bluuebunny/crossref_metadata_2025 huggingface dataset:
A Free Radical Cascade Difunctionalization of o‐Vinylanilides with Simple Ketones and Esters
Authors: Tian Yunfei , Ge Yaxin , Zheng Luping , Yan Qinqin , Ren Yingming , Wang Zhenguang , Zhang Kailin , Wang Zhiqiang , Zhao Jincan , Li Zejiang
Published: October 2019

An efficient free radical cascade difunctionalization of o‐vinylanilides with ketones/esters has been developed. Through the selective activation of the α‐C(sp3)−H of ketones and esters, an addition/cyclization of carbon centered radical to o‐vinylanilides has been achieved. Various benzoxazines can be conveniently synthesized in this reaction system. In addition, we carried out a series of mechanistic studies and optical experiments.
Eine neue Dimension von Koordinationspolymeren und Metall‐organischen Gerüsten: hin zu funktionellen Gläsern und Flüssigkeiten
Authors: Horike Satoshi , Nagarkar Sanjog S. , Ogawa Tomohiro , Kitagawa Susumu
Published: October 2019

Es gibt zwei Kategorien von Koordinationspolymeren (CPs): anorganische CPs (i‐CPs) und durch organische Liganden verbrückte CPs (o‐CPs). Aufbauend auf dem Kristall‐Engineering von CPs diskutieren wir hier das Potenzial nichtkristalliner Zustände und Funktionalitäten als neue Forschungsrichtung für CPs. Die Kontrolle über flüssige oder glasartige Phasenzustände im Material ist wesentlich zum Erzielen bestimmter Eigenschaften und Funktionen. Mehrere Arbeiten zeigen die Möglichkeit, durch Umsetzung von Designprinzipien Flüssig/Glas‐Zustände in o‐CPs zu erreichen. Die Kombination der Metallionen und organischen Brückenliganden zusammen mit der Flüssig/Glas‐Phasenumwandlung belegt die Ähnlichkeit der o‐CPs zu ionischen Flüssigkeiten und anderen weichen ionischen Materialien. Synchrotronmessungen und Rechnungen tragen zur Aufklärung der Struktur und Dynamik der Flüssig/Glas‐Zustände der o‐CPs bei. Dies eröffnet die Möglichkeit zur Regulierung von Porosität, Leitfähigkeit, Transparenz und weiteren Materialeigenschaften. Die einzigartige Energielandschaft der Flüssig/Glas‐o‐CPs ermöglicht Eigenschaften und Funktionen, die komplementär zu denen kristalliner o‐CPs sind.
A novel biosensor for early diagnosis of liver cancer cases using smart nano‐magnetic metal–organic framework
Authors: Sheta Sheta M. , El‐Sheikh Said M. , Abd‐Elzaher Mohkles M. , Salem Salem R. , Moussa Hanan A. , Mohamed Reda M. , Mkhalid Ibraheem A.
Published: October 2019

For the first time, alpha‐fetoprotein (AFP) quantification as an early test for liver cancer diagnosis competing with other interfering analytes and factors based on a novel nano‐magnetic metal–organic framework (MOF) was investigated. The novel nano‐magnetic MOF was synthesized via a simple preparation method, and characterized using various techniques. The X‐ray photoelectron spectrum of the nano‐magnetic MOF shows Cu 2p, O 1s, N 1s and C 1s peaks that evidence the presence of these elements in the sample without any impurities. Scanning and transmission electron microscopy images show the nano‐magnetic MOF with average size between 22 and 43 nm. The results of a photoluminescence study show that the nano‐magnetic MOF exhibits strong emission at 418 nm after excitation at 354 nm. Moreover, a Stern–Völmer graph shows a linear calibration curve over an AFP concentration range 1.0–520 ng ml−1 with a correlation coefficient of 0.997, detection limit of 1.18 ng ml−1 and quantitation limit of 3.58 ng ml−1. According to the marked quenching of the photoluminescence intensity of the nano‐magnetic MOF using various concentrations of AFP, it was successfully used as a biosensor for AFP in serum samples collected from hepatitis patients in addition to healthy males and females. The quenching mechanism was well studied, and found to be a dynamic type. The present work offers a simple, low‐cost, room‐temperature and rapid technique, being non‐time‐consuming, highly accurate, selective and highly sensitive compared with most published methods.
2‐Acetyloxymethyl‐substituted 5,6,7‐trihydroquinolinyl‐8‐ylideneamine‐Ni(II) chlorides and their application in ethylene dimerization/trimerization
Authors: Li Jiaxin , Zhang Qiuyue , Hu Xinquan , Ma Yanping , Solan Gregory A. , Sun Yang , Sun Wen‐Hua
Published: October 2019

Six examples of 2‐acetyloxymethyl‐substituted 5,6,7‐trihydroquinolinyl‐8‐ylideneamine‐nickel(II) chlorides, [2‐(CH2OC(O)Me)‐8‐{N(Ar)}C9H8N]NiCl2 (Ar = 2,6‐Me2C6H3 Ni1, 2,6‐Et2C6H3 Ni2, 2,6‐i‐Pr2C6H3 Ni3, 2,4,6‐Me3C6H2 Ni4, 2,6‐Et2–4‐MeC6H2 Ni5, 2,4,6‐t‐Bu3C6H2 Ni6), have been prepared by a one‐pot template reaction of 2‐(hydroxymethyl)‐6,7‐dihydroquinolin‐8(5H)‐one with nickel dichloride hexahydrate, the corresponding aniline and acetic acid. All complexes were characterized by elemental analysis and IR spectroscopy, while dinuclear Ni2 and mononuclear Ni3·OH2 have additionally been the subject of single crystal X‐ray diffraction studies; in both structures the acetyloxymethyl group remained uncoordinated. On activationof Ni1 – Ni6 with MMAO, hexenes (C6: ca. 48% 1‐hexene) formed the major product of ethylene oligomerization along with minor quantities of butenes (C4); high overall activities of up to 1.33 × 106 g·mol–1 (Ni)h–1 (for mesityl‐containing Ni4) were achieved at 30 oCand 10 atm C2H4. By comparison with MAO as co‐catalyst, Ni1 – Ni6 exhibited lower activities but displayed a specificity towards ethylene dimerization (C4: 64–99% 1‐butene). Furthermore, sizable induction periods were a feature of the MAO runs with Ni1/MAO reaching peak catalytic activity only after 45 mins.
A triple‐shape memory material fabricated by in situ crosslinking of poly(butylene adipate‐co‐terephthalate)/ε‐polycaprolactone via electron‐beam irradiation and its triple‐shape memory effects
Authors: Wu Xianyou , Qian Jing , fu Chao , Tan Zhongyang , Gao Yixing , Ma Antong , Nie Wei , Ran Xianghai
Published: October 2019

In this work, we fabricated a triple‐shape memory polymeric material though in situ crosslinking of poly(butylene adipate‐co‐terephthalate)/ε‐polycaprolactone blends induced by electron beam irradiation. The intrinsic property of irradiation crosslinking, crosslinking rule in this heterogeneous system, formation of interfacial bridge molecular, and the resulted interfacial strength were investigated. No obvious interfacial slips were observed in tensile test, and the elongation at break was above 900%. The high‐temperature relaxation and recovery experiments at nonlinear region confirmed the excellent hyperelasticity and recovery ratios (Rr) can be as high as 95% for samples irradiated above 96 kGy. The mismatch between heating rate and relaxation kinetics resulted in both instable temporary shapes and heating‐mode dependent recovery behavior during the recovery process. Self‐stability of the temporary shape at middle temperature was also emphasized in view of the phenomenon that the second Rr was above 100% in our experiments. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48588.
Ultrathin, Porous and Oxygen Vacancies‐Enriched Ag/WO3−x Heterostructures for Electrocatalytic Hydrogen Evolution
Authors: Ren Yumei , Chen Zhonghui , Yu Xiangrong
Published: October 2019

Exploring advanced electrocatalysts for electrocatalytic hydrogen evolution is highly desired but remains a challenge due to the lack of an efficient preparation method and reasonable structural design. Herein, we deliberately designed novel Ag/WO3−x heterostructures through a supercritical CO2‐assisted exfoliation‐oxidation route and the subsequent loading of Ag nanoparticles. The ultrathin and oxygen vacancies‐enriched WO3−x nanosheets are ideal substrates for loading Ag nanoparticles, which can largely increase the active site density and improve electron transport. Besides, the resultant WO3−x nanosheets with porous structure can form during the electrochemical cycling process induced by an electric field. As a result, the exquisite Ag/WO3−x heterostructures show an enhanced hydrogen evolution reaction (HER) activity with a low onset overpotential of ≈30 mV, a small Tafel slope of ≈40 mV dec−1 at 10 mA cm−2, and as well as long‐term durability. This work sheds light on material design and preparation, and even opens up an avenue for the development of high‐efficiency electrocatalysts.
Current landscape of prenatal genetic screening and testing
Authors: Krstić Nevena , Običan Sarah G.
Published: October 2019

Pregnant patients should be offered the option of prenatal genetic screening and diagnostic testing. The type of screening and testing offered to a patient may depend on various factors including but not limited to age, family history, fetal findings, exposures, and patient preferences. Prenatal screening is available for a variety of genetic conditions including aneuploidy, congenital abnormalities, and carrier status. Diagnostic testing options include karyotype, prenatal microarray, as well as next‐generation sequencing. The various options differ in methodology, accuracy, timing and indication for testing, and information they provide. Given that the technologies related to prenatal testing are rapidly evolving and improving, the array of available screening and testing modalities are increasing. This article reviews the current offerings in prenatal screening and diagnosis.
Population-based study of morbidity risk associated with pathological complete response after chemoradiotherapy for rectal cancer
Authors: van der Sluis F J , Couwenberg A M , de Bock G H , Intven M P W , Reerink O , van Leeuwen B L , van Westreenen H L
Published: October 2019

Background

Neoadjuvant chemoradiotherapy (nCRT) for locally advanced rectal cancer may induce a pathological complete response (pCR) but increase surgical morbidity due to radiation-induced fibrosis. In this study the association between pCR and postoperative surgical morbidity was investigated.

Methods

Patients in the Netherlands with rectal cancer who underwent nCRT followed by total mesorectal excision between 2009 and 2017 were included. Data were stratified into patients who underwent resection with creation of a primary anastomosis and those who had a permanent stoma procedure. The association between pCR and postoperative morbidity was investigated in univariable and multivariable logistic regression analyses.

Results

pCR was observed in 976 (12·2 per cent) of 8003 patients. In 3472 patients who had a primary anastomosis, the presence of pCR was significantly associated with surgical complications (122 of 443 (27·5 per cent) versus 598 of 3029 (19·7 per cent) in those without pCR) and anastomotic leak (35 of 443 (7·9 per cent) versus 173 of 3029 (5·7 per cent) respectively). Multivariable analysis also showed associations between pCR and surgical complications (adjusted odds ratio (OR) 1·53, 95 per cent c.i. 1·22 to 1·92) and pCR and anastomotic leak (adjusted OR 1·41, 1·03 to 2·05). Of 4531 patients with a permanent stoma, surgical complications were observed in 120 (22·5 per cent) of 533 patients with a pCR, compared with 798 (20·0 per cent) of 3998 patients with no pCR (adjusted OR 1·17, 0·94 to 1·46).

Conclusion

Patients with a pCR in whom an anastomosis was created were at increased risk of developing an anastomotic leak.
Extraction of methyl xanthines and their UHPLC–DAD determination in consumable beverages used in Eastern province of Saudi Arabia
Authors: Ahmad Rizwan , Ahmad Niyaz , AlOthman Fatimah , Mohammad Haya , AlZahrani Fatimah
Published: October 2019

Coffee and tea are the most widely consumed beverages worldwide. However, the consumer may be unaware of the exact amount of methyl xanthine (MX, i.e. caffeine [C], theobromine [TB] and theophylline [TH]) consumed, as most of the products do not list the proper amounts. This may lead to serious risks including cardiovascular, kidney and stimulant effects. The aim of the study was to determine the MX amount in ready‐to‐use beverages (coffee and tea) collected from various outlets in the city of Al‐Khobar, Saudi Arabia. Forty different samples of espresso, black coffee and red tea were collected. A fast, reliable and efficient UHPLC–DAD method was developed and validated for MX determination. Total lipids were extracted and fractionated in order to determine glycolipids, phospholipids and neutral lipids. The r2 value for the method was 0.980–0.988 in a linearity range of 0.5–200 ppm. The range for MX (C [0.02–2.39 mg/ml], TB [0.00–0.10 mg/ml] and TH [0.00–0.004 mg/ml]) and total lipids was 1–5 g. The amount of glycolipids (3.1 g) was higher among the lipid fractions followed by phospholipids (1.8 g) and neutral lipids (0.25 g). In general, espresso beverages (20–30 ml) contained high amounts of MX whereas black coffee beverages contained high amount of lipids. Most of the beverages expressed C, TB, TH, lipids or their fractions; however, the product with high amounts of MX and lipids at the same time was espresso (brands Chemistry and Wogard). Although the MX and lipid levels in these beverages well below the allowed limits, care must still be taken, especially when using the beverages with high serving volumes (200–250 ml) or coffee prepared via the filter method i.e. black coffee, using a high temperature for a longer time.
Comparative absorption kinetics of seven active ingredients of Eucommia ulmoides extracts by intestinal in situ circulatory perfusion in normal and spontaneous hypertensive rats
Authors: Hu Hejia , Wu Linlin , Li Mei , Xue Cun , Wang Guangcheng , Chen Siying , Huang Yong , Zheng Lin , Wang Aimin , Li Yueting , Gong Zipeng
Published: October 2019

Eucommia ulmoides Oliv. (E. ulmoides) is a valuable and nourishing medicinal herb in China that has been used in the treatment of hypertension. Given the fact that most traditional Chinese medicine is mainly used to treat disease, investigating the pharmacokinetics of traditional Chinese medicines in the pathological state is more useful than that in the normal state. However, the differences in the absorption kinetics of active ingredients of E. ulmoides extract between pathological and physiological conditions have not been reported. Therefore, in this study, the rat intestinal in situ circulatory perfusion model was used to investigate the differences in absorption kinetics of seven active ingredients of E. ulmoides extract in normal and spontaneously hypertensive rats, namely, genipinic acid, protocatechuic acid, neochlorogenic acid, chlorogenic acid, cryptochlorogenic acid, (+)‐pinoresinol di‐O‐β‐D‐glucopyranoside and (+)‐pinoresinol 4′‐O‐β‐D‐glucopyranoside. Our results indicate that the pathological state of spontaneous hypertension may change the absorption of active components of E. ulmoides extracts, and these findings may provide a reference for improving the rational use of E. ulmoides in the clinic.
Validation and application of a novel UHPLC–MS/MS method for the measurement of furanodienone in rat plasma
Authors: Deng Zhipeng , Liu Qian , Wu Weihong , Wang Hong
Published: October 2019

A sensitive ultra‐high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) method was established to analyze furanodienone in rat plasma. In the process of chromatographic separation, selected reaction monitoring transitions for furanodienone and patchouli alcohol (internal standard, IS) were m/z 231.1 → 83.2 and m/z 205.1 → 95.1, respectively. Great linearity of furanodienone in plasma samples was found in the corresponding concentration range (r > 0.995). Intra‐ and inter‐day precisions (RSD, %) were <11.3% in plasma, and the accuracy (RE, %) was within ±10.7%. This method was used to the furanodienone study on rat pharmacokinetics after a single oral dose of 10 mg/kg of furanodiene. The results indicated that the maximum observed plasma concentration was 52.4 ± 19.1 ng/ml at 1.2 ± 0.7 h with an elimination half‐life of 2.2 ± 0.7 h. The obtained data indicated that furanodienone could be moderately distributed and eliminated.
Adaptive learning in a numerical methods course for engineers: Evaluation in blended and flipped classrooms
Authors: Clark Renee M. , Kaw Autar
Published: October 2019

As use of adaptive learning technology in STEM courses gains traction, studies evaluating its impacts are important to undertake. Adaptive e‐learning platforms provide personalized, flexible learning via monitoring of student progress and performance and subsequent provision of an individualized learning path containing various resources. In this study, adaptive technology was utilized in blended and flipped versions of a numerical methods course. A particular challenge with flipped instruction is preclass preparation, in which videos with the same instruction for all students are often assigned. Therefore, to diversify preclass learning, the instructor developed adaptive lessons via an NSF grant and rigorously assessed outcomes in this flipped class with adaptive learning. In addition, to fully evaluate the lessons and respond to calls from the literature, the lessons were implemented and evaluated in a blended version of the course, which was lecture‐based with available online resources. Data from previous semesters of flipped and blended instruction (without adaptive learning were available), enabling a comparison of four instructional methods. The comparisons consisted of direct assessment (i.e., exam questions) and affective assessment via a survey (i.e., perceptions of the classroom environment). An analysis was performed for students collectively and for underrepresented minority students in engineering. Focus groups enabled a comparison of student perspectives of using adaptive technology in blended versus flipped classrooms as well as by demographic. Upon combining these outcomes, including a notable Cohen's d = 0.34 for open‐ended‐response performance, the flipped classroom with adaptive learning may be the best method for this STEM course.
Flipped classroom in engineering: The influence of gender
Authors: Chiquito María , Castedo Ricardo , Santos Anastasio P. , López Lina M. , Alarcón Covadonga
Published: October 2019

The flipped classroom technique has been applied to a part (“Strength of Materials”) of a second‐year compulsory course called “Technology of Materials.” Due to the number of students, the course is divided into two groups – one taught with the traditional methodology (98 students), and the other taught with the flipped one (97 students). In the traditional methodology, the teacher explains the lesson and solves the problems, with students as passive actors in the learning process. In the developed flipped classroom model, the students have edited videos on an institutional online platform, available before each face‐to‐face session. In addition, a linked activity is used to check the students’ knowledge before class. The in‐class time is dedicated to briefly reviewing the concepts explained in the video, with a special emphasis on the errors detected in the link activity, followed by groups of students solving problems. The aim of this study is to present quantitative results of the effect of the flipped classroom in engineering with a focus on the gender of the students. The results show that the flipped classroom model has a direct impact on student grades, especially for female students, which presents significant differences when compared with males of the same group. In addition, the grade standard deviation values were lower, ensuring a better general level. The students of the flipped classroom group also attended the exams in a higher ratio than others, as these students are likely to feel more confident in the knowledge they have acquired.
A new risk score for patients after first recurrence of stage 4 neuroblastoma aged ≥18 months at first diagnosis
Authors: Kreitz Kiana , Ernst Angela , Schmidt René , Simon Thorsten , Fischer Matthias , Volland Ruth , Hero Barbara , Berthold Frank
Published: October 2019

Background

The prognosis of patients with recurrences from stage 4 neuroblastoma is not uniformly dismal. The evaluation of new therapies therefore needs to consider the individual risks of the treated patients. This study aims to define clinically useful risk criteria.

Patients and Methods

Inclusion criteria were: first recurrence of neuroblastoma stage 4 aged ≥18 months and enrollment in first line trials between 1997 and 2016. Patients were randomized into a training set (N = 310) and an independent validation set (N = 159). The primary endpoint was secondary event‐free survival. The individual treatment elements the patients received during initial and recurrent disease were analyzed as binary and time‐dependent variables. A five‐step multiple time‐dependent Cox regression analysis was performed on the training set to identify prognostic variables adjusted for the individual frontline treatment. The selected variables resulted in a prognostic index (PI) and were used to build a risk score system. The score was validated with the validation set.

Results

Of the 469 patients, 372 were treated with curative intent and 97 with palliative intent. The PI included the variables number of recurrence organs (hazard ratio [HR] = 2.27), time to recurrence (HR = 2.03), liver metastasis at diagnosis (HR = 1.77), first recurrence at site of the primary tumor (HR = 1.55), and age (HR = 1.29). Three risk groups were built and confirmed in the validation set. The scoring system was likewise useful for the curatively or palliatively treated subgroups.

Conclusion

A new risk score system for patients with first recurrence of stage 4 neuroblastoma aged ≥18 months at diagnosis is proposed.
CD4/CD8 + T cells, DC subsets, Foxp3, and IDO expression are predictive indictors of gastric cancer prognosis
Authors: Li Fangxuan , Sun Yao , Huang Jinchao , Xu Wengui , Liu Juntian , Yuan Zhiyong
Published: October 2019

Background

The tumor microenvironment represents an abnormal niche containing numerous factors, such as T cells, dendritic cells (DCs), regulatory T cells (Tregs), and indoleamine 2,3‐dioxygenase (IDO), involved in maintaining immune homeostasis and tolerance. All these factors may influence the choice of therapy and the clinical outcomes.

Methods

Flow cytometry was performed to identify CD4+/CD8 + T cells and DCs, and immunohistochemistry was used to evaluate IDO and Forkhead Box P3 (Foxp3) expression; these experiments were performed in order to explore the clinical and prognostic significance of CD4/CD8 + T cells, DCs, Tregs, and IDO expression in gastric carcinoma.

Results

Smaller tumor size was correlated with higher expression levels of peripheral CD4 + T cells (P = .003) and CD8 + T cells (P = .002), and lower IDO expression (P = .044) in tumors. Well‐differentiated gastric carcinomas displayed higher peripheral (P = .029) and tumor‐infiltrating CD4 + T cell (P = .009) populations and a higher tumor‐infiltrating DC1/DC2 ratio (P = .048). Gastric cancer in the early T stages exhibited higher populations of peripheral DC2s (P = .044) and a higher tumor‐infiltrating DC1/DC2 ratio (P = .012). Gastric cancer at the N0 stage had lower tumor‐infiltrating DC2s (P = .032) and a higher DC1/DC2 ratio (P = .037). IDO expression was positively correlated with tumor‐infiltrating Foxp3 + Tregs (P < .001) as well as DC2s (P < .001), whereas it was negatively correlated with the tumor‐infiltrating CD4/CD8 + T cell ratio (P = .023). Tumor‐infiltrating Foxp3 + Treg was positively correlated with tumor‐infiltrating DC2s (r2 = 0.772; P < .001). At T, N, and TNM stages, the expression levels of peripheral DC2s, tumor‐infiltrating DC1/DC2 ratios, Foxp3 + Tregs, and IDO were significantly correlated with prognosis (P < .05). The T stage and peripheral DC2s were significant risk factors for overall survival.

Conclusion

Immunocompetent cells and humoral immune factors, including DC2s, CD4+/CD8 + T cells, Foxp3 + Tregs, and IDO, interact with each other to compose a complex community of tumor immune microenvironment, ultimately affecting tumor progression and survival of gastric cancer.
Activation of CaMKII via ER‐stress mediates coxsackievirus B3‐induced cardiomyocyte apoptosis
Authors: Nie Jungang , Ta Na , Liu Lijuan , Shi Guoxiang , Kang Ting , Zheng Zeqi
Published: October 2019

Cardiomyocyte apoptosis contributes to the development of coxsackievirus B3 (CVB3)‐induced myocarditis, but the mechanism for the apoptosis by CVB3 infection remains unclear. Here, we showed that CVB3‐induced endoplasmic reticulum (ER) stress response and apoptosis in cultured H9c2 cardiomyocytes. We found that Ca2+‐calmodulin‐dependent kinase II (CaMKII) was activated by ER stress‐dependent intracellular Ca2+ overload in the CVB3‐infected H9c2 cardiomyocytes. Treatment with an inhibitor of ER stress, 4‐phenylbutyric acid (4‐PBA), attenuated intracellular Ca2+ accumulation indirectly and reduced CaMKII activity. Inhibition of CaMKII with pharmacological inhibitor (KN‐93) or short hairpin RNA reduced CVB3‐induced H9c2 apoptosis and repressed cytochrome c release from mitochondria to cytoplasm; whereas overexpression of the activated mutant of CaMKII (CaMKII‐T287D) enhanced CVB3‐induced H9c2 apoptosis and mitochondrial cytochrome c release, which could be alleviated by blocking of mitochondrial Ca2+ uniporter or mitochondrial permeability transition pore. Further in vivo investigation revealed that blocking of CaMKII with KN‐93 prevented cardiomyocytes apoptosis and improved cardiac contractile function in CVB3‐infected mouse heart. Collectively, these findings provide a novel evidence that CaMKII plays a vital role in the promotion of CVB3‐induced cardiomyocyte apoptosis, which links ER stress and mitochondrial Ca2+ uptake.
Switching of Kinetically Relevant Reactants for the Aqueous Cathodic Process Determined by Mass‐transport Coupled with Protolysis
Authors: Shinagawa Tatsuya , Obata Keisuke , Takanabe Kazuhiro
Published: October 2019

Electrocatalytic energy conversion driven by renewably generated electricity is a key technology to achieve a sustainable society in the future, namely, CO2 reduction and hydrogen production. Despite increasing research efforts dedicated to these reactions, there is no consensus regarding the proton source directly participating in surface reactions under non‐acidic pH conditions: Free proton (H+) versus proton‐containing species (e. g., H2O, HxPO4x−3, HyCO3y−2). We herein addressed this issue by rigorously quantifying the diffusion flux and protolysis rate during the aqueous hydrogen evolution reaction (HER). Our analysis revealed that there exists the linear free‐energy relationship (LFER) between the pKa and the rate of protolysis (HA→H++A−). Furthermore, the diffusion flux of the free proton as a consequence of the mass transport and protolysis failed to account for the typical current density of interest on the order of −10 mA cm−2 at non‐acidic pH levels when the Ka value and the molarity of the buffering species were low; e. g., <−0.1 mA cm−2 was attainable at pH >5 in 1.0 M KHCO3 (pKa=10.3). As a result, under such circumstance, the proton‐containing species is suggested to directly react on the surface during the cathodic electrocatalytic reactions.
The Aurivillius Compound CoBi2O2F4 – an Efficient Catalyst for Electrolytic Water Oxidation after Liquid Exfoliation
Authors: Yu Xiaowen , Mitoudi‐Vagourdi Eleni , Johnsson Mats
Published: October 2019

Investigation of new high‐efficiency catalysts for the oxygen evolution reaction (OER) is important for propelling the practical applications of water splitting. Here we report the Aurivillius compound CoBi2O2F4 to be a novel catalyst for catalytic OER. After liquid exfoliation of CoBi2O2F4 crystals in isopropanol, the resulting thin sheets deliver a low overpotential of 334 mV and a small Tafel slope of 47 mV dec−1 for catalytic OER, exhibiting substantially higher activity and faster kinetics compared with as‐synthesized crystals. This attributes to the increase in accessible surface area and dangling bonds on the edges providing more active sites exposed on the surface after exfoliation. The positive effects of F− anions to benefit OH− adsorption/combination and p‐block Bi3+ cations to direct reactants to preferred sites are proposed to synergistically improve the Co‐active centers for catalysis; based on this, the OER reaction mechanism on this new catalyst is discussed.
Ultrathin Two‐Dimensional Semiconductors for Photocatalysis in Energy and Environment Applications
Authors: Hu Sujuan , Zhu Mingshan
Published: October 2019

The search for highly active photocatalysts remains one of the most challenging tasks for realizing efficient solar energy utilization. Inspired by their unique and excellent physicochemical properties, ultrathin two‐dimensional (2D) semiconductors present great advantages in photocatalytic researches. In this review, we summarize the state‐of‐art progress on the ultrathin 2D semiconductors with a particular emphasis on their recent advances in energy and environment applications. First, we introduce the historical developments of 2D nanomaterials, and outline their advantages in terms of photocatalysis. Second, the classifications of ultrathin 2D semiconductors are summarized based on their structure and compositions. Further, various energy and environment applications including water splitting, CO2 reduction, N2 fixation, organic syntheses, NOx removal, water treatment, and sterilization in recent years (mainly in the recent 3 years) are highlighted in detail. Finally, the personal perspectives on future challenges and outlooks in the field of energy and environment applications are featured.
Post‐installed mechanical fasteners in high strength and ultra‐high strength performance concrete
Authors: Schwenn Michael , Voit Klaus , Zeman Oliver , Bergmeister Konrad
Published: October 2019

Post‐installed fastening systems are essential in structural engineering nowadays. Triggered by the increasing popularity of high strength concrete (HSC) and ultra‐high performance concrete (UHPC), fastening in these basements is more and more frequently applied. This inevitably leads to the question of the applicability of conventional fastening systems and the corresponding design concepts with concrete showing a compressive strength of up to 200 N/mm2. According to EAD 330232‐00‐0601, mechanical fasteners have to be placed in predrilled holes in compacted reinforced or unreinforced concrete without fibers with strength classes in the range of C20/25 to C50/60 in compliance with EN 206. This means that concrete strength class C50/60 also provides the reference for higher concrete strength; the impact of fibers and accompanying increase of concrete ductility is also excluded. Within the framework of this contribution it is intended to analyze the following aspects: (a) proof of applicability of various fastening systems in unreinforced and fiber‐reinforced high strength concrete via experimental investigations and (b) making a statement regarding the currently valid European Assessment Document and provide experimental background for this issue.
Hollow Nanotube Ru/Cu2+1O Supported on Copper Foam as a Bifunctional Catalyst for Overall Water Splitting
Authors: Gao Jing , Yang Liu , Wang Di , Cao Dapeng
Published: October 2019

Hydrogen energy is considered as one of the ideal clean energies for solving the energy shortage and environmental issues, and developing highly efficient electrocatalysts for overall water splitting to produce hydrogen is still a huge challenge. Herein, for the first time, Ru‐doped Cu2+1O vertically arranged nanotube arrays in situ grown on Cu foam (Ru/Cu2+1O NT/CuF) are reported and further investigated for their catalytic properties for overall water splitting. The Ru/Cu2+1O NT/CuF presents ultrahigh catalytic activities for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline conditions, and it exhibits a small overpotential of 32 mV at 10 mA cm−2 in the HER, and only needs 210 mV overpotential to achieve a current density of 10 mA cm−2 in the OER. Importantly, the alkaline electrolyzer using Ru/Cu2+1O NT/CuF as a bifunctional electrocatalyst only needs 1.53 V voltage to deliver a current density of 10 mA cm−2, which is much lower than the benchmark of IrO2(+)/Pt(−) counterpart (1.64 V at 10 mA cm−2). The excellent performance of the Ru/Cu2+1O NT/CuF catalyst is attributed to its high conductive substrate and special Ru‐doped nanotube structure, which provides a high electrochemical active surface area and 3D gas diffusion channel.
Highly Chemoselective gem‐Difluoropropargylation of Aliphatic Alcohols
Authors: Okamura Toshitaka , Egoshi Syusuke , Dodo Kosuke , Sodeoka Mikiko , Iwabuchi Yoshiharu , Kanoh Naoki
Published: October 2019

Despite the potential of α‐fluoroethers in medicinal chemistry, their synthetic methods, especially etherification of aliphatic alcohols, have been limited. Herein, we developed two‐ and three‐step gem‐difluoropropargylation of aliphatic alcohols including amino acid derivatives and naturally occurring bioactive molecules. Highly chemoselective etherification proceeded by using the gem‐difluoropropargyl bromide dicobalt complex in the presence of silver triflate and triethylamine. Decomplexation of dicobalt complexes was achieved by using cerium ammonium nitrate or N,N,N′‐trimethylethylenediamine. The thus obtained gem‐difluoropropargyl ethers were converted to various α‐difluoroethers which are expected to be useful for medicinal chemistry.
Gleaming Uranium: An Emerging Emitter for Building X‐ray Scintillators
Authors: Wang Yumin , Yin Xuemiao , Chen Junfeng , Wang Yaxing , Chai Zhifang , Wang Shuao
Published: October 2019

Scintillators are a unique class of luminescent materials with specific applications towards radiation detection. The emitters within state‐of‐the‐art scintillators are mostly limited to bismuth, cerium, europium, thallium, lead, tungsten, etc. A shared feature of these elements is the relatively high atomic number, which is responsible for high radiation stopping power and radiation‐induced luminescence. Searching for new scintillating materials is an essential target aiming at specific applications. In this Concept article, we will discuss our recent works on the topic of “uranyl‐bearing scintillators”. As a virgin territory in this field, uranyl‐bearing scintillators show intrinsic merits for designing new materials with X‐ray detection capability, that is, the large photoelectric cross‐section, high X‐ray attenuation efficiency, and high crystal density. In addition, we also present challenges in the further development of the uranyl‐bearing scintillators.
A novel chiral inorganic mesoporous silica used as a stationary phase in GC
Authors: He Yu‐Yu , Zhang Jun‐Hui , Pu Qing , Xie Sheng‐Ming , Li Yan‐Xia , Luo Lan , Chen Xue‐Xian , Yuan Li‐Ming
Published: October 2019

Chiral mesoporous silica (CMS) has attracted widespread attention because of some unique properties, such as high surface area, uniformly structured nanoscale cavities, and excellent chemical and thermal stability. In this work, we report the utilization of a CMS as the stationary phase for the separation of racemates in gas chromatography (GC). A CMS‐coated capillary column was fabricated by a dynamic coating method. Eighteen racemates belonging to different classes of organic compounds were separated on this column, including chiral alcohols, aldehydes, ketones, organic acids, halohydrocarbons, alkenes, alcohol amines, epoxides, and amino acid derivatives. In addition, linear alkanes, alcohols, and aromatic hydrocarbons have also been resolved.
Luftfilterwahl ohne Qual
Authors:   Camfil
Published: October 2019

Bei der Auswahl geeigneter Filtermedien müssen verschiedene Aspekte berücksichtigt werden, um eine adäquate Luftqualität für bestimmte Produktionsprozesse auch unter Ökonomisch vertretbaren Bedingungen zu schaffen.
Perfektes Zusammenwirken
Authors: Bucher Klaus
Published: October 2019

Das Einbringen pulverförmiger Zellulose in Flüssigkeit zum Ansetzen einer Filterschicht für hohe Filterqualität ist nur mit Einhaltung aller Vorschriften zur Gefahrenabwehr von möglichen Zünd‐ und Explosionsereignissen zu vollziehen. Der Filterspezialist Leiblein, Hardheim, marktführend mit mechanischen Filtereinrichtungen für Prozesswasser, bringt als neues Anlagenprodukt eine Dosierstation für Zellulose, Atex geprüft, auf den Markt.
3.000 Wege zur Trennung
Authors: Anlauf Harald
Published: October 2019

Die Verfahren und Apparate zur mechanischen Flüssigkeitsabtrennung werden permanent weiter‐ oder gar neu entwickelt. Neue Erkenntnisse aus der Forschung fließen in die Apparatekonstruktion ein. Neue Werkstoffe und Fertigungstechniken, wie etwa der 3D‐Druck werden genutzt. Moderne Sensor‐ und Datenübertragungstechnik ermöglicht die Fernüberwachung und ‐diagnose von Trennapparaten. Fortschritte in der numerischen Simulation und bei der Digitalisierung zeigen ganz neue Möglichkeiten auf.
The role of vimentin in directional migration of rat fibroblasts
Authors: Vakhrusheva Anna , Endzhievskaya Sofia , Zhuikov Vsevolod , Nekrasova Tatyana , Parshina Evgenia , Ovsiannikova Natalia , Popov Vladimir , Bagrov Dmitry , Minin Alexander А. , Sokolova Olga S.
Published: October 2019

Cell migration is one of the most important processes in which the cytoskeleton plays a main role. The cytoskeleton network is formed by tubulin microtubules, actin filaments, and intermediate filaments (IFs). While the structure and functions of the two aforementioned proteins have been extensively investigated during the last decades, vimentin IFs structure and their role in cell migration and adhesion remain unclear. Here, we investigated polarity determination in rat fibroblasts with either a knocked out vim gene or with a mutation that blocks filament formation on the stage of unit‐length filaments (ULFs). Structured illumination microscopy has demonstrated the difference in the morphology of IFs in wild‐type fibroblasts and of ULFs in mutant fibroblasts. We have developed an approach to measure cell stiffness separately on the trailing and leading edges using atomic force microscopy. Young's modulus values on the leading and trailing edge of migrating rat fibroblasts differ approximately by two times, being larger on the leading edge. The knockout of the vim gene leads to having comparable values of Young's moduli on both edges. Vimentin‐null cells change the direction of migration more frequently than those expressing wild‐type or mutated vimentin. Our results have shown the principle role of vimentin, not only in the form of IFs, but also as ULFs, in the determination of the polarity and the directionality of fibroblast migration.
Blinatumomab compared with standard of care for the treatment of adult patients with relapsed/refractory Philadelphia chromosome–positive B‐precursor acute lymphoblastic leukemia
Authors: Rambaldi Alessandro , Ribera Josep‐Maria , Kantarjian Hagop M. , Dombret Hervé , Ottmann Oliver G. , Stein Anthony S. , Tuglus Catherine A. , Zhao Xiaoyue , Kim Christopher , Martinelli Giovanni
Published: October 2019

Background

A single‐arm, phase 2 trial demonstrated the efficacy and safety of blinatumomab, a bispecific T‐cell–engaging antibody construct, in patients with relapsed/refractory (r/r) Philadelphia chromosome–positive (Ph+) acute lymphoblastic leukemia (ALL), a rare hematologic malignancy with limited treatment options. This study compared outcomes with blinatumomab with those of a historical control treated with the standard of care (SOC).

Methods

The blinatumomab trial enrolled adult patients with Ph+ ALL who were r/r to at least 1 second‐generation tyrosine kinase inhibitor (n = 45). Propensity score analysis (PSA) was used to compare outcomes with blinatumomab with those of an external cohort of similar patients receiving SOC chemotherapy (n = 55). The PSA mitigated confounding variables between studies by adjusting for imbalances in the age at diagnosis and start of treatment, sex, duration from diagnosis to most recent treatment, prior allogeneic hematopoietic stem cell transplantation, prior salvage therapy, and number of salvage therapies. Bayesian data augmentation was applied to improve power to 80% with data from a phase 3 blinatumomab study in r/r Philadelphia chromosome–negative ALL.

Results

In the PSA, the rate of complete remission or complete remission with partial hematologic recovery was 36% for blinatumomab and 25% for SOC, and this resulted in an odds ratio of 1.54 (95% confidence interval [CI], 0.61‐3.89) or 1.70 (95% credible interval [CrI], 0.94‐2.94) with Bayesian data augmentation. Overall survival favored blinatumomab over SOC, with a hazard ratio of 0.81 (95% CI, 0.57‐1.14) or 0.77 (95% CrI, 0.61‐0.96) with Bayesian data augmentation.

Conclusions

These results further support blinatumomab as a treatment option for patients with r/r Ph+ ALL.
Controlling the Formation of Peptide Films: Fully Developed Helical Peptides are Required to Obtain a Homogenous Coating over a Large Area
Authors: De Zotti Marta , Corvi Gabriele , Gatto Emanuela , Di Napoli Benedetta , Mazzuca Claudia , Palleschi Antonio , Placidi Ernesto , Biondi Barbara , Crisma Marco , Formaggio Fernando , Toniolo Claudio , Venanzi Mariano
Published: October 2019

The influence of conformational dynamics on the self‐assembly process of a conformationally constrained analogue of the natural antimicrobial peptide Trichogin GA IV was analysed by spectroscopic methods, microscopy imaging at nanometre resolution, and molecular dynamics simulations. The formation of peptide films at the air/water interface and their deposition on a graphite or a mica substrate were investigated. A combination of experimental evidence with molecular dynamics simulation was used to demonstrate that only the fully developed helical structure of the analogue promotes formation of ordered aggregates that nucleate the growth of micrometric rods, which give rise to homogenous coating over wide regions of the hydrophilic mica. This work proves the influence of helix flexibility on peptide self‐organization and orientation on surfaces, key steps in the design of bioinspired organic/inorganic hybrid materials.
A Family of Heterocyclic Naphthalene Diimide (NDI) Analogues: Comparing Parent Isoquinoline Diimides and Phthalazine Diimides with NDI
Authors: Insuasty Alberto , Carrara Serena , Tang Linjing , Forsyth Craig , Hogan Conor F. , McNeill Christopher R. , Langford Steven J.
Published: October 2019

Parent isoquinoline diimide (IQDI) and phthalazine diimide (PTDI), as two new heterocyclic analogues of naphthalene diimides (NDIs), have been synthesized through an oxidative strategy in 35–79 % yield. X‐ray crystallography has been used to support the formation of IQDI, which also show fluorescence quantum yields of 3.5 %. The electrochemical and electrical properties of these molecules have been studied. The electrochemical results show an interesting trend in first reduction potential PTDI<IQDI<NDI and 0.1 eV changes in the optical band gap (Eg) leading to the trend IQDI<NDI<PTDI, as supported by DFT calculations. While initial top gate OFET devices yield charge mobilities less than NDIs, the basis of this study intimates that IQDIs and PTDIs hold promise for applications commensurate with NDIs.
Redefining Blood Pressure Assessment — The Role of the Ambulatory Blood Pressure Monitoring Study for Drug Safety
Authors: Garnett Christine , Johannesen Lars , McDowell Tzu‐Yun
Published: October 2019

According to models developed from large epidemiological studies, mean increases in systolic blood pressure of 2–3 mmHg can increase the risk of cardiovascular (CV) adverse events, especially in patients with a high risk for CV disease. There are new regulatory recommendations for the use of a safety ambulatory blood pressure monitoring (ABPM) study to assess the blood pressure (BP) effects of drugs used chronically. The ABPM study collects BP measurements over 24 hours at baseline and during treatment in patients with underlying CV risk. Our evaluation of ABPM studies submitted to the US Food and Drug Administration (FDA) shows these studies can provide precise estimates of BP changes and lack a pronounced placebo response. With the assessment of BP effects in development programs, opportunities exist for developing quantitative safety models to predict CV risk, support dose selection, identify patients with increased BP response, and provide insight into underlying mechanisms.
Enhanced Kinetics over VS4 Microspheres with Multidimensional Na+ Transfer Channels for High‐Rate Na‐Ion Battery Anodes
Authors: Li Wenbin , Huang Jianfeng , Li Ruizi , Cao Liyun , Li Xifei , Chen Shaoyi , Feng Liangliang
Published: October 2019

Developing 3 D self‐assembled nanoarchitectures with well‐defined crystal structures is an effective strategy to enhance the electrochemical performances of electrode materials. (1 1 0)‐oriented and bridged‐nanoblocks self‐assembled VS4 microspheres are controllably synthesized by a facile one‐step hydrothermal method. The (1 1 0)‐bridged structure sets up open pathways for Na+ diffusion among nanoblocks, and the (1 1 0)‐oriented structure provides unobstructed pathways for Na+ diffusion in the nanoblocks, which collectively constructs multidimensional Na+ transfer channels in the VS4 microspheres, promoting the electrochemical kinetics. As an anode for Na‐ion batteries (SIBs), this material exhibits pseudocapacitive Na+ storage and excellent rate capability, delivering high capacities of 339 and 270 mAh g−1 at rates of 0.1 and 2.0 A g−1, respectively, with a capacity retention of 79 % in the voltage window of 0.5–3.0 V. In particular, the reversible capacity reaches 575 mAh g−1 after 300 cycles even at 1.0 A g−1 in the voltage window of 0.05–3.0 V, outperforming those of the ever‐reported VS4‐based anode materials. This work presents an effective strategy to the exploration and design of high‐performance anodes for SIBs.
Accounting for heterogeneity in false‐positive detection rate in southeastern beach mouse habitat occupancy models
Authors: Stolen Eric D. , Oddy Donna M. , Gann Shanon L. , Holloway‐Adkins Karen G. , Legare Stephanie A. , Weiss Stephanie K. , Breininger David R.
Published: October 2019

Habitat occupancy models, designed to deal with non‐detection of a target species in occupied sites, have been expanded to allow for false‐positive detections when species are mistakenly detected in unoccupied sites. When a subset of the data are unambiguous detections, such occupancy models can produce reliable results. However, if not properly accounted for, heterogeneity in the rate of false‐positive detection between sites may bias estimates of habitat occupancy. We studied habitat occupancy of the southeastern beach mouse (Peromyscus polionotus niveiventris), a species along Florida's Atlantic coast that is threatened due to the reduction of its core range by over 79% since 1950. Southeastern beach mice were detected based on their footprints in track tubes, but because of co‐occurrence of the cotton mouse (Peromyscus gossypinus) with overlapping footprint size, we had to allow for possible false‐positive detections. Differences in the relative abundance of these two species between habitats may have resulted in heterogeneity in the false‐positive rate. By combining uncertain (track tube) and certain (live capture) detection methods, we were able to use covariates to account for heterogeneity in false‐positive detection rates between habitats. Southeastern beach mouse habitat occupancy was higher in coastal dune and strand habitat than in coastal scrub or interior scrub habitats. The rate of false‐positive detections was much higher in coastal scrub habitat than in coastal dune and strand habitat or interior scrub habitat, reinforcing the need for methods that accommodate heterogeneity in the rate of false positives to reduce bias in estimates of habitat occupancy. Using simulations, we show that heterogeneity in the false‐positive detection rate leads to bias in habitat occupancy estimates unless properly accounted for. We also discuss how differences in relative abundance between the target species and a confusing species can directly impact the heterogeneity of false‐positive detections.