular hydrogel networks assembled from highly branched cucurbit[8]uril‐threaded polyrotaxanes (HBP‐CB[8]) and naphthyl‐functionalized hydroxyethyl cellulose (HECNp) are reported, exploiting the CB[8] host–guest complexation. Mechanically locking CB[8] host molecules onto a highly branched hydrophilic polymer backbone, through selective binary complexation with viologen derivatives, dramatically increases the solubility of CB[8]. Additionally, the branched architecture enables tuning of material dynamics of the supramolecular hydrogel networks via both topological (spatial hierarchy) and kinetic (temporal hierarchy) control. Relationship between macroscopic properties (time‐ and temperature‐dependent rheological properties, thermal stability, and reversibility), spatiotemporal hierarchy, and chain dynamics of the highly branched polyrotaxane hydrogel networks is investigated in detail. Such kind of tuning of material mechanics through spatiotemporal hierarchy improves our understanding of the challenging relationship between design of supramolecular polymeric materials and their complex viscoelasticity, and also highlights a facile strategy to engineer dynamic supramolecular materials.
A Rapid Photopatterning Method for Selective Plating of 2D and 3D Microcircuitry on Polyetherimide
Authors: Marques‐Hueso Jose , Jones Thomas D. A. , Watson David E. , Ryspayeva Assel , Esfahani Mohammadreza Nekouie , Shuttleworth Matthew P. , Harris Russell A. , Kay Robert W. , Desmulliez Marc P. Y.
Published: December 2017

In this work, a method for the rapid synthesis of metallic microtracks on polyetherimide is presented. The method relies on the photosynthesis of silver nanoparticles on the surface of the polymer substrates from photosensitive silver chloride (AgCl), which is synthesized directly on the polyetherimide surface. The study reveals that the use of AgCl as a photosensitive intermediate accelerates the reactions leading to the formation of silver nanoparticles by up to two orders of magnitude faster than other photodecomposition schemes. The patterning can be conducted under blue light, with notable advantages over UV exposure. Polymers of significant interest to the microelectronics and 3D printing industries can be directly patterned by light using this photography‐inspired technique at throughputs high enough to be commercially advantageous. Light exposures as short as a few seconds are sufficient to allow the direct metallization of the illuminated polyetherimide surface. The results show that the silver required for the seed layer is minimal, and the later copper electroless plating results in the selective growth of conductive tracks for circuitry on the light‐patterned areas, both on flexible films and 3D printed surfaces.
Superhydrophobic Shape Memory Polymer Arrays with Switchable Isotropic/Anisotropic Wetting
Authors: Cheng Zhongjun , Zhang Dongjie , Lv Tong , Lai Hua , Zhang Enshuang , Kang Hongjun , Wang Yongzhen , Liu Pengchang , Liu Yuyan , Du Yi , Dou Shixue , Jiang Lei
Published: December 2017

Smart surfaces with tunable wettability have aroused much attention in the past few years. However, to obtain a surface that can reversibly transit between the lotus‐leaf‐like superhydrophobic isotropic and rice‐leaf‐like superhydrophobic anisotropic wettings is still a challenge. This paper, by mimicking microstructures on both lotus and rice leaves, reports such a surface that is prepared by creating micro/nanostructured arrays on the shape memory polymer. On the surface, the microstructure shapes can be reversibly changed between the lotus‐leaf‐like random state and the rice‐leaf‐like 1D ordered state. Accordingly, repeated switch between the superhydrophobic isotropic and anisotropic wettings can be displayed. Research results indicate that the smart controllability is ascribed to the excellent shape memory effect of the polymer, which endows the surface with special ability in memorizing different microstructure shapes and wetting properties. Meanwhile, based on the smart wetting performances, the surface is further used as a rewritable functional platform, on which various droplet transportation programmes are designed and demonstrated. This work reports a superhydrophobic surface with switchable isotropic/anisotropic wettings, which not only provides a novel functional material but also opens a new avenue for application in controlled droplet transportation.
NiCo Alloy Nanoparticles Decorated on N‐Doped Carbon Nanofibers as Highly Active and Durable Oxygen Electrocatalyst
Authors: Fu Yue , Yu Hai‐Yang , Jiang Cong , Zhang Tian‐Heng , Zhan Run , Li Xiaowei , Li Jian‐Feng , Tian Jing‐Hua , Yang Ruizhi
Published: December 2017

The exploring of catalysts with high‐efficiency and low‐cost for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the key issues for many renewable energy systems including fuel cells, metal–air batteries, and water splitting. Despite several decades pursuing, bifunctional oxygen catalysts with high catalytic performance at low‐cost, especially the one that could be easily scaled up for mass production are still missing and highly desired. Herein, a hybrid catalyst with NiCo alloy nanoparticles decorated on N‐doped carbon nanofibers is synthesized by a facile electrospinning method and postcalcination treatment. The hybrid catalyst NiCo@N‐C 2 exhibits outstanding ORR and OER catalytic performances, which is even surprisingly superior to the commercial Pt/C and RuO2 catalysts, respectively. The synergetic effects between alloy nanoparticles and the N‐doped carbon fiber are considered as the main contributions for the excellent catalytic activities, which include decreasing the intrinsic and charge transfer resistances, increasing CC, graphitic‐N/pyridinic‐N contents in the hybrid catalyst. This work opens up a new way to fabricate high‐efficient, low‐cost oxygen catalysts with high production.
Tunable Förster Resonance Energy Transfer in Colloidal Nanoparticles Composed of Polycaprolactone‐Tethered Donors and Acceptors: Enhanced Near‐Infrared Emission and Compatibility for In Vitro and In Vivo Bioimaging
Authors: Yang Cangjie , Wang Xiaochen , Huang Shuo , Wang Mingfeng
Published: December 2017

A near‐infrared (NIR) fluorescent donor/acceptor (D/A) nanoplatform based on Förster resonance energy transfer is important for applications such as deep‐tissue bioimaging and sensing. However, previously reported D/A nanoparticles (NPs) often show limitations such as aggregation‐induced fluorescence quenching and poor interfacial compatibility that reduces the efficiency of the energy transfer and also leads to leaching of the small molecular fluorophores from the NP matrix. Here highly NIR‐fluorescent D/A NPs with a fluorescence quantum yield as high as 46% in the NIR region (700–850 nm) and robust optical stability are reported. The hydrophobic core of each NP is composed of donor and acceptor moieties both of which are tethered with polycaprolactone (PCL), while the hydrophilic corona is composed of poly[oligo(ethylene glycol) methyl ether methacrylate] to offer colloidal stability and “stealthy” effect in aqueous media. The PCL matrix in each colloidal NP not only offers biocompatibility and biodegradability but also minimizes the aggregation‐caused fluorescence quenching of D/A chromophores and prevents the leakage of the NIR fluorophores from the NPs. In vivo imaging using these NIR NPs in live mice shows contrast‐enhanced imaging capability and efficient tumor‐targeting through enhanced permeability and retention effect.
Ascidian‐Inspired Fast‐Forming Hydrogel System for Versatile Biomedical Applications: Pyrogallol Chemistry for Dual Modes of Crosslinking Mechanism
Authors: Cho Jung Ho , Lee Jung Seung , Shin Jisoo , Jeon Eun Je , An Soohwan , Choi Yi Sun , Cho Seung‐Woo
Published: December 2017

Exploitation of unique biochemical and biophysical properties of marine organisms has led to the development of functional biomaterials for various biomedical applications. Recently, ascidians have received great attention, owing to their extraordinary properties such as strong underwater adhesion and rapid self‐regeneration. Specific polypeptides containing 3,4,5‐trihydroxyphenylalanine (TOPA) in the blood cells of ascidians are associated with such intrinsic properties generated through complex oxidative processes. In this study, a bioinspired hydrogel platform is developed, demonstrating versatile applicability for tissue engineering and drug delivery, by conjugating pyrogallol (PG) moiety resembling ascidian TOPA to hyaluronic acid (HA). The HA–PG conjugate can be rapidly crosslinked by dual modes of oxidative mechanisms using an oxidant or pH control, resulting in hydrogels with different mechanical and physical characteristics. The versatile utility of HA–PG hydrogels formed via different crosslinking mechanisms is tested for different biomedical platforms, including microparticles for sustained drug delivery and tissue adhesive for noninvasive cell transplantation. With extraordinarily fast and different routes of PG oxidation, ascidian‐inspired HA–PG hydrogel system may provide a promising biomaterial platform for a wide range of biomedical applications.
Nanocrystalline Perovskite Hybrid Photodetectors with High Performance in Almost Every Figure of Merit
Authors: Lin Yuanwei , Lin Guoming , Sun Baoyun , Guo Xuefeng
Published: December 2017

Conversion of photon into electron is a phenomenon of great importance in nature. Photodetectors based on this principle have immense potential applications at the frontiers of both scientific and industrial communities, thus affecting the daily life. Herein, a novel class of high‐quality organic–inorganic trihalide perovskite nanoscale hybrid photodetectors is presented based on carbon electrode−molecule junctions working at mild conditions. Almost every figure of merit with high performance, such as highest responsivity, highest photogain, high detectivity, high linear dynamic range, and a broad spectral response, could be achieved simultaneously in a single device under different biases. These significant achievements benefit from rational choices of novel energy loss‐prevented hybrid perovskite nanocrystals as active materials and optimized carbon electrode−molecule junctions as device architectures, which leads to a hybridization mechanism of photodiodes and photoconductors. These investigations demonstrate a useful photodetector platform that might lead to many future photoelectric conversion applications in the practical way.
Bio‐Inspired Anisotropic Wettability Surfaces from Dynamic Ferrofluid Assembled Templates
Authors: Shang Luoran , Yu Yunru , Gao Wei , Wang Yuetong , Qu Liangliang , Zhao Ze , Chai Renjie , Zhao Yuanjin
Published: December 2017

The biomimetic principle of harnessing topographical structures to determine liquid motion behavior represents a cutting‐edge direction in constructing green transportation systems without external energy input. Here, inspired by natural Nepenthes peristome, a novel anisotropic wettability surface with characteristic structural features of periodically aligned and overlapped arch‐shaped microcavities, formed by employing ferrofluid assemblies as dynamic templates, is presented. The magnetic strength and orientation are precisely adjustable during the generation process, and thus the size and inclination angle of the ferrofluid droplet templates could be tailored to make the surface morphology of the resultant polymer replica achieve a high degree of similarity to the natural peristome. The resultant anisotropic wettability surface enables autonomous unidirectional water transportation in a fast and continuous way. In addition, it could be tailored into arbitrary shapes to induce water flow along a specific curved path. More importantly, based on the anisotropic wettability surface, novel pump‐free microfluidic devices are constructed to implement multiphase flow reactions, which offer a promising solution to building low‐cost, portable platform for lab‐on‐a‐chip applications.
Local Built‐In Electric Field Enabled in Carbon‐Doped Co3O4 Nanocrystals for Superior Lithium‐Ion Storage
Authors: Yan Chunshuang , Zhu Yue , Li Yutao , Fang Zhiwei , Peng Lele , Zhou Xin , Chen Gang , Yu Guihua
Published: December 2017

In this work, a novel concept of introducing a local built‐in electric field to facilitate lithium‐ion transport and storage within interstitial carbon (C‐) doped nanoarchitectured Co3O4 electrodes for greatly improved lithium‐ion storage properties is demonstrated. The imbalanced charge distribution emerging from the C‐dopant can induce a local electric field, to greatly facilitate charge transfer. Via the mechanism of “surface locking” effect and in situ topotactic conversion, unique sub‐10 nm nanocrystal‐assembled Co3O4 hollow nanotubes (HNTs) are formed, exhibiting excellent structural stability. The resulting C‐doped Co3O4 HNT‐based electrodes demonstrate an excellent reversible capacity ≈950 mA h g−1 after 300 cycles at 0.5 A g−1 and superior rate performance with ≈853 mA h g−1 at 10 A g−1.
Efficacy and safety of rituximab for systemic lupus erythematosus‐associated immune cytopenias: A multicenter retrospective cohort study of 71 adults
Authors: Serris Alexandra , Amoura Zahir , Canouï‐Poitrine Florence , Terrier Benjamin , Hachulla Eric , Costedoat‐Chalumeau Nathalie , Papo Thomas , Lambotte Olivier , Saadoun David , Hié Miguel , Blanche Philippe , Lioger Bertrand , Gottenberg Jacques‐Eric , Godeau Bertrand , Michel Marc
Published: December 2017

The aim of the study was to assess the efficacy and safety of rituximab (RTX) for treating systemic lupus erythematosus (SLE)‐associated immune cytopenias. This multicenter retrospective cohort study of adults from French referral centers and networks for adult immune cytopenias and SLE involved patients ≥18 years old with a definite diagnosis of SLE treated with RTX specifically for SLE‐associated immune cytopenia from 2005 to 2015. Response assessment was based on standard definitions. In total, 71 patients, 61 women (85.9%), with median age 36 years [interquartile range 31‐48], were included. The median duration of SLE at the time of the first RTX administration was 6.1 years [2.6‐11.6] and the reason for using RTX was immune thrombocytopenia (ITP) for 44 patients (62.0%), autoimmune hemolytic anemia (AIHA) for 16 (22.5%), Evans syndrome for 10 (14.1%), and pure red cell aplasia for one patient. Before receiving RTX, patients had received a mean of 3.1 ± 1.3 treatments that included corticosteroids (100%), and hydroxychloroquine (88.5%). The overall initial response rate to RTX was 86% (91% with ITP, 87.5% with AIHA, and 60% with Evans syndrome), including 60.5% with complete response. Median follow‐up after the first injection of RTX was 26.4 months [14.3‐71.2]. Among 61 initial responders, relapse occurred in 24 (39.3%); for 18, RTX retreatment was successful in 16 (88.8%). Severe infections occurred after RTX in three patients, with no fatal outcome. No cases of RTX‐induced neutropenia were observed. In conclusion, RTX seems effective and relatively safe for treating SLE‐associated immune cytopenias.
Photochromie jenseits des Sichtbaren: Direkte, im biologischen Fenster addressierbare Einphotonen‐NIR‐Photoschalter
Authors: Klaue Kristin , Garmshausen Yves , Hecht Stefan
Published: December 2017

Der Erfolg der Photopharmakologie ist eng mit der Verfügbarkeit geeigneter Photoschalter verknüpft, die innerhalb des biologischen Fensters (λ=650–1450 nm) adressierbar sind, um eine maximale Eindringtiefe ins Gewebe zu ermöglichen. Mithilfe einer generellen Designstrategie wurde ein Dihydropyren‐Derivat entwickelt, das negative T‐Typ‐Photochromie aufweist und ein effizientes sowie nahezu quantitatives (95 %) Schalten unter Einwirkung von NIR‐Licht mit λ>800 nm ermöglicht. Die thermische Halbwertzeit des entfärbten, offenen meta‐Cyclophandien‐Isomers variiert zwischen Minuten und Stunden je nach Lösungsmittelpolarität und kann als Sonde für die lokale Umgebung wirken. Durch die eher geringen Strukturunterschiede zwischen den beiden Isomeren wären entsprechend modifizierte NIR‐Photoschalter mögliche Kandidaten für das Schalten im aktiven Zentrum eines biologischen Targets und ermöglichen prinzipiell eine reversible, lichtinduzierte Inhibitor‐Deaktivierung als einen alternativen Ansatz zur externen Regulation biologischer Funktionen.
Differentiation of Self: Enhancing Therapist Resilience When Working with Relational Trauma
Authors: MacKay Linda M.
Published: December 2017

Clinicians are charged with being diligent in gaining competency in the latest trauma‐informed interventions when working with relational trauma. This may invest therapists with an overresponsibility that is not only overwhelming and unrealistic, but serves to reduce autonomous functioning in family members. Therefore, clinicians need to become clear about what they are responsible for and what they are not, particularly when family members present as irresponsible or too anxious to think and act more effectively. Using a case vignette, this paper discusses how a clinician's focus on increasing their differentiation of self, a concept embeded in Bowen family systems theory, protects against vicarious traumatisation, secondary traumatic stress, and burnout whilst contributing to more autonomous functioning and better wellbeing outcomes for both clinicians and clients alike.
Development of a validated liquid chromatographic method for quantification of sorafenib tosylate in the presence of stress‐induced degradation products and in biological matrix employing analytical quality by design approach
Authors: Sharma Teenu , Khurana Rajneet Kaur , Jain Atul , Katare O.P. , Singh Bhupinder
Published: December 2017

The current research work envisages an analytical quality by design‐enabled development of a simple, rapid, sensitive, specific, robust and cost‐effective stability‐indicating reversed‐phase high‐performance liquid chromatographic method for determining stress‐induced forced‐degradation products of sorafenib tosylate (SFN). An Ishikawa fishbone diagram was constructed to embark upon analytical target profile and critical analytical attributes, i.e. peak area, theoretical plates, retention time and peak tailing. Factor screening using Taguchi orthogonal arrays and quality risk assessment studies carried out using failure mode effect analysis aided the selection of critical method parameters, i.e. mobile phase ratio and flow rate potentially affecting the chosen critical analytical attributes. Systematic optimization using response surface methodology of the chosen critical method parameters was carried out employing a two‐factor–three‐level–13‐run, face‐centered cubic design. A method operable design region was earmarked providing optimum method performance using numerical and graphical optimization. The optimum method employed a mobile phase composition consisting of acetonitrile and water (containing orthophosphoric acid, pH 4.1) at 65:35 v/v at a flow rate of 0.8 mL/min with UV detection at 265 nm using a C18 column. Response surface methodology validation studies confirmed good efficiency and sensitivity of the developed method for analysis of SFN in mobile phase as well as in human plasma matrix. The forced degradation studies were conducted under different recommended stress conditions as per ICH Q1A (R2). Mass spectroscopy studies showed that SFN degrades in strongly acidic, alkaline and oxidative hydrolytic conditions at elevated temperature, while the drug was per se found to be photostable. Oxidative hydrolysis using 30% H2O2 showed maximum degradation with products at retention times of 3.35, 3.65, 4.20 and 5.67 min. The absence of any significant change in the retention time of SFN and degradation products, formed under different stress conditions, ratified selectivity and specificity of the systematically developed method.
First in human evaluation of the vascular biocompatibility and biomechanical performance of a novel ultra high molecular weight amorphous PLLA bioresorbable scaffold in the absence of anti‐proliferative drugs: Two‐year imaging results in humans
Authors: Moncada Miguel , Delgado Juan A. , Colombo Antonio , Gasior Pawel , Ramzipoor Kamal , Estrada Alex , Lee Chang , Dokko Danny , Granada Juan F.
Published: December 2017

Objectives

In this first‐in‐human study, we prospectively studied the vascular compatibility and mechanical performance of a novel bare ultra‐high molecular weight amorphous PLLA bioresorbable scaffold (BRS, FORTITUDE®, Amaranth Medical, Mountain View, California) up to two years after implantation using multimodality imaging techniques.

Background

The vascular biocompatibility of polymers used in BRS has not been fully characterized in the absence of anti‐proliferative drugs.

Methods

A total of 10 patients undergoing single scaffold implantation were included in the final analysis and were followed up using optical coherence tomography (OCT) at 2‐years. All devices were implanted under angiographic and intravascular ultrasound (IVUS) guidance. Angiographic and IVUS follow up was performed at 6 months. Additionally, angiography and OCT imaging were performed at 2‐years.

Results

At 6 months, mean intra‐scaffold angiographic MLD slightly decreased from baseline procedural values. However, at 2 years, mean angiographic MLD increased (post procedure; 2.9 [2.7, 3.1] mm vs. 6 months; 2.1 [1.6, 2.5] vs. 2 years; 2.4 [2.1, 2.6], P = .001). Also, angiographic percent diameter stenosis decreased and late lumen gain increased between 6 months and 2 years follow up. Mean neointimal hyperplasia volume assessed by IVUS at 6 months was 26% [15.2, 29.3]. At 2 years OCT follow up neointimal hyperplasia volume was 24.2% [19.4, 28.9]. No presence of neoatherosclerosis was identified in any of the analyzed cases.

Conclusion

At 2 years, this novel PLLA‐based BRS induced expansive vascular remodeling from 6 to 24 months, a biological phenomenon that appears to be independent of the presence of anti‐proliferative drugs.
A Self‐Repairing Cathode Material for Lithium–Selenium Batteries: Se−C Chemically Bonded Selenium–Graphene Composite
Authors: Sha Linna , Gao Peng , Ren Xiaochen , Chi Qianqian , Chen Yujin , Yang Piaoping
Published: December 2017

Lithium–selenium batteries, employing selenium as a cathode material, exhibit some notable advantages, such as high discharge rates and good cycling performance, due to their high electrical conductivity, high output voltages, and high volumetric capacity density. However, an important problem, termed the “shuttle effect”, can lead to capacity decay in Li‐Se cells (and in Li‐S cells), which arises from aggregation and the loss of Se or S from the cathode into the electrolyte. In this work, in order to solve this problem, a new self‐repairing system has been devised, in which some Se atoms are chemically bonded to the carbon atoms of graphene and act as reclaiming points for dissociated Se atoms through the establishment of ‐Se‐Se‐Se‐ chains. Se‐decorated graphene (Se‐GE) was first constructed through a facile high‐energy ball‐milling process. Its formation was confirmed by XRD, SEM, HRTEM, XPS, and Raman analyses. As we anticipated, in examining cell properties, the as‐prepared Se‐GE composite underwent an initial capacity decay in the first 20 cycles (from 1050 mAh g−1 to 750 mAh g−1, ca. 29 % loss), but the capacity then reverted to 970 mAh g−1 (ca. 92 % of the initial value). Other measurements were also consistent with the recapture of dissociated Se atoms.
Bis(dioxaborine) Dyes with Variable π‐Bridges: Towards Two‐Photon Absorbing Fluorophores with Very High Brightness
Authors: Marín Á. Moneo , Telo João P. , Collado Daniel , Nájera Francisco , Pérez‐Inestrosa Ezequiel , Pischel Uwe
Published: December 2017

Bis(dioxaborine) dyes of the A‐π‐A format (A: acceptor, π: conjugated bridge) were prepared and photophysically characterized. The best performing dyes feature (a) visible‐light absorption (>400 nm), (b) high molar absorption coefficients (up to 70000 m−1 cm−1), (c) Stokes shifts in the range of ca. 2500–5800 cm−1, and (d) strong fluorescence emission with quantum yields of up to 0.74. This yields very bright‐emitting dyes for one‐photon excitation. However, the most intriguing feature of the dyes is their strong two‐photon absorption. This was achieved by means of increased π‐conjugation in the phenylene or phenylene‐thiophene bridges through the variation of the conjugation length and rigidity. This provided two‐photon absorption cross sections of up to 2800 GM (1 Goeppert‐Mayer (GM)=10−50 cm4 s photon−1). Considering the mentioned high fluorescence quantum yields, exceptionally bright‐emitting A‐π‐A two‐photon absorbing dyes with low molecular mass are obtained. Time‐dependent density‐functional theory calculations corroborated the experimental results.
Synthesis and Dimerization Studies of a Lipophilic Photoresponsive Aryl‐Extended Tetraurea‐Calix[4]pyrrole
Authors: Sekiya Ryo , Díaz‐Moscoso Alejandro , Ballester Pablo
Published: December 2017

We describe the syntheses of the lipophilic aryl‐extended α,α,α,α‐tetraurea‐phenyl‐calix[4]pyrrole 1, featuring four appended azo‐phenyl groups with two tert‐butoxy carbonyl meta‐substituents and its photo‐inactive counterpart 2. In CD2Cl2 solutions, both tetraurea‐calix[4]pyrroles self‐assemble into dimeric capsules by encapsulating one molecule of a suitable bis‐N‐oxide or two molecules of a mono‐N‐oxide. The dimeric capsules are mainly stabilized by a cyclic array of sixteen hydrogen bonds established between the eight unidirectionally oriented urea groups. Photoirradiation experiments demonstrated the trans‐to‐cis isomerization of the azo‐phenyl groups and the formation of a plethora of stereo isomeric cis‐azo‐enriched capsular assemblies. The highly cis‐azo enriched capsular assemblies seem to show a reduced stability and their involvement in equilibria with non‐capsular counterparts that also bind the N‐oxides. The thermally induced cis‐to‐trans interconversion processes demonstrated the reversibility of the photoisomerization and the photostability of most binding partners. An equimolar mixture of the two tetraureas produced two homodimeric capsules and the heterodimeric counterpart in a ratio close to statistical distribution.
Mechanistic Studies on NaHCO3 Hydrogenation and HCOOH Dehydrogenation Reactions Catalysed by a FeII Linear Tetraphosphine Complex
Authors: Marcos Rocío , Bertini Federica , Rinkevicius Zilvinas , Peruzzini Maurizio , Gonsalvi Luca , Ahlquist Mårten S. G.
Published: December 2017

We present a theoretical extension of the previously published bicarbonate hydrogenation to formate and formic acid dehydrogenation catalysed by FeII complexes bearing the linear tetraphosphine ligand tetraphos‐1. The hydrogenation reaction was found to proceed at the singlet surface with two competing pathways: A) H2 association to the Fe−H species followed by deprotonation to give a Fe(H)2 intermediate, which then reacts with CO2 to give formate. B) CO2 insertion into the Fe−H bond, followed by H2 association and subsequent deprotonation. B was found to be slightly preferred with an activation energy of 22.8 kcal mol−1, compared to 25.3 for A. Further we have reassigned the Fe−H complex, as a Fe(H)(H2), which undergoes extremely rapid hydrogen exchange.
Structural Origin of Metal Specificity in Isatin Hydrolase from Labrenzia aggregata Investigated by Computer Simulations
Authors: Uribe Lalita , Diezemann Gregor , Gauss Jürgen , Morth Jens Preben , Cascella Michele
Published: December 2017

We performed quantum‐chemical calculations, ab initio molecular dynamics, hybrid quantum mechanics/molecular mechanics (QM/MM) and enhanced sampling metadynamics simulations to investigate the origin of metal specificity in isatin hydrolase from Labrenzia aggregata. The peculiar octahedral binding geometry of the Mn2+ ion in the Michaelis complex includes both the isatin substrate and the catalytic water within the first coordination shell of the cation. Our calculations show that the same arrangement of the ligands cannot be efficiently achieved in the presence of other small divalent metal cations such as Zn2+ or Cu2+. On the contrary, bulkier alkaline‐earth cations such as Mg2+, which allow octahedral coordination, are not able to activate the catalytic water into the stronger OH− nucleophile required to attack the stable N‐aryl‐amide moiety of isatin.
Pyro‐Phyllobilins: Elusive Chlorophyll Catabolites Lacking a Critical Carboxylate Function of the Natural Chlorophylls
Authors: Li Chengjie , Wurst Klaus , Berghold Joachim , Podewitz Maren , Liedl Klaus R. , Kräutler Bernhard
Published: December 2017

A β‐keto ester grouping is a characteristic of ring E of the chlorophylls (Chls). Its presence has also reinforced the original identification of nonfluorescent Chl catabolites (NCCs) as colorless, amphiphilic phyllobilins (PBs). Polar NCCs were also detected in higher plants, in which a free carboxyl group replaced the ring E ester group. Such NCCs are surprisingly resistant to loss of this carboxyl unit, and NCCs lacking the latter, that is, pyro‐NCCs (pyNCCs), have not been reported. Intrigued by the question of the natural occurrence of pyro‐phyllobilins (pyPBs), we have prepared a representative pyNCC by decarboxylation of a natural NCC. We also converted the pyNCC into its yellow oxidation product, a pyro‐YCC (pyYCC). The solution structures of pyNCC and of pyYCC, and a crystal structure of the pyYCC methyl ester (pyYCC‐Me) were obtained. pyYCC‐Me features the same remarkable H‐bonded and π‐stacked dimer structure as the corresponding natural yellow Chl catabolite (YCC) with the ring E methyl ester group. Indeed, the latter substituent has little effect on the structure, as well as on the unique self‐assembly and photoswitch behavior of yellow PBs.
Direct, Metal‐free C(sp2)−H Chalcogenation of Indoles and Imidazopyridines with Dichalcogenides Catalysed by KIO3
Authors: Rafique Jamal , Saba Sumbal , Franco Marcelo S. , Bettanin Luana , Schneider Alex R. , Silva Lais T. , Braga Antonio L.
Published: December 2017

Herein, we report a greener protocol for the synthesis of 3‐Se/S‐indoles and imidazo[1,2‐a]pyridines through direct C(sp2)−H bond chalcogenation of heteroarenes with half molar equivalents of different dichalcogenides, using KIO3 as a non‐toxic, easy‐to‐handle catalyst and a stoichiometric amount of glycerol. The reaction features are high yields, based on atom economy, easy performance on gram‐scale, metal‐ and solvent‐free conditions as well as applicability to different types of N‐heteroarenes.
Total Synthesis of Sarpagine‐Related Bioactive Indole Alkaloids
Authors: Rahman M. Toufiqur , Deschamps Jeffrey R. , Imler Gregory H. , Cook James M.
Published: December 2017

Extension of the asymmetric Pictet–Spengler reaction to bulkier Nb‐alkylated tryptophan derivatives resulted in an improved stereospecific access to the key bicyclo[3.3.1]nonane core of bioactive C‐19 methyl substituted sarpagine/macroline/ajmaline indole alkaloids with excellent diastereoselectivity by internal asymmetric induction. Complete stereocontrol of the C‐19 methyl function in either the α‐ or β‐configuration was achieved, which enables the total synthesis of any member from this group of thirty alkaloids. We report herein, the total synthesis of macrocarpines (A‐C) 1–3, talcarpine 4, N(4)‐methyl‐N(4),21‐secotalpinine 5, dihydroperaksine 8 and deoxyperaksine 9.
Closing the Gap: Structural Evidence for the Missing Hexabromide Dianion [Br6]2−
Authors: Sonnenberg Karsten , Pröhm Patrick , Müller Carsten , Beckers Helmut , Steinhauer Simon , Lentz Dieter , Riedel Sebastian
Published: December 2017

The formation and experimental characterization of the first hexabromide dianion is presented. This dianion fills the last remaining gap in the series of polybromides from the tribromide [Br3]− to the undecabromide [Br11]−. The experimental results are compared to quantum‐chemical calculations. These calculations predict—based on electrostatic interactions—a T‐structure for the hexabromide dianion, while halogen–halogen bonding favors the hockey‐stick‐like structure experimentally found in the crystal structure. The hexabromide is built of two tribromide moieties, one of which is highly asymmetric. The classification of this unique anion as hexabromide dianion is discussed. The counter ion [C5H10N2Br]+ stabilizes the hexabromide dianion by additional σ‐hole interactions. The compound is fully characterized by mass spectrometry, NMR‐, IR and single crystal Raman spectroscopies as well as single‐crystal X‐ray diffraction.
A Priori Estimates for the Compressible Euler Equations for a Liquid with Free Surface Boundary and the Incompressible Limit
Authors: Lindblad Hans , Luo Chenyun
Published: December 2017

In this paper, we prove a new type of energy estimate for the compressible Euler equations with free boundary, with a boundary part and an interior part. These can be thought of as a generalization of the energies in Christodoulou and Lindblad to the compressible case and do not require the fluid to be irrotational. In addition, we show that our estimates are in fact uniform in the sound speed k. As a consequence, we obtain convergence of solutions of compressible Euler equations with a free boundary to solutions of the incompressible equations, generalizing the result of Ebin to when you have a free boundary. In the incompressible case our energies reduce to those in Christodoulou and Lindblad, and our proof in particular gives a simplified proof of their estimates with improved error estimates. Since for an incompressible irrotational liquid with free surface there are small data global existence results, our result leaves open the possibility of long‐time existence also for slightly compressible liquids with a free surface.© 2017 Wiley Periodicals, Inc.
Transient phenotypic changes in endothelial cells and pericytes in neonatal mouse retina following short‐term blockade of vascular endothelial growth factor receptors
Authors: Morita Akane , Mori Asami , Arima Shiho , Sakamoto Kenji , Nagamitsu Tohru , Ishii Kunio , Nakahara Tsutomu
Published: December 2017

Background: A short‐term interruption of vascular development causes structural abnormalities in retinal vasculature. However, the detailed changes in vascular components (endothelial cells, pericytes, and basement membranes) remain to be fully determined. The present study aimed to provide a detailed description of morphological changes in vascular components following a short‐term interruption of retinal vascular development in mice. Results: Two‐day treatment of neonatal mice with the vascular endothelial growth factor (VEGF) receptor tyrosine kinase inhibitor KRN633 (10 mg/kg, subcutaneously) on postnatal day (P)0 and P1 (P0/1) and P4 and P5 (P4/5) induced different degrees and patterns of impairment of retinal vascular development. Three days after completion of the treatment, the delayed radial vascular growth occurred in P0/1 group mice, whereas in P4/5 group mice, revascularization preferentially occurred in the central avascular area, and radial vascular growth remained suppressed by P10. Differences in α‐smooth muscle actin expression in pericytes were noted in the processes between normal vascular formation and vascular regrowth. The changes in vascular cells were associated with the hypoxia‐induced enhancement of VEGF expression in the superficial retinal layer. Conclusions: These findings suggest that the phenotype of vascular cells is altered following a short‐term interruption of vascular development in the retina. Developmental Dynamics 247:699–711, 2018. © 2017 Wiley Periodicals, Inc.