bluuebunny/crossref_metadata_2025 huggingface dataset:
Uptake and Intracellular Fate of Engineered Nanoparticles in Mammalian Cells: Capabilities and Limitations of Transmission Electron Microscopy—Polymer‐Based Nanoparticles
Authors: Reifarth Martin , Hoeppener Stephanie , Schubert Ulrich S.
Published: January 2018

In order to elucidate mechanisms of nanoparticle (NP)–cell interactions, a detailed knowledge about membrane–particle interactions, intracellular distributions, and nucleus penetration capabilities, etc. becomes indispensable. The utilization of NPs as additives in many consumer products, as well as the increasing interest of tailor‐made nanoobjects as novel therapeutic and diagnostic platforms, makes it essential to gain deeper insights about their biological effects. Transmission electron microscopy (TEM) represents an outstanding method to study the uptake and intracellular fate of NPs, since this technique provides a resolution far better than the particle size. Additionally, its capability to highlight ultrastructural details of the cellular interior as well as membrane features is unmatched by other approaches. Here, a summary is provided on studies utilizing TEM to investigate the uptake and mode‐of‐action of tailor‐made polymer nanoparticles in mammalian cells. For this purpose, the capabilities as well as limitations of TEM investigations are discussed to provide a detailed overview on uptake studies of common nanoparticle systems supported by TEM investigations. Furthermore, methodologies that can, in particular, address low‐contrast materials in electron microscopy, i.e., polymeric and polymer‐modified nanoparticles, are highlighted.
PdCo Alloy Nanonetworks−Polyallylamine Inorganic–Organic Nanohybrids toward the Oxygen Reduction Reaction
Authors: Xu Guang‐Rui , Han Cong‐Cong , Zhu Ying‐Ying , Zeng Jing‐Hui , Jiang Jia‐Xing , Chen Yu
Published: January 2018

Rationally controlling the morphology, chemical composition, and interfacial property of metal nanostructures can remarkably enhance their electrocatalytic performance, such as activity, selectivity, and durability. In this work, a facile functional molecule‐assisted cyanogel‐reduction method is developed to successfully synthesize the polyallylamine (PAA)‐functionalized PdCo alloy nanonetworks (PdCo‐NNW@PAA) inorganic–organic nanohybrids. The solid, double‐metal, and 3D backbone properties of jelly‐like K2PdCl4/K3Co(CN)6 cyanogel intermediate contribute to the high alloying degree and network structure of PdCo‐NNW@PAA nanohybrids. During the reduction, PAA molecules not only serve as surfactant to decrease the particle size but also act as functional molecule to modify the metal surface. The oxygen reduction reaction (ORR) polarization and chronoamperometry tests demonstrate that PdCo‐NNW@PAA nanohybrids have outstanding electrocatalytic activity, excellent resistance to alcohol crossover effect, and good durability toward the ORR in alkaline media. This work provides a new strategy for synthesizing the chemical functionalized multimetallic alloy nanonetworks at room temperature and reveals that the interfacial property of metal nanocrystals strongly affects their electrocatalytic activity and selectivity.
Second‐Harmonic Spectroscopy for Defects Engineering Monitoring in Transition Metal Dichalcogenides
Authors: Rosa Henrique G. , Junpeng Lu , Gomes Lídia C. , Rodrigues Manuel J. L. F. , Haur Sow Chorng , Gomes José C. V.
Published: January 2018

Defects engineering in transition metal dichalcogenides is a topic of intense research recently, since crystal properties can be controlled and tailored during and after fabrication. In this context, defects characterization is key to understand the material structure and enable specific applications. In this work, second‐harmonic generation (SHG) spectroscopy is used to map concentric triangular defective regions in as‐grown monolayer tungsten disulfide, demonstrating that SHG can be used for defects observation and characterization in layered noncentrosymmetric nanomaterials. In monolayer tungsten disulfide, in regions where sulfur atoms are replaced by vacancies, it is observed that the SHG signal experiences an enhancement of two orders of magnitude due to the presence of mid‐gap states. Moreover, SHG is anticorrelated with photoluminescence emission from the material, showing that both techniques can provide complementary information about the crystalline structure. In comparison with other optical characterization techniques, SHG provides fast response, does not depend on real energy transitions, and can be used for defects mapping in several other materials regardless the optical bandgap energy.
Heterogeneous impacts from a retail grocery acquisition: Do national and store brand prices respond differently?
Authors: Çakır Metin , Secor William G.
Published: January 2018

We investigate the extent to which a grocery retailer merger has different effects on the prices of national and store brands. Using retail scanner data, we retrospectively analyze a food retail acquisition in a large U.S. city. We focus on fluid milk and ready‐to‐eat (RTE) cereal categories, which represent a relatively homogenous and a relatively differentiated product category, respectively. We use a difference‐in‐difference estimation framework to obtain the causal effect of the acquisition on prices for the acquiring retailer. The primary finding is that the acquisition has heterogeneous price effects in the relatively differentiated RTE cereal category. The implications of results for consumers, food retailing, and merger analysis are discussed [EconLit citations: L11, L13, L22, L81].
Blue light‐emitting diodes induce autophagy in colon cancer cells by Opsin 3
Authors: Yoshimoto Toshiaki , Morine Yuji , Takasu Chie , Feng Rui , Ikemoto Tetsuya , Yoshikawa Kozo , Iwahashi Syuichi , Saito Yu , Kashihara Hideya , Akutagawa Masatake , Emoto Takahiro , Kinouchi Yosuke , Shimada Mitsuo
Published: January 2018

Background

Light emitting‐diodes (LED) have various effects on living organisms and recent studies have shown the efficacy of visible light irradiation from LED for anticancer therapies. However, the mechanism of LED's effects on cancer cells remains unclear. The aim of the present study was to investigate the effects of LED on colon cancer cell lines and the role of photoreceptor Opsin 3 (Opn3) on LED irradiation in vitro.

Methods

Human colon cancer cells (HT‐29 or HCT‐116) were seeded onto laboratory dishes and irradiated with 465‐nm LED at 30 mW/cm2 for 30 minutes. Cell Counting Kit‐8 was used to measure cell viability, and apoptosis and caspase 3/8 expression were evaluated by AnnexinV/PI and reverse transcription‐polymerase chain reaction (RT‐PCR), respectively. Autophagy and expression of LC‐3 and beclin‐1 were also evaluated by autophagy assays, RT‐PCR and Western blotting. We further tested Opn3 knockdown by Opn3 siRNA and the Gi/o G‐protein inhibitor NF023 in these assays.

Results

Viability of HT‐29 and HCT‐116 cells was lower in 465‐nm LED‐irradiated cultures than in control cultures. LC‐3 and beclin‐1 expressions were significantly higher in LED‐irradiated cultures, and autophagosomes were detected in irradiated cells. The reductive effect of cancer cell viability following blue LED irradiation was reversed by Opn3 knockdown or NF023 treatment. Furthermore, increased LC‐3 and beclin‐1 expression that resulted from blue LED irradiation was suppressed by Opn3 knockdown or NF023 treatment.

Conclusion

Blue LED irradiation suppressed the growth of colon cancer cells and Opn3 may play an important role as a photoreceptor.
Detection of gas components as a novel diagnostic method for colorectal cancer
Authors: Ishibe Atsushi , Ota Mitsuyoshi , Takeshita Akemi , Tsuboi Hiroshi , Kizuka Satoko , Oka Hidenori , Suwa Yusuke , Suzuki Shinsuke , Nakagawa Kazuya , Suwa Hirokazu , Momiyama Masashi , Watanabe Jun , Taguri Masataka , Kunisaki Chikara , Endo Itaru
Published: January 2018

Background

The fecal occult blood test (FOBT) is widely accepted as the most economic and non‐invasive screening method for colorectal cancer (CRC). However, the FOBT is inconvenient because it requires a fecal sample and shows limited accuracy. Alternatively, we hypothesized that fecal gas compounds from bowel movements may be a non‐invasive biomarker for CRC.

Methods

Gas compounds were collected from the bowel movements of 30 patients with CRC and from 26 healthy controls. The patient group comprised 17 males and 13 females, and the average age was 68 years. Additionally, 22 patients had colon cancer, and eight patients had rectal cancer. Gas compounds were analyzed using gas chromatography and compared with those from healthy controls.

Results

In the gas analysis, methyl mercaptan was significantly higher in the CRC group than in the control group. Hydrogen was significantly lower in the CRC group than in the control group and was correlated with tumor depth and advanced disease stage. Sensitivity, specificity, and accuracy of detection by a discriminant formula were 90%, 57.7%, and 75%, respectively.

Conclusion

Gas compounds from defecation constitute a promising, novel non‐invasive approach for CRC screening. (UMIN000028256)
Light‐Driven Shape‐Memory Porous Films with Precisely Controlled Dimensions
Authors: Wang Wei , Shen Dingfeng , Li Xiao , Yao Yuan , Lin Jiaping , Wang Aurelia , Yu Jiwoo , Wang Zhong Lin , Hong Suck Won , Lin Zhiqun , Lin Shaoliang
Published: January 2018

Shape‐memory polymers (SMPs) are an intriguing class of smart materials possessing reversible shape change and recovery capabilities. Effective routes to shape‐memory porous films (SMPFs) are few and limited in scope owing to the difficulty in manipulating the shape change of pores by conventional methods. Herein we report an unconventional strategy for crafting light‐driven SMPFs by judiciously constructing highly ordered porous films via a facile “breath figure” approach, followed by sequential vapor crosslinking and nondestructive directional light manipulation. Micropores can thus be transformed into other shapes including rectangle, rhombus and size‐reduced micropores at room temperature. The transformed micropores can be reverted to their original shapes by either thermal annealing or UV irradiation. As such, this strategy expands the rich diversity of SMPs accessible.
Dikationische E4‐Ketten (E=P, As, Sb, Bi) eingebettet in der Koordinationssphäre von Übergangsmetallen
Authors: Dütsch Luis , Fleischmann Martin , Welsch Stefan , Balázs Gábor , Kremer Werner , Scheer Manfred
Published: January 2018

Es wird ein Vergleich der Oxidationschemie der Komplexe [{CpMo(CO)2}2(μ,η2:η2‐E2)] (E=P (A), As (B), Sb (C), Bi (D)) präsentiert. Die Oxidation von A–D mit [Thia]+ (=[C12H8S2]+) führt zur selektiven Bildung der dikationischen E4‐Komplexe [{CpMo(CO)2}4(μ4,η2:η2:η2:η2‐E4)]2+ (E=P (1), As (2), Sb (3), Bi (4)), die von vier [CpMo(CO)2]‐Fragmenten stabilisiert werden. Die Bildung der entsprechenden Monokationen [A]+, [C]+ und [D]+ konnte weder durch Cyclovoltammetrie noch durch EPR‐ oder NMR‐Spektroskopie nachgewiesen werden. Dies deutet auf eine schnelle Dimerisierung und keine Dissoziation in Lösung hin, was auch durch DFT‐Rechnungen prognostiziert wurde. Allerdings belegen EPR‐Messungen von 2 die Existenz geringer Mengen des Radikalkations [B]+ in Lösung. Die Einkristall‐Röntgenstrukturanalysen zeigen, dass die Produkte 1 und 2 im Festzustand eine Zickzack‐E4‐Kette aufweisen, wohingegen 3 und 4 über einen zentralen E4‐Käfig mit einer verzerrten, Butterfly‐artigen Geometrie verfügen. Darüber hinaus kann 1 einfach und reversibel in eine symmetrische und eine asymmetrische Form umgewandelt werden.
Active Intracellular Delivery of a Cas9/sgRNA Complex Using Ultrasound‐Propelled Nanomotors
Authors: Hansen‐Bruhn Malthe , de Ávila Berta Esteban‐Fernández , Beltrán‐Gastélum Mara , Zhao Jing , Ramírez‐Herrera Doris E. , Angsantikul Pavimol , Vesterager Gothelf Kurt , Zhang Liangfang , Wang Joseph
Published: January 2018

Direct and rapid intracellular delivery of a functional Cas9/sgRNA complex using ultrasound‐powered nanomotors is reported. The Cas9/sgRNA complex is loaded onto the nanomotor surface through a reversible disulfide linkage. A 5 min ultrasound treatment enables the Cas9/sgRNA‐loaded nanomotors to directly penetrate through the plasma membrane of GFP‐expressing B16F10 cells. The Cas9/sgRNA is released inside the cells to achieve highly effective GFP gene knockout. The acoustic Cas9/sgRNA‐loaded nanomotors display more than 80 % GFP knockout within 2 h of cell incubation compared to 30 % knockout using static nanowires. More impressively, the nanomotors enable highly efficient knockout with just 0.6 nm of the Cas9/sgRNA complex. This nanomotor‐based intracellular delivery method thus offers an attractive route to overcome physiological barriers for intracellular delivery of functional proteins and RNAs, thus indicating considerable promise for highly efficient therapeutic applications.
(Benzyl isocyanide)gold(I) pyrimidine‐2‐thiolate complex: Synthesis and biological activity
Authors: Fereidoonnezhad Masood , Shahsavari Hamid R. , Lotfi Elaheh , Babaghasabha Mojgan , Fakhri Motahareh , Faghih Zeinab , Faghih Zahra , Hassan Beyzavi M.
Published: January 2018

The reaction of [(Me2S)AuCl] with an equimolar amount of benzyl isocyanide (PhCH2NC) ligand led to the formation of complex [(PhCH2NC)AuCl] (1). The solid‐state structure of 1 was determined using the X‐ray diffraction method. Through a salt metathesis reaction, the chloride ligand in 1 was replaced by pyrimidine‐2‐thiolate (SpyN−) to afford the complex [(PhCH2NC)Au(η1‐S‐Spy)] (2), which was characterized spectroscopically. The cytotoxic activities of 1 and 2 were evaluated against three human cancer cell lines: ovarian carcinoma (SKOV3), lung carcinoma (A549) and breast carcinoma (MCF‐7). Complex 2 showed higher cytotoxicity than cisplatin against SKOV3 and MCF‐7 cancer cell lines. It showed a strong anti‐proliferative activity with IC50 of 7.80, 6.26 and 6.14 μM, compared with that measured for cisplatin which was 7.62, 12.36 and 11.47 μM, against A549, SKOV3 and MCF‐7 cell lines, respectively. The induction of cellular apoptosis by 2 was also studied on MCF‐7 cell line. Our results indicated that 2 could induce apoptosis in cancerous cells in a dose‐dependent manner.
Theoretical insight into the photodeactivation pathway of the tetradentate Pt(II) complex: The π‐conjugation effect
Authors: Zuo Ke , Luo Yafei , Sun Xin , Shen Wei , Tang Dianyong , Hu Jianping
Published: January 2018

In this work, density functional theory and time‐dependent density functional theory were used to investigate the effects of π‐conjugation of the ligand on the photophysical properties, radiative/nonradiative processes and phosphorescence quantum efficiency of tetradentate cyclometalated Pt (II) complex with carbazolyl‐pyridine ligands PtNON. By simulating the absorption spectra and emission wavelengths, increasing the π‐conjugation of the ligand could cause the absorption and emission wavelengths to red‐shift. The results of the computation of key parameters in the radiative decay process, such as singlet‐triplet splitting energy, transition dipole moment and spin‐coupled matrix element between the lowest triplet and singlet excited states, showed that the expansion of π‐conjugation on the carbazole ligand of PtNON resulted in reduction of these parameters, thereby reducing the radiation rate constant. The analyses of the PtNON nonradiative pathway also found that the high activation energy of PtNON made it one of the reasons for the high phosphorescence quantum yield. At the same time, enhancing the molecular orbital delocalization of the ligand further enlarged the energy barrier of the nonradiative pathway, and was conducive to the improvement of phosphorescence quantum yield.
Anticancer platinum‐based complexes with non‐classical structures
Authors: Cai Linxiang , Yu Congtao , Ba Linkui , Liu Qinghua , Qian Yunxu , Yang Bo , Gao Chuanzhu
Published: January 2018

Although classical platinum drugs such as cisplatin, carboplatin and oxaliplatin play a vitally important role in cancer treatment, nonselective distribution of platinum drugs in normal and tumor cells can induce serious gastrointestinal reaction, nephrotoxicity, ototoxicity, neurotoxicity and cross resistance, limiting their applications. Over the past few years, a great number of platinum complexes of non‐classical structures have been extensively investigated and evaluated in vitro and in vivo, some of them exhibiting considerable activity. In this review, platinum‐based complexes with non‐classical structures which have anticancer potential are described and several representative examples are discussed with their mechanism of action.
Hybridization of Al2O3 microspheres and acrylic ester resins as a synergistic absorbent for selective oil and organic solvent absorption
Authors: Zhang Tao , Yue Xuejie , Yang Dongya , Guo Qing , Qiu Fengxian , Li Zhangdi
Published: January 2018

In this study, we have focused on the synthesis, characterization, and oil absorption properties of Al2O3 microspheres/acrylic ester resin (AER) hybrids. The Al2O3 microspheres are prepared by a combined hydrothermal and sintering processes, followed by surface modification with silane coupling agent (KH 570). The Al2O3 microspheres/AER hybrids with a rough surface are synthesized by a microwave polymerization route by using modified Al2O3 microspheres as modifiers. In this hybrid materials system, the Al2O3 microspheres with porous structures may provide fast oil absorption due to the low oils absorption energy and short diffusion lengths. The resin hybrids exhibited reversible oils and organic solvents adsorption with maximum absorption capacities up to 29.85 g/g. This study suggests potential environmental advantage in using metal oxide microspheres in improving the oil absorption properties of oil‐absorbing resins as absorbents for recovering oil and organic solvent from water.
The reduction of 4‐nitrophenol and 2‐nitroaniline by palladium catalyst based on a KCC‐1/IL in aqueous solution
Authors: Baghbamidi Sakineh Esfandiari , Hassankhani Asadollah , Sanchooli Esmael , Sadeghzadeh Seyed Mohsen
Published: January 2018

KCC‐1/IL/Pd NPs can used as an excellent support for the synthesis of highly sparse homogeneous catalyst. KCC‐1 has high surface area that was functionalized with ionic liquid phase acting as the strong performers so that the Pd catalyst was well‐dispersed without aggregation on the framework of the KCC‐1/IL. This nano catalyst was specified by TGA, XRD, TEM, SEM, FT‐IR, and ICP. For reduction of 2‐nitroaniline and 4‐nitrophenol used from the KCC‐1/IL/Pd NPs as a green catalyst that showed excellent catalytic activities. Compared with the traditional substrate, KCC‐1 substantially increases protection and the accessibility of the nanoparticle sites due to its three dimensional hierarchical structure.
Nature of MoH···I bonds in Cp2Mo(L)H···I‐C≡C‐R Complexes (L=H, CN, PPh2, C(CH3)3; R=NO2, Cl, Br, H, OH, CH3, NH2)
Authors: Dang Yaru , Wang Weihua , Meng Lingpeng , Li Qingzhong , Li Xiaoyan
Published: January 2018

The nature of the MoH···I bond in Cp2Mo(L)H···I‐C≡C‐R (L= H, CN, PPh2, C(CH3)3; R=NO2, Cl, Br, H, OH, CH3, NH2) was investigated using electrostatic potential analysis, topological analysis of the electron density, energy decomposition analysis and natural bond orbital analysis. The calculated results show that MoH···I interactions in the title complexes belong to halogen‐hydride bond, which is similar to halogen bonds, not hydrogen bonds. Different to the classical halogen bonds, the directionality of MoH···I bond is low; Although electrostatic interaction is dorminant, the orbital interactions also play important roles in this kind of halogen bond, and steric interactions are weak; the strength of H···I bond can tuned by the most positive electrostatic potential of the I atom. As the electron‐withdrawing ability of the R substituent in the alkyne increases, the electrostatic potential maximum of the I atom increases, which enhances the strength of the H···I halogen bond, as well as the electron transfer.
Untersuchungen zur Rissentstehung in den historischen Pfeilern der Elstertalbrücke Pirk
Authors: Keuser Manfred , Niederwald Michael
Published: January 2018

Der Bau der Elstertalbrücke Pirk wurde im Jahr 1938 begonnen und 1940 kriegsbedingt eingestellt. Bis dahin waren die aus einem Stampfbetonkern und einer Granitmauerwerksschale bestehenden Pfeiler sowie die zwischen den Brückenpfeilern spannenden Gewölbebögen errichtet. Bis zur deutschen Wiedervereinigung blieb die Brücke aufgrund ihrer Lage im Grenzsperrgebiet der DDR ungenutzt und wurde im Jahr 1993 nach einer Sanierung durch die Herstellung der fehlenden Überbauten vervollständigt. Seitdem kam es im Bereich der Pfeilerköpfe zu einer vertikalen Rissbildung im Granitmauerwerk, die sich nach unten fortsetzt. Zur Feststellung der Rissursache wurden zunächst Finite‐Elemente‐Berechnungen durchgeführt, in denen das Tragverhalten und die Beanspruchungen der Pfeiler und insbesondere des Pfeilerkopfs untersucht wurden. Des Weiteren wurden nichtlineare Finite‐Elemente‐Simulationen eines Granitmauerwerksverbands vorgenommen, um die bis zur Bildung eines Risses übertragbaren Zugspannungen beurteilen zu können.
Performance‐Indikatoren für die Bewertung von Strukturen aus Konstruktionsbeton auf europäischer Ebene nach COST TU1406
Authors: Strauss Alfred , Ivankovic' Ana Mandic' , Mold Lisa , Bergmeister Konrad , Matos José C. , Casas Joan R.
Published: January 2018

Das Qualitätsmanagement von Strukturen aus Stahl‐ und Spannbeton, insbesondere jener von Straßenbrücken unterscheidet sich innerhalb Europas stark von Staat zu Staat. Diese Publikation gibt nicht nur einen Überblick über den aktuellen Stand der Technik, sondern es wird ein Vorschlag für eine holistische Performance‐Bewertung von Brücken aus Konstruktionsbeton vorgestellt. Um die Vorgehensweise bei der Qualitätskontrolle von Straßenbrücken und infolgedessen die Entscheidungsfindung zur Umsetzung von Instandhaltungsmaßnahmen auf einen einheitlichen Standard zu bringen, hat sich das europäsche Forschungsprojekt COST (European Cooperation in Science & Technology) Action TU1406 zum Ziel gesetzt, eine in Europa allgemein gültige Richtlinie zur Erstellung von Qualitätskontrollplänen zu entwickeln. Die COST TU 1406 befasst sich mit der Erhebung der für die Zustandsbeurteilung von Straßenbrücken relevanten Leistungsindikatoren (performance indicators). Um Daten in Bezug auf diese Performance‐Indikatoren zu sammeln, wurden die Mitgliedsstaaten der COST Action ersucht, sämtliche Informationen aus bereits in Anwendung befindlichen Dokumenten, wie Richtlinien und Normen, sowie aus Forschungsdokumenten zu erheben. In diesem Beitrag werden die Prozesse hinsichtlich der Erhebung und Dokumentation der Daten sowie deren Evaluierung eingehend beleuchtet. Ein wesentlicher Teil war auch die Homogenisierung und Kategorisierung der Ergebnisse aus den Erhebungen, um in weiterer Folge Performance‐Indikatoren zu identifizieren und diese dann sogenannten Key‐Performance‐Indikatoren zuzuordnen. Die Erhebung der Performance‐Indikatoren und die Definition von Key‐Performance‐Indikatoren waren wesentliche Schritte zur Entwicklung einer standardisierten Richtlinie zur Erstellung von Qualitätskontrollplänen für Straßenbrücken auf europäischer Ebene.
Impact of bistrand abasic sites and proximate orientation on DNA global structure and duplex energetics
Authors: Minetti Conceição A. , Sun Jeffrey Y. , Jacobs Daniel P. , Kang Inkoo , Remeta David P. , Breslauer Kenneth J.
Published: January 2018

Bistrand lesions embedded within a single helical turn of tridecameric deoxyoligonucleotide duplexes represent a model system for exploring the impact of clustered lesions that occur in vivo and pose a significant challenge to cellular repair machineries. Such investigations are essential for understanding the forces that dictate lesion‐induced mutagenesis, carcinogenesis, and cytotoxicity within a context that mimics local helical perturbations caused by an ionizing radiation event. This study characterizes the structural and energy profiles of DNA duplexes harboring synthetic abasic sites (tetrahydrofuran, F) as models of clustered bistrand abasic (AP) lesions. The standard tridecameric dGCGTACCCATGCG·dCGCATGGGTACGC duplex is employed to investigate the energetic impact of single and bistrand AP sites by strategically replacing one or two bases within the central CCC/GGG triplet. Our combined analysis of temperature‐dependent UV and circular dichroism (CD) profiles reveals that the proximity and relative orientation of AP sites within bistrand‐damaged duplexes imparts a significant thermodynamic impact. Specifically, 3′‐staggered lesions (CCF/GFG) exert a greater destabilizing effect when compared with their 5′‐counterpart (FCC/GFG). Moreover, a duplex harboring the central bistrand AP lesion (CFC/GFG) is moderately destabilized yet exhibits distinct properties relative to both the 3′ and 5′‐orientations. Collectively, our energetic data are consistent with structural studies on bistrand AP‐duplexes of similar sequence in which a 3′‐staggered lesion exerts the greatest perturbation, a finding that provides significant insight regarding the impact of orientation on lesion repair processing efficiency.
Stenting of the inter‐atrial septum in infants and small children: Indications, techniques and outcomes
Authors: Mainzer Gur , Goreczny Sebastian , Morgan Gareth J. , Qureshi Shakeel , Krasemann Thomas , Dryzek Pawel , Moll Jadwiga A , Moszura Tomasz , Rosenthal Eric
Published: January 2018

Objectives

To evaluate the procedural success and outcome of inter‐atrial stenting.

Background

Inter‐atrial stenting has been shown to be an effective way to maintain inter‐atrial blood flow, however it is considered a high risk procedure, usually performed urgently in patients with significant hemodynamic compromise.

Methods

Between September 2004 and August 2016, inter‐atrial stenting was attempted in 29 children. Procedural, clinical, and follow‐up data were collected retrospectively.

Results

The procedures were completed successfully in 27 patients. Twenty‐five procedures were undertaken percutaneously, with the remaining four being performed as hybrid procedures. The patients were considered as high risk for adverse events (82% scored as CRISP 4 and 5) with four deaths during the first 24 hr (14%). Procedural complications occurred in eight patients (28%) with related death in three patients (10%). One further patient died after an uncomplicated technically successful stent implantation performed as a salvage procedure. Procedural complications (71% vs. 14%) and mortality (43% vs. 5%) were higher in those, who weighed 3 kg or less (P < 0.05). Patency of the stents was maintained until planned staged surgery in 22 patients at a mean of 302 days. Three patients underwent further balloon dilation for flow restriction at 58–201 days. In two un‐operated patients the stents remained patent at follow‐up. One patient with severe pulmonary hypertension died with a patent stent.

Conclusions

Inter‐atrial stenting produces reliable patency with a very good success rate. Morbidity and mortality were related to low weight at the time of the procedure.
Validation of contemporary risk scores in predicting coronary thrombotic events and major bleeding in patients with acute coronary syndrome after drug‐eluting stent implantations
Authors: Song Li , Guan Changdong , Yan Hongbing , Qiao Shubin , Wu Yongjian , Yuan Jinqing , Dou Kefei , Yang Yuejin , Dangas George D. , Xu Bo
Published: January 2018

Objectives

We aimed to assess the prognostic ability of the ST score, DAPT score, and PARIS score in a Chinese population.

Background

Recently, several risk scores predicting the long‐term risk of coronary thrombotic events [CTE, defined as the composite of definite or probable stent thrombosis (ST) and myocardial infarction] and bleeding have been developed and initially validated in Western populations.

Methods

A total of 6,088 consecutive patients with acute coronary syndrome (mean age 58.3 ± 10.4; women 23.1%) treated with drug‐eluting stents in 2013 at our single institution were enrolled. We calculated risk scores and evaluated their performance for predicting definite or probable ST, CTE and major bleeding (MB, defined as the occurrence of a Bleeding Academic Research Consortium type 3 or 5 bleed). The prognostic value of risk scores was assessed by receiver‐operating characteristic curves.

Results

The ST score, DAPT score, and PARIS score all showed unsatisfactory discrimination to predict 2‐year or 1‐ to 2‐year ST and CTE (c‐statistic = 0.51–0.59). With respect to bleeding outcomes, the PARIS score showed unsatisfactory discrimination in predicting 2‐year MB (c‐statistic = 0.56); the DAPT score performed slightly better than the PARIS score in predicting occurrence of later MB events between 1 and 2 years, whereas its discriminative capacity was only modest (c‐statistic = 0.71).

Conclusions

The current three risk scores, derived and initially validated in Western populations, may not be applicable to the Chinese population, although DAPT score was determined to be a modestly accurate quantitative tool for prediction of later MB.
Methanation of Carbon Dioxide over Zeolite‐Encapsulated Nickel Nanoparticles
Authors: Goodarzi Farnoosh , Kang Liqun , Wang Feng Ryan , Joensen Finn , Kegnæs Søren , Mielby Jerrik
Published: January 2018

Efficient methanation of CO2 relies on the development of more selective and stable heterogeneous catalysts. Herein, we present a simple and effective method to encapsulate Ni nanoparticles in zeolite silicalite‐1. In this method, the zeolite is modified by selective desilication, which creates intraparticle voids and mesopores that facilitate the formation of small and well‐dispersed nanoparticles upon impregnation and reduction. Transmission electron microscopy and X‐ray photoelectron spectroscopy analyses confirm that a significant part of the Ni nanoparticles are situated inside the zeolite rather than on the outer surface. The encapsulation results in increased metal dispersion and, consequently, high catalytic activity for CO2 methanation. With a gas hourly space velocity of 60 000 mL gcatalyst−1 h−1 and H2/CO2=4, the zeolite‐encapsulated Ni nanoparticles result in 60 % conversion at 450 °C, which corresponds to a site‐time yield of approximately 304 mol
 molNi−1 h−1. The encapsulated Ni nanoparticles show no change in activity or selectivity after 50 h of operation, although postcatalysis characterization reveals some particle migration.
Volumetric Heat Transfer Coefficient in Fluidized‐Bed Dryers
Authors: Poós Tibor , Szabó Viktor
Published: January 2018

In literature, there are several Nu=f(Re) equations to specify the heat transfer coefficient between solids and the drying gas, but these equations differ significantly because of the inaccuracy of determining the contact surface between the two phases. A pilot‐plant fluidized‐bed dryer is developed to study the heat and mass transfer phenomena during the drying process. A volumetric heat transfer coefficient is applied for modeling fluidized‐bed dryers. A modified Nusselt number is defined to compare the experimental results and those of the literature. The modified Nu'=f(Re) equation exhibits a proper correlation between the results of the experiments in the literature and those of our experiments.
Enhanced Stability of Lithium Metal Anode by using a 3D Porous Nickel Substrate
Authors: Yu Lu , Canfield Nathan L. , Chen Shuru , Lee Hongkyung , Ren Xiaodi , Engelhard Mark H. , Li Qiuyan , Liu Jun , Xu Wu , Zhang Ji‐Guang
Published: January 2018

Lithium (Li) metal is considered as the “holy grail” anode for high energy density batteries, but its applications in rechargeable Li metal batteries are still hindered by the formation of Li dendrites and low coulombic efficiency for Li plating/stripping. An effective strategy to stabilize Li metal is to embed a Li metal anode in a three‐dimensional (3D) current collector. Here, a highly porous 3D Ni substrate is reported to effectively stabilize a Li metal anode. By using a galvanostatic intermittent titration technique combined with scanning electron microscopy, the underlying mechanism of the improved stability of the Li metal anode is revealed. It is clearly demonstrated that the porous 3D Ni substrate can effectively suppress the formation of “dead” Li and support the generation of a dense surface passivation layer, while a highly porous “dead” Li layer is accumulated on the two‐dimensional (2D) Li metal, which eventually limits mass transport. X‐ray photoelectron spectroscopy results further reveal the compositional differences in the solid‐electrolyte interphase layer formed on the Li metal embedded in the porous 3D Ni substrate and the 2D Li metal substrate. These results indicate that the use of 3D conductive host is critical for the long‐term stability of Li metal batteries.
Understanding the Unexpected Product Distribution in the Aerial Oxidation of Carbene‐Stabilized Diphosphorus Complex
Authors: Ghosh Boyli , Banerjee Ambar , Paul Ankan
Published: January 2018

Oxidation of nonmetallic singlet molecules by oxygen has its own share of intricacies. Herein, by means of DFT and ab initio techniques, mechanistic details of the aerial oxidation of an N‐heterocyclic carbene (NHC) stabilized diphosphorus complex are revealed. This particular oxidation process is known to produce an unexpected P−P bond containing diphosphorus tetroxide complex, instead of the more thermodynamically stable oxo‐bridged (P−O−P) compound. These findings suggest that the P−P bond containing less stabilized species is a kinetically controlled product (KCP) and obtained due to the presence of lower lying transition states (TSs) in the pathway leading to its formation, relative to the higher lying corresponding minimum‐energy crossing points (MECPs) present in the pathway involved in the formation of the oxo‐bridged species, which is the thermodynamically controlled product (TCP). Thus, an intriguing variant of the well‐known KCP/TCP phenomenon is presented here, in which the KCP is formed not by merely traditionally known lower barrier heights of TSs involved in the formation of KCP, but by faster transmission of a system through a low barrier TS relative to a higher lying MECP. Additionally, the faster kinetics of an irreversible unimolecular O−O dissociation step, which avoids the formation of the TCP is a contributing factor in dictating the fate of the reaction. The insights provided herein may help to understand the oxidation of other P−P‐containing species, such as black phosphorene.
Selective Single‐Site Pd−In Hydrogenation Catalyst for Production of Enhanced Magnetic Resonance Signals using Parahydrogen
Authors: Burueva Dudari B. , Kovtunov Kirill V. , Bukhtiyarov Andrey V. , Barskiy Danila A. , Prosvirin Igor P. , Mashkovsky Igor S. , Baeva Galina N. , Bukhtiyarov Valerii I. , Stakheev Aleksandr Yu. , Koptyug Igor V.
Published: January 2018

Pd−In/Al2O3 single‐site catalyst was able to show high selectivity (up to 98 %) in the gas phase semihydrogenation of propyne. Formation of intermetallic Pd−In compound was studied by XPS during reduction of the catalyst. FTIR−CO spectroscopy confirmed single‐site nature of the intermetallic Pd−In phase reduced at high temperature. Utilization of Pd−In/Al2O3 in semihydrogenation of propyne with parahydrogen allowed to produce ≈3400‐fold NMR signal enhancement for reaction product propene (polarization=9.3 %), demonstrating the large contribution of pairwise hydrogen addition route. Significant signal enhancement as well as the high catalytic activity of the Pd−In catalyst allowed to acquire 1H MR images of flowing hyperpolarized propene gas selectively for protons in CH, CH2 and CH3 groups. This observation is unique and can be easily transferred to the development of a useful MRI technique for an in situ investigation of selective semihydrogenation in catalytic reactors.
A Synthetic Binder of Breast Cancer Stem Cells
Authors: Chen Luxi , Long Chao , Tran Kha Andy Minh , Lee Jiyong
Published: January 2018

Cancer stem cells (CSCs) are associated with drug resistance, metastasis and recurrence of cancer. A synthetic binder of CSCs can provide a valuable tool to study the biology of CSCs and a lead to develop imaging, diagnostic and therapeutic agents targeting CSCs. Herein, a synthetic ligand (1) that specifically binds to CSCs over non‐CSCs of breast cancer cells was identified for the first time via a cell‐binding screening of a chemical library. The ligand 1 showed specific binding to CD24−/CD44+/ALDH+ CSC population of MCF‐7 and MDA‐MB‐231. We have demonstrated that 1‐immobilized beads can be used as matrices for affinity isolation of 1‐binding CSC population from breast cancer cells. The 1‐binding population showed significantly increased expressions of stemness‐associated transcription factors. Importantly, the 1‐binding population demonstrated accelerated tumor growth in vivo, and the resulting tumor displayed an increased migratory activity and high expressions of CSC markers.
Synthesis of Benzofuranones via Palladium‐Catalyzed Intramolecular Alkoxycarbonylation of Alkenylphenols
Authors: Hirschbeck Vera , Fleischer Ivana
Published: January 2018

Herein, a new catalytic system to synthesize benzofuranones is reported. A palladium‐catalyzed intramolecular alkoxycarbonylation is employed to generate 3‐substituted‐benzofuran‐2(3H)‐ones from alkenylphenols under mild reaction conditions, linked to an ex situ formation of CO from N‐formylsaccharin. The carefully chosen catalytic system enables an efficient reaction with a novel functional group tolerance, despite the high polymerization tendency of the starting material.
Two‐Pot Synthesis of Chiral 1,3‐syn‐Diols through Asymmetric Organocatalytic Aldol and Wittig Reactions Followed by Domino Hemiacetal/Oxy‐Michael Reactions
Authors: Hayashi Yujiro , Saitoh Takanobu , Arase Hiromu , Kawauchi Genki , Takeda Naohiro , Shimasaki Yasuharu , Sato Itaru
Published: January 2018

A two‐pot synthetic method to construct the chiral syn‐1,3‐diol unit has been developed from three aldehydes and either Wittig or Horner–Wadsworth–Emmons reagents. In the first pot, chiral δ‐hydroxy α,β‐unsaturated ketones are synthesized with excellent enantioselectivity by the organocatalyst‐mediated asymmetric direct aldol reaction of two different aldehydes, followed by either Wittig or Horner–Wadsworth–Emmons reactions. In the second pot, domino acetalization with an aldehyde and subsequent oxy‐Michael reaction proceeds in the presence of NaClO4 and a catalytic amount of Bi(OTf)3 (OTf=trifluoromethanesulfonate) to provide the chiral 1,3‐syn‐diol derivative with excellent diastereoselectivity. Diospongin C and yashabushidiol A have been synthesized efficiently by using the present method as a key step.
Highly Stable, New, Organic‐Inorganic Perovskite (CH3NH3)2PdBr4: Synthesis, Structure, and Physical Properties
Authors: Liu Xixia , Huang Tang Jiao , Zhang Liuyang , Tang Baoshan , Zhang Nengduo , Shi Diwen , Gong Hao
Published: January 2018

Lead halide perovskites have attracted striking attention recently, due to their appealing properties. However, toxicity and stability are two main factors restricting their application. In this work, a less toxic and highly stable Pd‐based hybrid perovskite was experimentally synthesized, after exploring different experimental conditions. This new hybrid organic‐inorganic perovskite (CH3NH3)2PdBr4 was found to be an orthorhombic crystal (Cmce, Z=4) with lattice parameters a=8.00, b=7.99, c=18.89 Å. The Cmce symmetry and lattice parameters were confirmed using Pawley refinement and the atoms positions were confirmed based on DFT calculation. This perovskite compound was determined to be a p‐type semiconductor, with a resistivity of 102.9 kΩ cm, a carrier concentration of 3.4 ×1012 cm−3, and a mobility of 23.4 cm2 (V s)−1. Interestingly, XRD and UV/Vis measurements indicated that the phase of this new perovskite was maintained with an optical gap of 1.91 eV after leaving in air with a high humidity of 60 % for 4 days, and unchanged for months in N2 atmosphere; much more stable than most existing organic‐inorganic perovskites. The synthesis and various characterizations of this work further the understanding of this (CH3NH3)2PdBr4 organic‐inorganic hybrid perovskite material.
Revisiting empirical rules for the determination of the absolute configuration of cascarosides and other (ox‐)anthrones
Authors: Demarque Daniel P. , Pinho Danielle R. , Lopes Norberto P. , Merten Christian
Published: January 2018

The introduction of the C10‐stereocenter of (ox‐)anthrones by plant organisms is not stereospecific. Consequently, often, both (10S)‐ and (10R)‐diastereomers can be found in the same plant. Motivated by the importance of a correct assignment of the configuration at C10, this study revisits the nuclear magnetic resonance and electronic circular dichroism‐based empirical rules for the determination of the absolute configuration by molecular dynamic simulations and electronic circular dichroism spectrum calculations. Furthermore, a vibrational circular dichroism spectroscopic characterization of these large and conformationally very flexible molecules reveals spectral signatures, which can be used to specifically distinguish the C10 stereochemistry. A detailed analysis of the underlying vibrational modes suggests that the observed spectral pattern of the investigated cascarosides may be generally characteristic for the C10‐stereocenter of (ox‐)anthrones and that they can be used for empirical spectra‐structure correlations.
Ein Enzym für alle Fälle
Authors: Tetsch Larissa
Published: January 2018

Fruchtkörper von Ständerpilzen werden häufig Opfer von gefräßigen Insektenlarven. Dagegen verteidigen sie sich durch die Bildung von bioaktiven Substanzen. Hierzu gehören zwei unterschiedlich lange, verzweigtkettige Polyene, die der Schichtpilz BY1 als Reaktion auf eine Verletzung herstellt. Katalysiert wird ihre Synthese über eine einzige, neu entdeckte Polyketidsynthase, die dabei acht bzw. neun Doppelbindungen verschieben muss.
A Pharmacokinetic Study of an Ibuprofen Topical Patch in Healthy Male and Female Adult Volunteers
Authors: Lewis Fraser , Connolly Mark P. , Bhatt Aomesh
Published: January 2018

The pharmacokinetics of a novel locally applied ibuprofen topical patch was evaluated. Healthy subjects (n = 28) were administered a 200‐mg ibuprofen patch every 24 hours for 5 days, and steady‐state pharmacokinetics was determined. The amount of ibuprofen remaining in the patch following each patch removal was also assessed. The maximum steady‐state drug concentration and area under the concentration curve from time 0 on day 5 (t = 0) to the 24‐hours sample on day 6 were 514 ng/mL (95% CI 439 to 603 ng/mL) and 9.78 kg·h/mL (95% CI 8.43 to 11.4 kg·h/mL), respectively. Maximum ibuprofen concentration on day 5 occurred at 20 hours post–patch application. No evidence of drug accumulation was observed, and steady state was achieved between days 2 and 5. Ibuprofen levels attenuated rapidly to baseline within 24 hours after treatment discontinuation. The amount of ibuprofen remaining in the patch was high (≥80%). Treatment‐emergent adverse events were generally mild, with the most prevalent being headache (n = 6; 21.4%). Only 4 TEAEs were considered related to the ibuprofen patch: paresthesia (n = 1), headache (n = 2), and pruritic rash (n = 1). The study found that the systematic absorption of ibuprofen from a 200‐mg patch was low and that the levels of ibuprofen leaving the patch over a 24‐hour period are consistent with levels required for therapeutic relief as shown in other studies.
Theoretical Investigation of the Infrared Spectrum of 5‐Bromo‐2,4‐pentadiynenitrile from a CCSD(T)/B3LYP Anharmonic Potential
Authors: Dargelos Alain , Karamanis Panaghiotis , Pouchan Claude
Published: January 2018

On the grounds of a hybrid CCSD(T)/B3LYP/aug‐cc‐pVTZ anharmonic potential and the use of a variational and variational–perturbational methods, the IR spectra of 5‐bromo‐2,4‐pentadiynenitrile (BrC5N) is revisited in the mid‐infrared region up to 4500 cm−1. A position and intensity analysis of our theoretical results allow us to assign the fundamental bands together with their combinations and overtones, in the aforementioned range of frequencies. The main objective of this work is to give an “a priori” complete IR spectrum of BrC5N, which can be used as a guide for the low‐intensity bands in areas not completely studied so far.
Ultrathin Bismuth Nanosheets as a Highly Efficient CO2 Reduction Electrocatalyst
Authors: Su Panpan , Xu Wenbin , Qiu Yanling , Zhang Taotao , Li Xianfeng , Zhang Huamin
Published: January 2018

Electrochemical reduction of CO2 to value‐added products is an important and challenging reaction for sustainable energy study. Herein, bismuth nanosheets with thickness of around 10 nm were prepared through the electrochemical reduction of Bi3+. Ultrathin Bi nanosheets with numerous low‐coordination sites can efficiently reduce CO2 to formate in aqueous solution. Within the potential range of −0.9 to −1.2 V vs. reversible hydrogen electrode (RHE), the faradaic efficiency of formate is over 90 %, outperforming many Bi catalysts. At −0.7 V, the Bi nanosheets exhibit much higher current for formate generation than that of bulk Bi, attributed to a high surface area and also modified intrinsic electronic properties brought about by the ultrathin structure. DFT calculations demonstrate that Bi nanosheets have much higher density of states at the Fermi level compared to bulk Bi, favoring improved CO2 reduction on Bi nanosheets. At −1.0 V, Bi nanosheets exhibit high selectivity for formate and excellent stability during 5 h of electrolysis.
Low‐complexity energy efficient power allocation scheme for DAS with maximum power constraint
Authors: Yu Xiangbin , Wang Hao , Wen Benben , Liu Tao
Published: January 2018

In this paper, a low‐complexity optimal power allocation (PA) scheme is developed to maximize energy efficiency (EE) in a distributed antenna system (DAS) under maximum power constraint and target bit error rate (BER) requirement. Composite Rayleigh fading, multiple receive antennas, and dynamic circuit power consumption are all considered in the system. Unlike conventional schemes, the presented scheme provides a closed‐form expression of PA. Firstly, the optimization problem is formulated according to the definition of EE. Using the Karush‐Kuhn‐Tucker conditions, a general form of the optimal PA, in which the number of active antennas and corresponding power allocation are required only, is then proposed. With this general form, an effective algorithm is presented to yield the closed‐form PA. The proposed scheme can be applied to the system with static circuit power consumption and/or without target BER constraint to obtain optimal PA. Simulation results corroborate the effectiveness of the developed scheme, and the scheme can achieve the same EE performance as the existing optimal schemes with lower complexity. Moreover, the distributed antenna system with multiple receive antennas has higher EE than that with single receive antenna.
A series representation for multidimensional Rayleigh distributions
Authors: Wiegand Martin , Nadarajah Saralees
Published: January 2018

The Rayleigh distribution is of paramount importance in signal processing and many other areas, yet an expression for random variables of arbitrary dimensions has remained elusive. In this note, we generalise the results of Beard and Tekinay for quadrivariate random variables to cases of unconstrained order and provide a simple algorithm for evaluation. The assumptions of cross‐correlation between in‐phase and quadrature, as well as nonsingularity of the covariance matrix, are retained throughout our computations.