bluuebunny/crossref_metadata_2025 huggingface dataset:
Predicting the Success of Ensemble Algorithms in the Banking Sector
Authors: Dağ Özge Hüsniye Namlı
Published: September 2019

The banking sector, like other service sector, improves in accordance with the customer's needs. Therefore, to know the needs of customers and to predict customer behaviors are very important for competition in the banking sector. Data mining uncovers relationships and hidden patterns in large data sets. Classification algorithms, one of the applications of data mining, is used very effectively in decision making. In this study, the c4.5 algorithm, a decision trees algorithm widely used in classification problems, is used in an integrated way with the ensemble machine learning methods in order to increase the efficiency of the algorithms. Data obtained via direct marketing campaigns from Portugal Banks was used to classify whether customers have term deposit accounts or not. Artificial Neural Networks and Support Vector Machines as Traditional Artificial Intelligence Methods and Bagging-C4.5 and Boosted-C.45 as ensemble-decision tree hybrid methods were used in classification. Bagging-C4.5 as ensemble-decision tree algorithm achieved more powerful classification success than other used algorithms. The ensemble-decision tree hybrid methods give better results than artificial neural networks and support vector machines as traditional artificial intelligence methods for this study.
On Integration Linguistic Factors to Fuzzy Similarity Measures and Intuitionistic Fuzzy Similarity Measures
Authors: Phong Pham Hong , Hue Vu Thi
Published: September 2019

The article is concerned with integrating linguistic elements into fuzzy similarity measures and intuitionistic fuzzy similarity measure. Some new concepts are proposed: a fuzzy linguistic value (FLv), a fuzzy linguistic vector (FLV), an intuitionistic fuzzy linguistic vector (ILV) and similarity measures. The proposed measures are used to build classification algorithms. As predicted theoretically, experiments show that with the same type of similarity measures, the linguistic-aggregated similarity measures produce better results in classification problems.
Amiodarone-Induced Thyrotoxicosis in a Pediatric Patient: A Rare and Demanding Clinical Case
Authors: Oliveira Sofia , Marques Bernardo , Laranjo Sérgio , Lopes Lurdes
Published: September 2019

Thyroid dysfunction is one of the most common adverse effects of amiodarone therapy, ranging from subclinical changes to overt clinical thyrotoxicosis (AIT) and/or hypothyroidism. Due to its heterogeneity, AIT lasts as a defiant entity, leading to a thorny treatment course, particularly in pediatrics. AIT can be classified as either type 1, type 2 or mixed form based on its pathophysiology. Differentiating between the main AIT subtypes is quite relevant, since there is specific treatment for both, however, this distinction may be difficult in clinical practice. We describe a rare case of AIT in a pediatric patient, with an uncommon congenital cardiac malformation, that started amiodarone therapy due to paroxysmal supraventricular tachycardia. AIT was reported 26 months after drug onset, with a sudden and explosive emerging. This case highlights the current AIT management challenges on the highdemanding pediatric field pursuing, ultimately, an enhanced patient´'s care.
A Cidadania Submersa. O Trabalho Doméstico na Itália entre os Séculos XIX e XX
Authors: Passaniti Paolo
Published: September 2019

O artigo retoma o tema da história do trabalho doméstico enquanto cidadania invisível, grande contradição da ordem jurídica burguesa que se afirma em torno da unificação do sujeito de direito: uma sociedade nivelada com base na igualdade entre cidadãos proprietários, em que não há mais lugar para a condição servil, ao menos em teoria. Em virtude da nítida separação entre família e trabalho, na família burguesa o trabalho doméstico se torna sempre mais uma prerrogativa feminina. Um trabalho sem direitos, fundado ainda sob uma ideia de benevolênciaque não pode ser contratualizada. O trabalho doméstico foi regulado na Itália em 1958, momento em que, na era da modernização social e do milagre econômico, as famílias encontraram sempre mais dificuldades para achar profissionais domésticos. O serviço doméstico, cada vez mais em declínio no plano social, reaparece nos anos noventa no trabalho de cuidadores dentro do fenômeno da assistência aos idosos não autossuficientes. Encontram-se, assim, duas debilidades que o direito vê somente em parte: a fragilidade e a solidão dos idosos de um lado, e a pobreza das cuidadoras que, na busca por um futuro melhor, aceitam uma condição fora dos parâmetros do direito do trabalho.
Mundos do trabalho em diálogo: a importância das interseções para a História do Trabalho
Authors: Silva Alessandra Belo Assis
Published: September 2019

SURIANO, Juan; SCHETTINI, Cristiana (org.). Historias cruzadas: diálogos historiográficos sobre el mundo del trabajo en Argentina y Brasil. Buenos Aires: Teseo, 2019.
O XI Congresso Nacional das Trabalhadoras Domésticas e a luta por direitos no Brasil
Authors: Sousa Juliana
Published: September 2019

Articulando as dimensões de raça, gênero e classe social, este artigo analisa a luta coletiva das trabalhadoras domésticas remuneradas por direitos no Brasil, a partir das discussões realizadas em encontros da categoria, com destaque para o XI Congresso Nacional das Trabalhadoras Domésticas promovido pela FENATRAD, em 2016, no Rio de Janeiro.
Photolysis and oxidation by OH radicals of two carbonyl nitrates:
4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone
Authors: Picquet-Varrault Bénédicte , Suarez-Bertoa Ricardo , Duncianu Marius , Cazaunau Mathieu , Pangui Edouard , David Marc , Doussin Jean-François
Published: September 2019

Abstract. Multifunctional organic nitrates, including carbonyl nitrates, are important species formed in NOx rich atmospheres by the degradation of VOCs. These compounds have been shown to play a key role in the transport of reactive nitrogen and consequently in the ozone budget, but also to be important components of the total organic aerosol. However, very little is known about their reactivity in both gas and condensed phases. Following a previous study we published on the gas-phase reactivity of β-nitrooxy ketones, the photolysis and the reaction with OH radicals of 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone, respectively a β-nitrooxy ketone and a γ-nitrooxy ketone, were investigated for the first time in simulation chambers. Ambient photolysis frequencies calculated for 40° latitude North were found to be (4.2 ± 0.6) × 10−5 s−1 and (2.2 ± 0.7) × 10−5 s−1 for 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone, respectively. These results demonstrate that photolysis is a very efficient sink for these compounds with atmospheric lifetimes of few hours. It was also concluded that, similarly to α-nitrooxy ketones, β-nitrooxy ketones have enhanced UV absorption cross sections and quantum yields equal or close to unity. γ-nitrooxy ketones have been shown to have lower enhancement of cross sections which can easily be explained by the increasing distance between the two chromophore groups. Thanks to a products study, branching ratio between the two possible photodissociation pathways are also proposed. Rate constants for the reaction with OH radicals were found to be (2.9 ± 1.0) × 10−12 cm3 molecule−1 s−1 and (3.3 ± 0.9) × 10−12 cm3 molecule−1 s−1, respectively. These experimental data are in good agreement with rate constants estimated by the SAR of Kwok and Atkinson (1995) when using the parametrization proposed by Suarez-Bertoa et al. (2012) for carbonyl nitrates. Comparison with photolysis rates suggests that OH-initiated oxidation of carbonyl nitrates is a less efficient sink that photodissociation but is not negligible in polluted area.
LASER SCANNING FOR BIM AND RESULTS VISUALIZATION USING VR
Authors: Pavelka jr. K. , Michalík B.
Published: September 2019

Abstract. Virtual Reality (VR) is a highly topical subject in many branches of science and industry. Thanks to the rapid development and advancement of computer technology in recent years, it can now be used to a large extent, with more detail to show and is now more affordable than before. The use of virtual reality is currently devoted to many disciplines and it can be expected that its popularity will grow progressively over the next few years. The Laboratory of Photogrammetry at the Czech Technical University in Prague is also interested in VR and focuses mainly on documentation and visualization of historical buildings and objects. Our opinion is that in the field of virtual reality there is great potential and extensive possibilities. 3D models of historical objects, primarily created by photogrammetric IBRM technology (image based modelling and rendering) or by laser scanning, gain a completely different perspective in VR. In general, most of the newly designed buildings are now being implemented into BIM. For certain projects, historical buildings or constructions should also have implemented into BIM. As a basic input into BIM, an accurate 3D spatial documentation of the condition is needed with special accent to additional information like engineering networks, materials, etc. Creating BIM is one thing, visualizing a model is another. The historical object is irregular and it is difficult to create its simplified form as the CAD model; it is much easier with modern buildings. The question is always the appropriate type of visualization, where virtual reality can be a very useful technology. So-called game engines such as Unreal engine or Unity are used to create a virtual world. These are highly sophisticated tools that make it possible to create a suitable environment, where you can place created models and then view and analyse them with the help of VR glasses. In our contribution, we would like to show an example of a technology line that allows you to convert an object documented by laser scanning into virtual reality. An older industrial building prepared for future reconstruction was chosen as a case study. This object was scanned by a laser scanner, a 3D model was created and material types and engineering networks were added into the model.
IMMERSIVE VISUALISATION OF CONSTRUCTION SITE POINT CLOUD DATA, MESHES AND BIM MODELS IN A VR ENVIRONMENT USING A GAMING ENGINE
Authors: Vincke S. , de Lima Hernandez R. , Bassier M. , Vergauwen M.
Published: September 2019

Abstract. By adopting Building Information Modelling (BIM) software, the architecture, engineering and construction (AEC) industry shifted from a two-dimensional approach to a three-dimensional one in the design phase of a building. However, a similar three-dimensional approach for the visualisation of the current state of the construction works is lacking. Currently, progress reports typically include numerous pictures of the construction site or elements, alongside the appropriate parts of the 3D as-design BIM model. If a proper transition to a 3D design versus 3D current state were achieved, the evolved type of reports would become more comprehensible, resulting in more well-informed decision-making. This requires a single, unique software platform that is able to import, process, analyse and visualise both the as-design BIM model as well as the recorded data of the current construction state. At present however, the visualisation and interpretation of the different datasets alone requires already multiple software packages.As a partial solution this work presents a platform to easily visualise and interpret various data sources such as point clouds, meshes and BIM models and analysis results. Recent advances of gaming engines focus on and allow for an excellent visualisation of mesh data. Therefore all of the aforementioned data sources are converted into mesh objects upon importing. Moreover, gaming engines provide the necessary tools to traverse the scene intuitively allowing construction site managers and other stakeholders to gain a more complete and better oversight of the construction project. Furthermore, these engines also provide the possibility to take the immersion to the next level: incorporating the 3D entities into a Virtual Reality (VR) environment makes the visualised data and the executed analyses even more comprehensible.By means of a case study, the potential of the presented approach is showcased. The real-world construction site recordings, models and analyses are visualised and implemented in VR using the Unity gaming engine.
BIM, STRUCTURAL ANALYSIS AND COMMUNICATION USING COMMON DATA ENVIRONMENT (CDE) IN THE FIELD OF WATER MANAGEMENT
Authors: Vlasák P. , Čerbák B.
Published: September 2019

Abstract. Presentation consists of three parts, which are interconnected:BIM application for plants treatment and other complicated structures in the field of water managementStatics of water management structures in the BIM environmentApplication of Common Data Environment (CDE) for water managementTwo areas – statics and water management technology – are crucial for water management structures. Speaking of statics, we mean the statics of reinforced concrete structures. In our company AQUA PROCON s.r.o. we deal with this area comprehensively, ie. from the initial design in the BIM architectural and construction software, through transferring a load-bearing model to BIM software for 3D reinforcement modelling to evaluating model in static design software. All communication is held in Common Data Environment (CDE). Within this environment, a three-way communication is carried out by the designer, contractor and contracting authority. Part of our performance is also above-standard support for reinforced concrete contractors. We provide models of reinforced concrete structures in LOD 400. The use of Common Data Environment (CDE) does not concern only statics, but also the work of all other professions and project participants. Our activities and workflows are based on the philosophy of OPENBIM and IFC.
The Homosexual Male Gaze: Normalizing Homosexuality through the Use of Heteronormative Narrative Techniques in Film
Authors: Rohrs Lauren
Published: September 2019

An examination of the use of Mulvey’s “male gaze” by a homosexual character in the 2017 adaptation of Beauty and the Beast. Explores the potential of the use of this heteronormative narrative technique in the normalization of homosexuality in film and society.
The Effect of Portfolio Diversification for the Bursa Malaysia
Authors: Mohd Norsiman Nadia Nadira , Yakob Noor Azuddin , Jr Carl B. McGowan,
Published: September 2019

This paper examines the effect of portfolio diversification for stocks listed on the Malaysian stock exchange. We determine the extent to which the unsystematic risk component can be reduced through diversification posited by Modern Portfolio Theory. Prices of randomly selected stocks were obtained from Yahoo! Finance for the five year period starting from January 2010 to March 2014. In order to analyze the robustness of the empirical results, three sets of portfolios were tested in this study and each set contained 55 stocks. The total sample of 165 stocks was chosen from different sectors that are listed under Bursa Malaysia. In addition, the three samples were tested for two type of differencing intervals, daily and weekly, to obtain more robust results. The empirical findings of the study show that increasing the number of stocks in the sample portfolio leads to decreasing standard deviation (unsystematic risk) the investment portfolio for Malaysia Stock Market stocks until each portfolio is well-diversified. The uniqueness in this study is that the empirical results show that, the level of data frequency significantly influences changes in stock portfolio size required to obtain optimal portfolio diversification.  Using the daily differencing interval, 45 stocks are need to eliminate unsystematic risk and using the weekly differencing interval, only 35 stocks are required to obtain a well-diversified portfolio.
Learner Translator Corpus: Italogreco or Another Way to Confirm Teachers’ Intuitions
Authors: Florou Katerina
Published: September 2019

This paper describes a project developed within an ongoing study at the University of Athens. In our previous studies we analyzed the errors of Greek learners of Italian language, using Learner Corpora evidence and we retrieved useful information about their interlanguage and its interaction to the language learning process. In this study we assume interlanguage is a tool that can help us to distinguish the language errors from the translation errors and identify the most frequent errors and the causes. For this reason, we focus on specific linguistic areas and we examine a learner translator Corpus. The results are interestingly different from the ones that a language teacher would expect.
Methylmercury Determination in Fish by Direct Mercury Analyzer
Authors: Kim Tae-Hun , Cho Min-Ja , Lee Yongmin , Kim Ji Hui , Hwang Jeong-Yun , Lee Hye-Eun , Kim Sheen-Hee , Choi Jang-Duck , Kang Gil-Jin
Published: September 2019

Background: There are two methods for quantifying methylmercury (MeHg) in fish using GC–electron capture detection (ECD): AOAC INTERNATIONAL Official Method 988.11 and the Korean Food Code (KFC) method. Both of these methods consume a large amount of chemicals and require long pretreatment times because of several complicated MeHg extraction steps. Objective: In this study, a new method for the simple and rapid determination of MeHg in fish has been developed. The method is based on the investigation of oxygen combustion–gold amalgamation using a direct mercury analyzer (DMA) after the complete removal of MeHg by organic extraction and back-extraction to an aqueous medium. Methods: The DMA is suitable for the analysis of both solid and liquid materials and has a good detection limit. The developed method was validated by comparing the MeHg recoveries (%) of both certified reference materials and the market-purchased fish samples with the MeHg concentration obtained using the KFC method. Results: The following parameters pertaining to the developed method were established: detection limit, 1.02 μg/kg; LOQ, 3.09 μg/kg; linearity (r), 0.9998; range, 0.1–300 μg/kg; and recovery, 95–97%. Conclusions: Our method is a promising alternative by virtue of its much simpler and faster sample pretreatment procedure, with a MeHg recovery as high as that of the KFC method. Highlights: The developed method enables the simultaneous analysis of total Hg and MeHg with only DMA equipment.
Gerichtsstandsklauseln in der privaten Durchsetzung des EU-Kartellrechts
Authors: Westerhoven Polina
Published: September 2019

This book explores the issues surrounding cartel damage claims from an EU law perspective. It follows an analysis of the existing EU legal framework for private competition law enforcement with a thorough examination of the relevant rules on international jurisdiction. Against this background, the author focuses on the role of jurisdiction agreements in the area of private enforcement. The study covers both the choice of Member State courts as well as the prorogation of third state forums and provides an interesting perspective on the various questions that arise in this context. With regard to the highly debated issue of the interpretation of choice-of-court clauses, it highlights the need to observe the guidelines deriving from the Brussels I Regulation itself. It furthermore outlines the system applicable to third state prorogations and examines how to deal with situations in which the choice of a third state forum may lead to the circumvention of EU competition rules.
Gastrointestinal Pathologies Recorded at the Felix Houphouet-boigny University Community Health Center from 2013 to 2017 (Abidjan - Ivory Coast)
Authors: N’gbesso N’gbesso Jean-Paul , Demedeiros Kanga , Ahoua Allou Aimé Constantin , Landry Arra A. Juli , Cisse Doumbia Mariamou , Mambey Serge , N’guessan Okoubo Née Nicaise A.
Published: September 2019

Background: Gastrointestinal pathologies constitute a significant public health problem for the Ivory Coast, particularly for populations living under conditions of poor hygiene.

Aims: The purpose of this study is to evaluate the prevalence of gastrointestinal pathologies within the student body attending the Felix Houphouet-Boigny University Community Health Center.

Place and Duration of Study: The study was conducted in the university center of the university Felix Houphouet-Boigny de Cocody to the south of the Ivory Coast between January to February 2018.

Methodology: It consisted of a documentary investigation which was carried out by consulting the medical files of the patients.

Results: The results revealed that gastrointestinal pathologies constituted the third principal cause of affection in the students with 16% of the consultations. This study permitted to evaluate the level of prevalence of gastrointestinal pathologies of 2013 to 2017.

Conclusion: From this study, it was concluded that gastrointestinal pathology was a health problem for this student population.
Surgical Venous Cutdown for the Insertion of Totally Implantable Venous Access Devices
Authors: Tsukiyamam Naofumi , Shimomura Manabu , Toyota Kazuhiro , Karakuchi Nozomi , Ono Kosuke , Shishida Masayuki , Oishi Koichi , Miyamoto Kazuaki , Ikeda Masahiro , Sadamoto Seiji , Egi Hiroyuki , Ohdan Hideki , Takahashi Tadateru
Published: September 2019

Purpose:

Stable insertion of totally implantable venous access devices (TIVADs) is mandatory for the administration of chemotherapy and parenteral nutrition. Subclavian venipuncture is the most popular route; however, perioperative complications occur in up to 12% of patients. We inserted TIVADs by surgical venous cutdown of the cephalic vein at the deltopectoral groove with the intention of a safe and stable implantation.

Methods:

We implanted TIVADs in 318 consecutive patients (331 cases) from January 2011 to December 2015. We retrospectively analyzed short- and long-term treatment outcomes and risk factors for primary failure of implantation and removal due to catheter-related complications.

Results:

The aim of implantation was chemotherapy in 198 cases, nutrition in 92 cases, and frequent intravenous drip in 41 case. Surgical venous cutdown was performed in 321 of 331 cases (97%); primary failure occurred in 42 cases (13.1%). Short-term complications occurred in 4 cases (1.2%), and there were no serious complications, such as pneumothorax. In the analysis of risk factors for primary failure, aim of implantation (chemotherapy versus nutrition versus frequent intravenous drip) was the only risk factor (P = 0.02). Removals occurred in 35 cases (11.5%). In the analysis of risk factors for removal due to complications, presence of infectious disease was identified as the only significant risk factor (P < 0.001).

Conclusions:

We confirmed the safety and efficacy of the cutdown method and clarified the risk factors for primary failure and removal. The cutdown method was safe and was not associated with serious complications; however, selective implantation was needed to achieve a high success rate.
Intrinsic mitotic activity supports the human salivary gland acinar cell population
Authors: Ingalls Matthew H. , Hollomon Andrew J. , Newlands Shawn D. , McDavid Andrew N. , Ovitt Catherine E.
Published: September 2019

To develop treatments for salivary gland dysfunction, it is important to understand how human salivary glands are maintained under normal homeostasis. Previous data from our lab demonstrated that murine salivary acinar cells maintain the acinar cell population through self‐duplication under conditions of homeostasis, as well as after injury. Early studies suggested that human acinar cells are mitotically active, but the identity of the resultant daughter cells was not clear. Using markers of cell cycle activity and mitosis, as well as an ex vivo 5‐Ethynyl‐2´‐deoxyuridine assay, we show that human salivary gland acinar cells divide to generate daughter acinar cells. As in mouse, our data indicate that human salivary gland homeostasis is supported by the intrinsic mitotic capacity of acinar cells.
Improving treatment efficiency via photon optimizer (PO) MLC algorithm for synchronous single‐isocenter/multiple‐lesions VMAT lung SBRT
Authors: Sanford Lana , Pokhrel Damodar
Published: September 2019

Purpose

Elderly patients with multiple primary or oligometastases (<5 lesions) lesions with associated co‐morbidities may not retain their treatment position for the traditional long SBRT treatment time with individual isocenters for each lesion. Treating multiple lesions synchronously using a single‐isocenter volumetric arc therapy (VMAT) plan would be more efficient with the use of the most recently adopted photon optimizer (PO) MLC algorithm and improve the patient comfort. Herein, we quantified the clinical performance of PO versus its predecessor progressive resolution optimizer (PRO) algorithm for single‐isocenter/multiple‐lesions VMAT lung SBRT.

Materials and methods

Fourteen patients with metastatic non‐small‐cell lung cancer lesions (two to five, both uni‐ and bilateral lungs) received a highly conformal single‐isocenter co/non‐coplanar VMAT (2–6 arcs) SBRT treatment plan. Patients were treated with a 6X‐FFF beam and Acuros algorithm with a single‐isocenter placed between/among the lesions, using PO for MLC optimization. Average isocenter to tumor distance was 5.5 ± 1.9 cm. Mean combined PTV derived from 4D‐CT scans was 38.7 ± 22.7 cc. Doses were 54 Gy/50 Gy in 3/5 fractions prescribed to 70%–80% isodose line so that at least 95% of the PTV receives 100% of prescribed dose. Plans were re‐optimized using PRO algorithm. Plans were compared via ROTG‐0915 protocol criteria for target conformity, heterogeneity and gradient indices, and dose to organs‐at‐risk (OAR). Additionally, total number of monitor units (MU), modulation factor (MF) and beam‐on time were compared.

Results

All plans met SBRT protocol requirements for target coverage and OAR doses. Comparison of target coverage and dose to the OAR showed no statistical significance between the two plans. PO had 1042 ± 753 (P < 0.001) less MU than PRO resulting in a beam‐on time of about 0.75 ± 0.5 min (P < 0.001) less, on average. For similar dose distribution, a significant reduction of beam delivery complexity was observed with PO (average MF = 3.7 ± 0.7) vs PRO MLC algorithm (average MF = 4.4 ± 1.3) (P < 0.001).

Conclusions

PO MLC algorithm improved treatment efficiency without compromising plan quality when compared to PRO algorithm for single‐isocenter/multi‐lesions VMAT lung SBRT. Shorter beam‐on time can potentially reduce intrafraction motion errors and improve patient compliance. PO MLC algorithm is recommended for future clinical lung SBRT plan optimization.
New lawsuit over UBH's guidelines could yield windfall for providers
Authors: Enos Gary
Published: September 2019

Following a court ruling earlier this year against United Behavioral Health's (UBH's) former level‐of‐care and coverage determination guidelines (see ADAW, Aug. 5), the managed behavioral health insurance giant now faces an action that is potentially much more far‐reaching — and this time, directly beneficial to substance use and mental health treatment providers.
Senate appropriations committee issues Labor‐HHS bill
Authors: Knopf Alison
Published: September 2019

The Senate Committee on Appropriations last week released its FY 2020 recommendations for the Labor, Health and Human Services, Education, and Related Agencies (Labor‐HHS) Appropriations bill.
A Virus‐Mimicking pH‐Responsive Acetalated Dextran‐Based Membrane‐Active Polymeric Nanoparticle for Intracellular Delivery of Antitumor Therapeutics
Authors: Wannasarit Saowanee , Wang Shiqi , Figueiredo Patrícia , Trujillo Claudia , Eburnea Francesca , Simón‐Gracia Lorena , Correia Alexandra , Ding Yaping , Teesalu Tambet , Liu Dongfei , Wiwattanapatapee Ruedeekorn , Santos Hélder A. , Li Wei
Published: September 2019

Achieving cellular internalization and endosomal escape remains a major challenge for many antitumor therapeutics, especially macromolecular drugs. Viral drug carriers are reported for efficient intracellular delivery, but with limited choices of payloads. In this study, a novel polymeric nanoparticle (ADMAP) is developed, resembling the structure and functional features of a virus. ADMAP is synthesized by grafting endosomolytic poly(lauryl methacrylate‐co‐methacrylic acid) on acetalated dextran. The endosomolytic polymer mimics the capsid protein for endosomal escape, and acetalated dextran resembles the viral core for accommodating payloads. After polymer synthesis, the subsequent controlled nanoprecipitation on a microfluidic device yields uniform nanoparticles with high encapsulation efficiency. At late endosomal pH (5.0), the ADMAP particles successfully destabilize endosomal membranes and release the drug payloads synergistically, resulting in a greater therapeutic efficacy compared with that of free anticancer drugs. Further conjugation of a tumor‐penetrating peptide enhances the antitumor efficacy toward 3D spheroids and finally leads to spheroid disintegration. The unique structure along with the synergistic endosomal escape and drug release make ADMAP nanoparticles favorable for intracellular delivery of antitumor therapeutics.
Unlocking the Potential of Disordered Rocksalts for Aqueous Zinc‐Ion Batteries
Authors: Ding Junwei , Du Zhiguo , Li Bin , Wang Lizhen , Wang Shiwen , Gong Yongji , Yang Shubin
Published: September 2019

Owing to the intense charge repulsion of multivalent ions and intrinsic slugggish kenetics, vast and fast storage of zinc ions into electrode materials has remained unattainable. Here, an efficient strategy to unlock the electrochemical activity of rocksalt vanadium oxynitride is developed via the substitution of low‐valent oxygen for high‐valent nitrogen, forming disordered rocksalt with abundant vacancies/defects due to the charge‐compensating function. Unexpectedly, the disordered rocksalt not only provides plentiful active sites for zinc ions but is also beneficial for the rapid diffusion of zinc ions, owing to the large presence of vacancies/defects in the matrix. Hence, a very high reversible capacity (603 mAh g−1, 0.2C) and high rate capability (124 mAh g−1at 600C) are achieved for zinc storage. This should open a new and efficient avenue for the design of electrode materials with both high energy and power densities for aqueous zinc‐ion batteries.
Uniform and Size‐Controlled Synthesis of Pt Nanoparticle Catalyst by Fluidized Bed Reactor Atomic Layer Deposition for PEMFCs
Authors: Lee Woo‐Jae , Bera Susanta , Shin Heon‐Cheol , Hong Woong‐Pyo , Oh Seung‐Jeong , Wan Zhixin , Kwon Se‐Hun
Published: September 2019

Pt nanoparticles (NPs) on a carbon support (Pt/C) are deposited by a simple fluidized bed reactor atomic layer deposition (FBR‐ALD) technique. The growth characteristics of the Pt NPs are investigated as a function of ALD cycles from 5 to 30 cycles. The excellent characteristics of FBR‐ALD offer highly dispersed and dense Pt particles with a size of ≈1 nm at low ALD cycles (5 cycles). However, as the number of ALD cycles increases above 5, the NPs increase in size and agglomerate due to preferential growth of incoming Pt NPs on previously deposited Pt surfaces. An electrochemical study shows that low ALD cycles (5 cycles) for the Pt/C catalyst result in a high electrochemical active surface area (ECSA) (114.67 m2 g−1). With increasing the number of cycles, ECSA is found to decrease, but still apparently higher than that of commercial Pt catalyst with the similar Pt wt% loading. Finally, ALD Pt/C catalysts with various cycles are applied to fuel cell testing for power generation. The electrode prepared with 20 ALD cycles of the Pt/C catalyst shows the best fuel cell performance (1.58 A cm−2 at 0.6 V) due to an adequate combination of activity and mass transfer characteristics of the electrode.
Dichroic Plasmon Superstructures of Au Nanorods over Macroscopic Areas via Directed Self‐Assemblies of Diblock Copolymers
Authors: Kang Heejung , Kim Sung‐Soo , Yoo Seong Il , Sohn Byeong‐Hyeok
Published: September 2019

The ability to organize metal nanoparticles over the macroscopic length scale has fundamental implications for advanced plasmonic applications. In particular, linear assemblies of anisotropic nanorods (NRs) may represent a dichroic superstructure, in which plasmonic extinction is inherently dependent on the direction of light polarization. As plasmonic properties are interconnected with optics, electronics, catalysis, and sensing, dichroism in plasmonic systems can stimulate interesting opportunities in many fields of chemistry. However, the preparation of dichroic structures with a single orientation at the centimeter scale remains a significant challenge. Herein, directed self‐assemblies of polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) diblock copolymers on lithographical patterns are applied to produce a linear pattern of Au NRs. Periodic nanogrooves from plasma‐etched PS‐b‐PMMA nanodomains facilitate the dense packing of Au NRs into end‐to‐end alignment, which entail strong plasmonic coupling among longitudinal plasmonic modes. Because the resulting NR assemblies have uniform orientation, their dichroic functions can be examined by conventional UV–vis spectroscopy without the aid of single‐particle measurements. Interestingly, both transverse and longitudinal localized surface plasmonic resonance peaks can be turned on and off under two polarized lights in orthogonal directions. Moreover, the resulting superstructures can be transferred onto various substrates, allowing the implantation of dichroic functions for numerous plasmonic applications.
Synthesis of Spiro‐Δ2‐Pyrrolin‐4‐One Pseudo Enantiomers via an Organocatalyzed Sulfa‐Michael/Aldol Domino Sequence
Authors: Grošelj Uroš , Ciber Luka , Gnidovec Jan , Testen Žan , Požgan Franc , Štefane Bogdan , Tavčar Gašper , Svete Jurij , Ričko Sebastijan
Published: September 2019

Δ2‐Pyrrolin‐4‐ones undergo organocatalyzed sulfa‐Michael/aldol domino spirocyclizations with mercaptoacetaldehyde dimer. The products contain three contiguous stereocenters (ee up to 99%, dr up to 95:5, 25 examples) and can be transformed into analogues of natural products. With the use of a single catalyst, the absolute configuration of the products were determined by the configuration of the exocyclic double bond of the starting material. These results point at the possibility of a widespread use of unsaturated Δ2‐pyrrolin‐4‐ones in various (organo)catalyzed (cascade) transformations for accessing libraries of 3D‐rich pyrrolone‐based (spiro)heterocycles.

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Unexpected Cascade Reactions of Ortho‐Hydroxyenaminones and β,γ‐Unsaturated α‐Ketoesters to Access Hydrogenated Benzoxazolepolycycles and Pyrrole−Phenol Atropisomers
Authors: Bai Xuguan , Wang Lele , Zhang Ziying , Zhang Kuan , Bu Zhanwei , Wu Yufeng , Zhang Wenjing , Wang Qilin
Published: September 2019

An unexpected BF3 ⋅ OEt2‐catalyzed Michael addition/cyclization/dehydration sequence of ortho‐hydroxyenaminones with aromatic or aliphatic aldehyde‐derived β,γ‐unsaturated α‐ketoesters has been achieved to afford a wide range of fused hydrogenated benzoxazole polycycles in 67–95% yields in a highly diastereoselective manner. When isatin‐derived β,γ‐unsaturated α‐ketoesters were employed as substrates, completely different reactivities were observed, delivering an array of new atropisomers with an oxindole‐substituted N−C axially chiral pyrrole−phenol backbone in up to 97% yield. Moreover, DFT calculations were conducted to account for the possible reaction pathway and the stereochemistry.

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On the Origin of the Large Remanent Polarization in La:HfO2
Authors: Schenk Tony , Fancher Chris M. , Park Min Hyuk , Richter Claudia , Künneth Christopher , Kersch Alfred , Jones Jacob L. , Mikolajick Thomas , Schroeder Uwe
Published: September 2019

The outstanding remanent polarization of 40 µC cm–2 reported for a 10 nm thin La:HfO2 film in 2013 has attracted much attention. However, up to now, no explanation for this large remanent polarization has been presented. Density functional theory and X‐ray diffraction are used to shine light onto three major aspects that impact the macroscopically observed remanent polarization: phase fraction, spontaneous polarization, and crystallographic texture. Density functional theory calculations show that the spontaneous polarization (Ps) of La:HfO2 is indeed a bit larger than for other HfO2‐ or ZrO2‐based compounds; however, the Ps is not large enough to explain the observed differences in remanent polarization. While neither phase fractions nor spontaneous polarization nor strain are significantly different from those in other HfO2 films, a prominent 020/002 texture distinguishes La doped from other HfO2‐based ferroelectric films. Angular‐dependent diffraction data provide a pathway to calculate the theoretically expected remanent polarization, which is in agreement with the experimental observations. Finally, an interplay of the in‐plane strain and texture is proposed to impact the formation of the ferroelectric phase during annealing. Further aspects of the special role of La as a dopant are collected and discussed to motivate future research.
Evaporation‐Free Nonfullerene Flexible Organic Solar Cell Modules Manufactured by An All‐Solution Process
Authors: Han Yong Woon , Jeon Sung Jae , Lee Hyoung Seok , Park Hongkwan , Kim Kwang Su , Lee Ho‐Won , Moon Doo Kyung
Published: September 2019

To ensure laboratory‐to‐industry transfer of next‐generation energy harvesting organic solar cells (OSCs), it is necessary to develop flexible OSC modules that can be produced on a continuous roll‐to‐roll basis and to apply an all‐solution process. In this study, nonfullerene acceptors (NFAs)‐based donor polymer, SMD2, is newly designed and synthesized to continuously fabricate high‐performance flexible OSC modules. Also, multifunctional hole transport layers (HTLs), WO3/HTL solar bilayer HTLs, are developed and applied via an all‐solution process called “ProcessOne” into inverted structure. SMD2, the donor terpolymer, has a deep highest occupied molecular orbital (HOMO) level and can achieve a power conversion efficiency (PCE) of 11.3% with NFAs without any pre‐/post‐treatment because of its optimal balance between crystallinity and miscibility. Furthermore, the integration of multifunctional HTLs enables the recovery of the drop in open circuit voltage (VOC) caused by a mismatch in energy levels between the deep HOMO level of the NFAs‐based bulk‐heterojunction layer and the solution‐processed HTLs. Also, the photostability under ultraviolet‐exposure necessary for “ProcessOne” is greatly improved because of the integration of multifunctional HTLs. Consequently, because of the synergistic effects of these approaches, the flexible OSC modules fabricated in an industrial production line have a PCE of 5.25% (Pmax = 419.6 mW) on an active area of 80 cm2.
How to build distylous flowers: comparative floral development and evolution of distylous species across the angiosperms
Authors: Cohen James I.
Published: September 2019

Premise

Distyly, a plant breeding system characterized by two floral morphs that have reciprocal positioning of anthers and stigmas, is known from at least 27 angiosperm families, making it an excellent example of convergent evolution. The various manners in which patterns of floral development produce the distinct anther and stigma heights in each morph remain largely unexplored from developmental and evolutionary perspectives.

Methods

In 15 species representing at least 12 origins of distyly, heights and lengths of floral organs in each morph throughout development were examined using light microscopy. Patterns of floral organ development were determined and compared among species. Family‐level phylogenies of distylous species and relatives were reconstructed, and patterns of ancestral herkogamy were resolved.

Results

Differences in floral development between morphs resulted in 12 patterns leading to the anther and stigma positions characterizing distyly. Distylous species evolved from ancestors with different types of herkogamy, with approach herkogamy and lack of herkogamy resolved most frequently.

Conclusions

Seven of the 12 patterns of floral development are known from only one species, with three other patterns described among pairs of close relatives. The most common pattern of floral development, described from at least seven genera, involves for anther heights, distinct intermorph growth rates and for stigma heights, growth rates that differ between morphs only during later development. This pattern is common among subclass Lamiidae, suggesting canalized development within the taxon. Among distylous species, the same type of ancestral herkogamy can give rise to different patterns of floral development.
Hybrid Halide Perovskites: Discussions on Terminology and Materials
Authors: Mercier Nicolas
Published: September 2019

Hybrid halide perovskites (HP) have emerged in the last decade as a new class of semiconductors with superior performances in photovoltaic and electronic devices. The literature about these halide semiconductors is abundant and a lot of names/expressions are used to define networks, structures, or materials. In this context, there is a need to offer some discussions about the relevance of using the word “perovskite” and the associated expressions (“RP” (Ruddlesden–Popper), “DJ” (Dion–Jacobson), “ACI” (alternating cations in the interlayer space), “hexagonal perovskites”, “hollow perovskites”, “d‐HP” (deficient 3D HP),…). Moreover, the description of perovskite networks through elimination/substitution processes from the ABX3 structure will be compared to the known dimensional reduction concept.
Palladium(0)‐Catalyzed Directed syn‐1,2‐Carboboration and ‐Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary
Authors: Liu Zhen , Chen Jiahao , Lu Hou‐Xiang , Li Xiaohan , Gao Yang , Coombs John R. , Goldfogel Matthew J. , Engle Keary M.
Published: September 2019

We report the development of palladium(0)‐catalyzed syn‐selective 1,2‐carboboration and ‐silylation reactions of alkenes containing cleavable directing groups. With B2pin2 or PhMe2Si‐Bpin as nucleophiles and aryl/alkenyl triflates as electrophiles, a broad range of mono‐, di‐, tri‐ and tetrasubstituted alkenes are compatible in these transformations. We further describe a directed dearomative 1,2‐carboboration of electron‐rich heteroarenes by employing this approach. Through use of a removable chiral directing group, we demonstrate the viability of achieving stereoinduction in Heck‐type alkene 1,2‐difunctionalization. This work introduces new avenues to access highly functionalized boronates and silanes with precise regio‐ and stereocontrol.
Controlling the Reactivity of the [P8W48O184]40− Inorganic Ring and Its Assembly into POMZite Inorganic Frameworks with Silver Ions
Authors: Zhan Cai‐Hong , Zheng Qi , Long De‐Liang , Vilà‐Nadal Laia , Cronin Leroy
Published: September 2019

The construction of pure‐inorganic framework materials with well‐defined design rules and building blocks is challenging. In this work, we show how a polyoxometalate cluster with an integrated pore, based on [P8W48O184]40− (abbreviated as {P8W48}), can be self‐assembled into inorganic frameworks using silver ions, which both enable reactions on the cluster as well as link them together. The {P8W48} was found to be highly reactive with silver ions resulting in the in situ generation of fragments, forming {P9W63O235} and {P10W66O251} in compound (1) where these two clusters co‐crystallize and are connected into a POMZite framework with 11 Ag+ ions as linkers located inside clusters and 10 Ag+ linking ions situated between clusters. Decreasing both the concentration of Ag+ ions, and the reaction temperature compared to the synthesis of compound (1), leads to {P8W51O196} in compound 2 where the {P8W48} clusters are linked to form a new POMZite framework with 9 Ag+ ions per formula unit. Further tuning of the reaction conditions yields a cubic porous network compound (3) where {P8W48} clusters as cubic sides are joined by 4 Ag+ ions to give a cubic array and no Ag+ ions were found inside the clusters.
In‐Operando Mapping of pH Distribution in Electrochemical Processes
Authors: Fuladpanjeh‐Hojaghan Behzad , Elsutohy Mohamed M. , Kabanov Vladimir , Heyne Belinda , Trifkovic Milana , Roberts Edward P. L.
Published: September 2019

In aqueous electrochemical processes, the pH evolves spatially and temporally, and often dictates the process performance. Herein, a new method for the in‐operando monitoring of pH distribution in an electrochemical cell is demonstrated. A combination of pH‐sensitive fluorescent dyes, encompassing a wide pH range from ≈1.5 to 8.5, and rapid electrochemically coupled laser scanning confocal microscopy is used to observe pH changes in the cell. Using electrocoagulation as an example process, we show that the method provides new insights into the reaction mechanisms. The pH close to the aluminium electrode surface is influenced by the applied current density, hydrolysis of aluminium cations, and gas evolution. Through quantification of the pH at the anode, along with gas analysis, we find that hydrogen is evolved at the anode due to a non‐Faradaic chemical reaction. This leads to increased production of coagulant, which may open new routes to enhance the process performance. This method for in‐operando dynamic visualization of pH paves the way for studies of electrochemical processes, including other water treatment, electrosynthesis, and batteries.
Intermolecular Carbonyl–olefin Metathesis with Vinyl Ethers Catalyzed by Homogeneous and Solid Acids in Flow
Authors: Rivero‐Crespo Miguel Ángel , Tejeda‐Serrano María , Pérez‐Sánchez Horacio , Cerón‐Carrasco José Pedro , Leyva‐Pérez Antonio
Published: September 2019

The carbonyl–olefin metathesis reaction has experienced significant advances in the last seven years with new catalysts and reaction protocols. However, most of these procedures involve soluble catalysts for intramolecular reactions in batch. Herein, we show that recoverable, inexpensive, easy to handle, non‐toxic, and widely available simple solid acids, such as the aluminosilicate montmorillonite, can catalyze the intermolecular carbonyl–olefin metathesis of aromatic ketones and aldehydes with vinyl ethers in‐flow, to give alkenes with complete trans stereoselectivity on multi‐gram scale and high yields. Experimental and computational data support a mechanism based on a carbocation‐induced Grob fragmentation. These results open the way for the industrial implementation of carbonyl–olefin metathesis over solid catalysts in continuous mode, which is still the origin and main application of the parent alkene–alkene cross‐metathesis.
A Chalcogen‐Bonding Cascade Switch for Planarizable Push–Pull Probes
Authors: Macchione Mariano , Goujon Antoine , Strakova Karolina , Humeniuk Heorhii V. , Licari Giuseppe , Tajkhorshid Emad , Sakai Naomi , Matile Stefan
Published: September 2019

Planarizable push–pull probes have been introduced to demonstrate physical forces in biology. However, the donors and acceptors needed to polarize mechanically planarized probes are incompatible with their twisted resting state. The objective of this study was to overcome this “flipper dilemma” with chalcogen‐bonding cascade switches that turn on donors and acceptors only in response to mechanical planarization of the probe. This concept is explored by molecular dynamics simulations as well as chemical double‐mutant cycle analysis. Cascade switched flipper probes turn out to excel with chemical stability, red shifts adding up to high significance, and focused mechanosensitivity. Most important, however, is the introduction of a new, general and fundamental concept that operates with non‐trivial supramolecular chemistry, solves an important practical problem and opens a wide chemical space.