bluuebunny/crossref_metadata_2025 huggingface dataset:
Marx. Da teoria da educação à teoria da auto-emancipação do proletariado
Authors: Viparelli Irene
Published: January 2019

<span style="font-size: 10pt; font-family: Garamond; mso-bidi-font-weight: bold; mso-fareast-font-family: Calibri; mso-bidi-font-family: 'Times New Roman'; mso-ansi-language: PT-BR; mso-fareast-language: EN-US; mso-bidi-language: AR-SA;">Este texto debate a questão da educação do proletariado a partir de Marx, expressa na terceira tese ad Feuerbach: “o educador tem ele próprio de ser educado”. Situa a problemática, já equacionada na obra a Ideologia Alemã, retomada em outras obras, em relação ao pensamento dos hegelianos de esquerda, de maneira a superar o “entendimento do desenvolvimento da história como resultado da consciência subjetiva e da educação da “Massa” como tarefa revolucionária da filosofia”. Esclarece como Marx estabeleceu os limites da perspectiva idealista e do “velho materialismo”, na concepção da história, educação do proletariado e defesa da auto-educação e emancipação do proletariado. Elabora possíveis contradições entre esta perspectiva e o papel dos comunistas no trabalho de “vanguarda” da educação para a revolução. Conclui a superação da contradição pela teoria das “tendências” do desenvolvimento histórico.
Ética e educação: a opção marxista
Authors: Freitas Francisco Máuri de Carvalho
Published: January 2019

<span style="font-size: 10pt; font-family: Garamond; mso-fareast-font-family: 'Times New Roman'; mso-bidi-font-family: 'Times New Roman'; mso-ansi-language: PT-BR; mso-fareast-language: PT-BR; mso-bidi-language: AR-SA;">Trata o presente estudo, na perspectiva da tradição marxista, de localizar a relação indissociável entre ética e educação ou tendo por opção metodológica o marxismo como instrumento de análise da realidade objetiva e dos determinantes sociais da ética e da educação na cidade do capital. Neste sentido, aponta o estudo que diante de proclamada “exaustão” do marxismo enquanto método de investigação, método de exposição e, sobretudo, linha revolucionária à transformação do capitalismo o transfugir (da esquerda à direita) é um ato imoral à medida que o trânsfuga serve a classe dominante e mantém uma distância asséptica da luta de classes. Este estudo de cunho descritivo assume como tarefa primordial da crítica marxista reportar que, com raras exceções, os intelectuais em geral e os da educação em particular carentes de imaginação porque carentes de razão procuram imobilizar os educandos na confusão dos paradoxos. Enfim, na análise da realidade buscamos distinguir o principal do secundário, o determinante do determinado, distinção sem a qual não é possível edificar uma sólida crítica radical às teorias que protelam a compreensão da educação como instrumento necessário à luta dos operários e trabalhadores e à construção de outro modo de produção da existência para além do capital. 
PEDAGOGIA HISTÓRICO-CRÍTICA E PSICOLOGIA HISTÓRICO CULTURAL: INFERÊNCIAS PARA A FORMAÇÃO E O TRABALHO DE PROFESSORES
Authors: Haddad Cristhyane Ramos , Pereira Maria de Fátima Rodrigues
Published: January 2019

Este artigo apresenta a pedagogia histórico crítica e a psicologia histórico cultural, ensaia, ainda, fazer inferências para a formação de professores no Brasil. Para tanto, buscou-se a fundamentação teórica em autores como Dermeval Saviani, Newton Duarte, Vigotski, Leontiev, Lígia Márcia Martins, Marilda Facci, Marta Sforni. A pedagogia histórico crítica postula que o ato educativo caracteriza-se pela intencionalidade, tendo como objetivo a apropriação do conhecimento sistematizado pelo aluno. Nesse mesmo sentido, a psicologia histórico cultural compreende que a aprendizagem dos conhecimentos escolares são fundamentais para o desenvolvimento das funções psicológicas superiores. O bom ensino nessa perspectiva é aquele que promove o desenvolvimento do indivíduo que é sempre um desenvolvimento social e histórico. Estas abordagens fazem o enfrentamento e a superação das pedagogias do aprender a aprender que encontram seus fundamentos no construtivismo e que apregoam que mais importante do que ensinar ou aprender é levar o aluno a encontrar caminhos para o aprender a aprender. O trabalho do professor, segundo essas pedagogias, seria o de um facilitador da aprendizagem, o que tem levado a um esvaziamento de sua função acarretando sérias consequências para o processo do ensino aprendizagem dos alunos em sala de aula. Finalmente, este artigo aponta segundo a perspectiva marxista a defesa da formação omnilateral dos professores como elemento imprescindível para o avanço rumo à consolidação de um ensino público de qualidade. 
TRAJETÓRIA DE ELABORAÇÃO DA PROPOSTA PEDAGÓGICA PARA A EDUCAÇÃO INFANTIL NO SISTEMA DE ENSINO DE BAURU NA PERSPECTIVA TEÓRICA DA PEDAGOGIA HISTÓRICO-CRÍTICA E TEORIA HISTÓRICO-CULTURAL
Authors: Corrêa Marta De Castro Alves
Published: January 2019

O presente artigo tem como objetivo apresentar a trajetória de implantação da pedagogia histórico-crítica e teoria histórico-cultural na Educação Infantil do Sistema Municipal de Ensino de Bauru e enfatiza o processo de formulação colaborativa de uma nova proposta pedagógica ancorada na perspectiva marxista, discutindo os avanços e dificuldades encontrados na elaboração do referido documento para garantir os princípios desta concepção na orientação teórico-prática do coletivo escolar. Para tanto, foi necessário recuperar a memória do trabalho desenvolvido nesta etapa de ensino desde sua implantação no município; pois entende-se que, ao investigar as ações educativas passadas, é possível compreender o posicionamento teórico adotado para a efetivação do caráter formal que a escola da infância assume no contexto desta pedagogia. Para a organização do estudo, optamos pelo relato de experiência, por melhor adequar-se aos propósitos deste trabalho e permitir conhecer as variáveis que contribuíram para a opção pela pedagogia histórico-crítica e teoria histórico-cultural como unidade teórica privilegiada para o ensino da criança de zero a cinco anos.
EDUCAÇÃO E HEGEMONIA: A FORMAÇÃO DE INTELECTUAIS NA ITÁLIA DOS ANOS 20, A ORGANIZAÇÃO DA INDUSTRIALIZAÇÃO EM SÃO PAULO E A CONSTRUÇÃO DA HEGEMONIA BURGUESA NO BRASIL
Authors: Villela Fábio Fernandes
Published: January 2019

A formação de intelectuais, sob uma perspectiva gramsciana (GRAMSCI, 2000), foi abordada ao longo de nossa trajetória acadêmica, por exemplo, Villela (2003; 2008; 2009; 2010-2012; 2011; 2012; 2014). Este artigo tem como objetivo retomar algumas relações entre a educação dos intelectuais na Itália dos anos 1920, a organização da industrialização em São Paulo e a construção da hegemonia burguesa no Brasil. Neste trabalho revejo minha dissertação de mestrado, Villela (2003), cujo objetivo foi compreender a racionalização dos processos de trabalho em escritórios de arquitetura. Esta dissertação de mestrado possibilitou traçar, entre outros aspectos, outra história da relação entre arquitetura e Estado no Brasil a partir da industrialização em São Paulo. Baseados na noção de intelectuais de Gramsci, discutimos a concepção ampliada de Estado e vislumbramos um determinado tipo de Estado que, em nosso caso, é o Estado Industrialista. E nos interessava relacionar as políticas públicas desse Estado para a industrialização às indústrias projetadas pelo escritório Rino Levi Arquitetos Associados SC Ltda. (ERLAA) que desenvolveu, ao longo de suas atividades das décadas de 1920 a 1990, muitos projetos na cidade de São Paulo. A relação ora proposta é inédita. Alicerçados nesta relação, colocamos em cena outra acerca da formação dos intelectuais e a hegemonia, de um ponto de vista gramsciano. 
FLORESTAN FERNANDES E A CRISE DO CAPITAL: A URGÊNCIA DA EDUCAÇÃO E FORMAÇÃO DA CONSCIÊNCIA CRÍTICA
Authors: Pinassi Maria Orlanda
Published: January 2019

Educação e formação da consciência efetivamente crítica e revolucionária só podem ser conquistadas a partir da realidade das lutas travadas contra o capital, da experiência que emana da agudeza das contradições da atualidade. Pois é a crítica dos movimentos sociais de massas, a crítica dos movimentos sindicais e dos partidos políticos que ousam transgredir as regras impostas pela “coisa pública” que incomoda o capital. É essa crítica, que associa teoria e práxis, que vem sendo criminalizada, reprimida, violentada pelo capital, na vigência de uma forma muito atual de democracia cada vez mais intolerante e mais parecida com o autoritarismo do regime militar. 
AS RAÍZES DA REGRESSÃO NO MUNDO ÁRABE
Authors: Roio Marcos Del
Published: January 2019

A partir da mobilização popular que colocou abaixo a ditadura vigente na Tunísia a mídia difundiu a expressão “primavera árabe” para a série de eventos que se sucediam. Percebe-se agora que forma eventos diferenciados e com muitos vetores, que se manifestam quase todos no conflito armado que corrói a Síria. No entanto, o objetivo deste texto é oferecer um amplo panorama para sugerir a explicação da forte regressividade presente no mundo árabe, mesmo com a presença de micro regiões de incrível riqueza. 
The European Cancer Patient Coalition and its central role in connecting stakeholders to advance patient‐centric solutions in the mission on cancer
Authors: de Lorenzo Francesco , Apostolidis Kathi
Published: January 2019

There is an urgent need for solutions to the economic and social inequalities in cancer care that still exist in many European countries. Patient preferences, ‘big data’, mobile digital technology and molecular and genomic profiling are among the innovative research topics that connect cancer patients to comprehensive cancer centres, and link translational research to cancer diagnosis, treatment and care. The question is whether Europe can deliver the complex infrastructure needed for universal coverage and equitable access to cancer care. The European Cancer Patient Coalition (ECPC), the leading ‘umbrella’ cancer patient organisation in Europe, has a central role in bringing the unmet needs of patients with cancer to the forefront of cancer policy, care and research. The ECPC is a respected and reliable partner in the oncology community and has effectively collaborated with institutional stakeholders and organisations, as well as with the European Commission, on cancer research projects and in the development of tools to advance health care and cancer policies at the European and national level. The ECPC believes that innovation cannot emerge and grow without patient involvement and is fully committed to increasing patient education and contribution in cancer research through its active participation in various European cancer research programmes and educational resources. The ECPC is expected to play a major role in the mission on cancer, given its previous achievements in policy and research to help overcome the inequalities in cancer prevention, treatment, rehabilitation and survivorship care. The mission on cancer will be facilitated by active collaboration between patient organisations and scientists, clinicians, politicians and industry, with the aim of identifying important research questions regarding quality of life and social issues for cancer patients of all ages.
Fabrication and Characterization of Highly Porous FeAl‐Based Intermetallics by Thermal Explosion Reaction
Authors: Liu Yanan , Cai Xiaoping , Sun Zhi , Zhang Hanzhu , Akhtar Farid , Czujko Tomasz , Feng Peizhong
Published: January 2019

Porous FeAl‐based intermetallics with different nominal compositions ranging from Fe–40 at% Al to Fe–60 at% Al are prepared by a novel process of thermal explosion (TE) mode. The results show that the Al content significantly affects the combustion behavior of the specimens, the ignition temperature of the Fe–Al intermetallics varies from 641 to 633 °C and the combustion temperature from 978 to 1179 °C. The porous materials exhibit uniform pore structures with porosities and average pore sizes of 52–61% and 20–25 µm, respectively. The TE reaction is the dominant pore formation mechanism regardless of the alloy composition. However, differences in the porosity and average pore size are observed depending on the Al content. The compressive strength of porous Fe–Al intermetallics is in the range of 23–34 MPa, duly applied as filters. Additionally, a surface alumina layer is formed at the early stage and both of the oxidation process and the sulfidation process follows the familiar parabolic rate law in the given atmosphere, exhibiting excellent resistance to oxidation and sulfidation. These results suggest that the porous Fe–Al intermetallics are promising materials for applications in harsh environments with a high‐temperature sulfide‐bearing atmosphere, such as in the coal chemical industry.
Micellar‐Mediated Block Copolymer Ordering Dynamics Revealed by In Situ Grazing Incidence Small‐Angle X‐Ray Scattering during Spin Coating
Authors: Fleury Guillaume , Hermida‐Merino Daniel , Jingjin Dong , Aissou Karim , Bytchkov Aleksei , Portale Giuseppe
Published: January 2019

Spin coating is one of the most versatile methods to generate nanostructured block copolymer (BCP) thin films which are highly desired for many applications such as nanolithography or organic electronics. The self‐assembly pathways through phase separation, both in solvent and in bulk, strongly influence the final BCP structure obtained after spin coating. As a demonstration, the formation of highly ordered in‐plane lamellae is elucidated herein by using in situ grazing incidence small‐angle X‐ray scattering. A key step in this complex fast organization process is the formation of intermediate micellar phases triggered by solvent affinity toward one of the block. Indeed, directional coalescence of a short‐lived intermediate hexagonal structure of cylindrical micelles enables the development of a final highly ordered lamellar structure, predominantly oriented parallel to the substrate surface. These results suggest that the existence of such transient micellar phases is a crucial process in order to produce highly ordered structures with a specific orientation directly after the BCP thin film deposition; and should be the focus of further optimization for the directed self‐assembly and, more generally, in the bottom‐up nanostructure fabrication.
Tumor‐Specific Drug Release and Reactive Oxygen Species Generation for Cancer Chemo/Chemodynamic Combination Therapy
Authors: Wang Sheng , Wang Zhantong , Yu Guocan , Zhou Zijian , Jacobson Orit , Liu Yijing , Ma Ying , Zhang Fuwu , Chen Zhi‐Yi , Chen Xiaoyuan
Published: January 2019

The combination of chemotherapeutic drugs and reactive oxygen species (ROS) is a promising strategy to achieve improved anticancer effect. Herein, a nanomedicine (LaCIONPs) that can achieve tumor‐specific chemotherapeutic drug release and ROS generation is developed for cancer chemo/chemodynamic combination therapy. The LaCIONPs are constructed by encapsulation of iron oxide nanoparticles (IONPs) and β‐lapachone (La) in nanostructure assembled by hydrogen peroxide (H2O2)‐responsive polyprodrug and pH‐responsive polymer. Through the enhanced permeability and retention effect, the nanosized LaCIONPs can accumulate in tumor tissue. After the LaCIONPs are internalized by tumor cells, the structure of LaCIONPs is disintegrated in acidic intracellular environment, leading to rapid release of La and iron ions. Then the released La generates massive H2O2 through tumor specific catalysis. On the one hand, H2O2 further reacts with iron ions to produce highly toxic hydroxyl radicals for chemodynamic therapy. On the other hand, H2O2 also activates the release of camptothecin from the polyprodrug for chemotherapy. The potent antitumor effect of the LaCIONPs is demonstrated by both in vitro and in vivo results. Therefore, the LaCIONP is a promising nanomedicine for tumor‐specific chemo/chemodynamic combination therapy.
New Floating Gate Memory with Excellent Retention Characteristics
Authors: Wang Shuopei , He Congli , Tang Jian , Lu Xiaobo , Shen Cheng , Yu Hua , Du Luojun , Li Jiafang , Yang Rong , Shi Dongxia , Zhang Guangyu
Published: January 2019

In current flash memory, there is an inevitable tradeoff between the operation voltage and the retention time due to the incorporation of very thin tunneling layer in the device structure. In this work, a new type of robust floating gate nonvolatile memory based on 2D materials is introduced to reduce the operation voltage and promote the data retention time. By taking the advantage of a dual‐gate structure, as‐fabricated devices exhibit excellent performance with low operation voltage (as low as 5 V even the tunneling layer t
BN ≥ 10 nm), long retention time (on/off ratio with negligible degeneration over 105 s), and ultralow off‐leakage current (10−13 A, which is very attractive for ultralow‐power applications). Charges trapped in the top gate originated from the capacitive coupling between the back and top gates are found to be responsible for the nonvolatile behavior. The new charge trapping mechanism, which is distinguished from that in the conventional single‐gate memory devices, enables charge tunneling through a thicker tunneling layer at a low operation voltage. The achieved MoS2 nonvolatile memory with outstanding performances has great potentials for future information storage.
Cellulose Nanopaper with Monolithically Integrated Conductive Micropatterns
Authors: Hajian Alireza , Wang Zhen , Berglund Lars A. , Hamedi Mahiar M.
Published: January 2019

This work presents a route to fabricate micropatterned conductive structures where the conductors are monolithically integrated with nanocellulose‐based paper. To fabricate conductive features, microstructures are patterned on filter papers using wax‐printing, followed by vacuum filtration of carbon nanotubes (CNTs) or silver nanowires (AgNWs) dispersed in aqueous cellulose nanofibrils (CNFs). These patterns are then laminated onto a pure CNF substrate (both in gel‐state) and dried to form cellulose nanopapers with integrated conductive micropatterns. Resolutions of the conductive features are shown down to 400 µm wide, 250 nm thick, and with conductivity values of 115 ± 5 S cm−1 for the CNF–CNT and 3770 ± 230 S cm−1 for the CNF–AgNW micropatterns. The nanopaper and the conductive patterns both constitute random fibrous networks, and they display similar ductility and swelling behavior in water. Thus, the integrated conductive micropatterns can withstand folding, as well as wetting cycles. This stability of the micropatterns makes them useful in various devices based on nanocellulose substrates. As an example, an electroanalytical nanopaper device that operates in wet conditions is demonstrated.
An experimental investigation of interfacial instability in separated blood
Authors: Wood Ryan L. , Whitehead Jared P. , Hunter Alex K. , McClellan Daniel S. , Pitt William G.
Published: January 2019

Experiments are done with separated human blood decelerated at constant rates to determine the maximum deceleration rate while avoiding remixing of the layers, which have different densities and viscosities. The deceleration rate affects both the stability and separation of particles through sedimentation. The velocity at onset of instability for a constant deceleration rate is experimentally determined for a 12‐cm‐diameter disk. Parameters of cell pack thickness, plasma thickness, and total thickness are investigated experimentally, and the only statistically significant parameter to affect stability is rate of deceleration. The data describe a correlation separating regions of stability and instability. To understand stability in decelerating flow of separated blood plasma and cells, the equations of motion are solved for a two‐layer fluid flow with a moving boundary and free surface. Inclusion of non‐Newtonian rheology of blood predicts large discontinuities in the shear rate, which is proposed as the cause of the interfacial instabilities. © 2019 American Institute of Chemical Engineers AIChE J, 65: 1376–1386, 2019
Silicosis prevalence and incidence among Medicare beneficiaries
Authors: Casey Megan L. , Mazurek Jacek M.
Published: January 2019

Introduction

Existing epidemiologic information on silicosis relies on mortality data.

Methods

We analyzed health insurance claims and enrollment information from 49 923 987 fee‐for‐service (FFS) Medicare beneficiaries aged ≥65 from 1999 to 2014. Three different definitions were developed to identify silicosis cases and results are presented as ranges of values for the three definitions.

Results

Among FFS beneficiaries, 10 026‐19 696 fit the silicosis case definitions (16‐year prevalence: 20.1‐39.5 per 100 000) with the highest prevalence among North American Natives (87.2‐213.6 per 100 000) and those in New Mexico (83.9‐203.4 per 100 000). The annual average prevalence had a significant (P < 0.05) 2‐5% annual decline from 2005 to 2014. The average annual number of incident cases had a significant 3‐16% annual decline from 2007 to 2014.

Conclusions

Silicosis is a prevalent disease among Medicare beneficiaries aged ≥65, with variation across the country. Morbidity data from health insurance claims can provide a more complete picture of silicosis burden.
Long‐term olfaction outcomes in transnasal endoscopic skull‐base surgery: a prospective cohort study comparing electrocautery and cold knife upper septal limb incision techniques
Authors: Puccinelli Cassandra L. , Yin Linda X. , O'Brien Erin K. , Van Gompel Jamie J. , Choby Garret W. , Van Abel Kathryn M. , Janus Jeffrey R. , Stokken Janalee K.
Published: January 2019

Background

Olfactory nerve fibers are at risk of injury during transnasal endoscopic skull‐base approaches. Olfactory outcomes for various techniques have not been thoroughly investigated. This study aims to report long‐term olfactory outcomes when a cold knife upper septal limb incision technique is used compared to monopolar cautery.

Methods

A prospective cohort study was performed at a tertiary referral center. Adult patients undergoing endoscopic approaches with septal incisions were randomized to cold knife or monopolar cautery groups. Patient demographics, clinical history, surgical data, and outcomes were collected. Preoperative, 3‐month, and 12‐month postoperative scores on the University of Pennsylvania Smell Inventory Test (UPSIT) and 22‐item Sino‐Nasal Outcome Test (SNOT‐22) were measured. Fisher's exact tests were performed for categorical variables and t tests were performed for continuous variables.

Results

Twenty‐two (22) patients (10 cold knife, 12 cautery) were enrolled between March 2016 and August 2017. The average age ± standard deviation was 50.2 ± 14.0 years (p = 0.59), 54% (p = 0.69) were female, and the primary pathology was pituitary adenoma (73%, p = 1.00). Preoperative, 3‐month, and 12‐month postoperative UPSIT scores were similar between the cold knife and cautery groups (32.8 vs 32.4, p = 0.80; 33.1 vs 33.0, p = 0.96; 33.6 vs 33.3, p = 0.84). On the “sense of smell/taste” question of the SNOT‐22, there was also no difference at all time points (p > 0.22).

Conclusion

There was no significant change in patient UPSIT scores 1 year after transnasal skull‐base approaches, and no short‐term or long‐term differences between cold knife and cautery upper septal limb incision techniques. Our study supports an individualized approach based on surgeon preference.
Outcomes and imaging findings of respiratory epithelial adenomatoid hamartoma: a systematic review
Authors: Safi Chetan , Li Carol , Tabaee Abtin , Ramakrishna Rohan , Riley Charles A.
Published: January 2019

Background

Respiratory epithelial adenomatoid hamartoma (REAH) is a recently classified histopathologic diagnosis often identified incidentally following endoscopic sinus surgery (ESS) for presumed chronic rhinosinusitis. Limited data exist defining preoperative imaging features and surgical outcomes. The purpose of this study is to examine characteristic imaging findings of REAH and postoperative olfactory and recurrence outcomes.

Methods

A systematic review was performed according to the Preferred Reporting Items for Systematic Reviews and Meta‐Analysis (PRISMA) guidelines on articles published from 1995 to present. PubMed, EMBASE, and Ovid MEDLINE databases were queried for studies pertinent to imaging findings of REAH and surgical outcomes. Quality of articles was assessed using the Methodological Index for Non‐Randomized Studies (MINORS).

Results

A total of 294 articles were identified, with 15 meeting inclusion criteria. Seven articles assessed both imaging findings and surgical outcomes. Three articles focused exclusively on imaging, whereas 5 examined surgical outcomes. Olfactory cleft (OC) widening greater than 10 mm on computed tomography (CT) was characteristic of REAH. A total of 441 patients with REAH were included; 221 patients (50.1%) had concurrent nasal polyposis, whereas 154 patients (34.9%) had isolated REAH. Surgical intervention ranged from simple excision to complete ESS. Sixty‐five percent (65%) of patients reported improved olfaction; 4.1% of patients recurred with follow‐up ranging from 4 months to 5 years.

Conclusion

A widened OC may suggest the presence of REAH. This disease process has been identified in patients with nasal polyposis or encountered as an isolated lesion. Targeted surgery may result in improved olfaction and a low likelihood of recurrence, though long‐term prospective studies are necessary.
Racemic Vinylallenes in Catalytic Enantioselective Multicomponent Processes: Rapid Generation of Complexity through 1,6‐Conjugate Additions
Authors: Huang Youming , Torker Sebastian , Li Xinghan , del Pozo Juan , Hoveyda Amir H.
Published: January 2019

Racemic vinylallenes are shown to be effective substrates for catalytic multicomponent diastereo‐ and enantioselective 1,6‐conjugate addition of multifunctional allyl moieties to easily accessible α,β,γ,δ‐unsaturated diesters. Reactions may be catalyzed by 5.0 mol % of a readily accessible NHC‐Cu complex at ambient temperature, and other than a vinylallene, involve B2(pin)2 and an α,β,γ,δ‐unsaturated diester. A variety of vinylallenes were converted to products bearing a Z‐trisubstituted alkenyl‐B(pin) moiety, a vinyl group, a β,γ‐unsaturated diester unit, and vicinal stereogenic centers in up to 67 % yield, 87:13 Z/E ratio, >98:2 d.r., and 98:2 e.r. Chemoselective modifications involving the alkenyl‐B(pin), the vinyl, or the 1,2‐disubstituted olefin moieties were carried out to demonstrate versatility and utility. Stereochemical models, based on mechanistic and DFT studies, demonstrate the dynamic behavior of intermediated Cu‐allyl species and account for various selectivity profiles.
Polymer Dots Compartmentalized in Liposomes as a Photocatalyst for In Situ Hydrogen Therapy
Authors: Zhang Boyu , Wang Fei , Zhou Hua , Gao Duyang , Yuan Zhen , Wu Changfeng , Zhang Xuanjun
Published: January 2019

Semiconducting polymer dots (Pdots) have recently attracted considerable attention because of their photocatalytic activity as well as tunable optical band gap. In this contribution, we describe the therapeutic application of Pdots through in situ photocatalytic hydrogen generation. Liposomes were employed as nanoreactors to confine the Pdot photocatalyst, reactants, intermediates, and by‐products. Upon photon absorption by the Pdots, the catalytic cycle is initiated and repeated within the aqueous interior, while the H2 product diffuses across the lipid bilayer to counteract reactive oxygen species (ROS) overexpressed in diseased tissues. Ensemble and single‐particle Förster resonance energy transfer microscopy confirmed the proposed nanoreactor model. We demonstrate that a liposomal nanoreactor containing Pdots and a sacrificial electron donor is a potential photocatalytic nanoreactor for in situ hydrogen therapy.
Control of Excited‐State Conformations in B,N‐Acenes
Authors: Lu Zhenpin , Quanz Henrik , Ruhl Julia , Albrecht Georg , Logemann Christian , Schlettwein Derck , Schreiner Peter R. , Wegner Hermann A.
Published: January 2019

We present a new concept to control the conformations of molecules in the excited state through harvesting negative hyperconjugation. The strategy was realized with the 2,3,1,4‐benzodiazadiborinane scaffold, which was prepared by a new synthetic procedure. Photochemical studies identified dual light emission, which was assigned to well‐defined conformers. The emission at longer wavelength can be switched off by restricting the rotational degrees of freedom in the solid state as well as by controlling the energy levels of the excited states through adjusting the solvent polarity.
Lugdunomycin, an Angucycline‐Derived Molecule with Unprecedented Chemical Architecture
Authors: Wu Changsheng , van der Heul Helga U. , Melnik Alexey V. , Lübben Jens , Dorrestein Pieter C. , Minnaard Adriaan J. , Choi Young Hae , van Wezel Gilles P.
Published: January 2019

The angucyclines form the largest family of polycyclic aromatic polyketides, and have been studied extensively. Herein, we report the discovery of lugdunomycin, an angucycline‐derived polyketide, produced by Streptomyces species QL37. Lugdunomycin has unique structural characteristics, including a heptacyclic ring system, a spiroatom, two all‐carbon stereocenters, and a benzaza‐[4,3,3]propellane motif. Considering the structural novelty, we propose that lugdunomycin represents a novel subclass of aromatic polyketides. Metabolomics, combined with MS‐based molecular networking analysis of Streptomyces sp. QL37, elucidated 24 other rearranged and non‐rearranged angucyclines, 11 of which were previously undescribed. A biosynthetic route for the lugdunomycin and limamycins is also proposed. This work demonstrates that revisiting well‐known compound families and their producer strains still is a promising approach for drug discovery.
Enzyme‐Modulated Anaerobic Encapsulation of Chlorella Cells Allows Switching from O2 to H2 Production
Authors: Su Dongyue , Qi Jiarui , Liu Xiaoman , Wang Lei , Zhang Hao , Xie Hui , Huang Xin
Published: January 2019

Single‐cell encapsulation has become an effective strategy in cell surface engineering; however, the construction of cell wall‐like layers that allow the switching of the inherent functionality of the engineered cell is still rare. In this study, we show a universal way to create an enzyme‐modulated oxygen‐consuming sandwich‐like layer by using polydopamine, laccase, and tannic acid as building blocks, which then could generate an anaerobic microenvironment around the cell. This layer protected the encapsulated C. pyrenoidosa cell against external stresses and enabled it to switch from normal photosynthetic O2 production to photobiological H2 production. The layer showed an smaller effect on the PSII activity, which contributed a significant enhancement on the rate (0.32 μmol H2 h−1 (mg chlorophyll)−1) and the duration (7 d) of H2 production. This strategy is expected to provide a pathway for modulating the functionality of cells and for breakthroughs in the development of green energy alternatives.
Adenine Components in Biomimetic Metal–Organic Frameworks for Efficient CO2 Photoconversion
Authors: Li Ning , Liu Jiang , Liu Jing‐Jing , Dong Long‐Zhang , Xin Zhi‐Feng , Teng Yun‐Lei , Lan Ya‐Qian
Published: January 2019

Visible‐light driven photoconversion of CO2 into energy carriers is highly important to the natural carbon balance and sustainable development. Demonstrated here is the adenine‐dependent CO2 photoreduction performance in green biomimetic metal–organic frameworks. Photocatalytic results indicate that AD‐MOF‐2 exhibited a very high HCOOH production rate of 443.2 μmol g−1 h−1 in pure aqueous solution, and is more than two times higher than that of AD‐MOF‐1 (179.0 μmol g−1h−1) in acetonitrile solution. Significantly, experimental and theoretical evidence reveal that the CO2 photoreduction reaction mainly takes place at the aromatic nitrogen atom of adenine molecules through a unique o‐amino‐assisted activation rather than at the metal center. This work not only serves as an important case study for the development of green biomimetic photocatalysts used for artificial photosynthesis, but also proposes a new catalytic strategy for efficient CO2 photoconversion.
Profiling of the Beneficial and Potentially Harmful Components of Trichodesma indicum Seed and Seed Oil Obtained by Ultrasound‐Assisted Extraction
Authors: Górnaś Paweł , Picron Jean‐François , Perkons Ingus , Mišina Inga , Rudzińska Magdalena , Sobieszczańska Natalia , Chakradhari Suryakant , Patel Khageshwar Singh
Published: January 2019

The beneficial and potentially harmful bioactive components in the seeds and seed oil of Trichodesma indicum L. (Boraginaceae) were investigated in the present study. The T. indicum seeds were rich in oil (29.0%), phenolic compounds (PC, 1881.2 mg per 100 g), and pyrrolizidine alkaloids (PA, 2,702,338 ng g−1). Seven PC were identified in T. indicum seeds by liquid chromatography‐quadrupole‐time‐of‐flight mass spectrometry system (LC‐Q‐TOF‐MS). Rosmarinic acid (67%) and isomers of salvianolic acid B/E/L (26%) were the main phenolics, while melitric acid A and sebestenoid C/D constituted 6% and 1%, respectively. Only a minor part of the total PC and PA was transferred from the seeds into the oil fraction during the extraction procedure (<0.03%). The T. indicum seed oil was predominated by the following polyunsaturated fatty acids (PUFA):linoleic (23.2%), γ‐linolenic (6.0%), α‐linolenic (26.8%), and stearidonic (5.9%). High levels were also observed for oleic (26.7%) and palmitic (7.4%) acids. Additionally, notable amounts of γ‐tocopherol (92% of total tocochromanols) and β‐sitosterol (53% of total sterols) were found in T. indicum seed oil. The total content of tocochromanols, sterols, and carotenoids in T. indicum seed oil was 102.7, 236.0, and 0.6 mg per 100 g oil, respectively. Among 10 detected hepatotoxic PA in T. indicum seeds, intermedine/lycopsamine/indicine (90.9%), intermedine N‐oxide (4.9%), and lycopsamine N‐oxide (4.1%) consisted 99.9% of the total PA concentration. The T. indicum seeds should be used carefully due to the presence of PA.
Feature‐based recursive observer design for homography estimation and its application to image stabilization
Authors: Hua Minh‐Duc , Trumpf Jochen , Hamel Tarek , Mahony Robert , Morin Pascal
Published: January 2019

This paper presents a new algorithm for online estimation of a sequence of homographies applicable to image sequences obtained from robotic vehicles equipped with vision sensors. The approach taken exploits the underlying Special Linear group structure of the set of homographies along with gyroscope measurements and direct point‐feature correspondences between images to develop temporal filter for the homography estimate. Theoretical analysis and experimental results are provided to demonstrate the robustness of the proposed algorithm. The experimental results show excellent performance and robustness even in the case of very fast camera motions (relative to frame rate) and severe occlusions.
A Comparison of Formation Methods for Graphite//LiFePO4 Cells
Authors: Moretti Arianna , Sharova Varvara , Carvalho Diogo V. , Boulineau Adrien , Porcher Willy , de Meatza Iratxe , Passerini Stefano
Published: January 2019

The sequence of initial cycles necessary for the build‐up of the solid electrolyte interphase (SEI) on the anode surface of Li‐ion batteries (usually called formation) is a cost‐ and time‐consuming process, thus requiring further optimization. Herein, three different protocols are compared to explore possibilities to reduce the formation time of the cells without negatively affecting the electrochemical performance. XPS and HRTEM analyses are used to identify the main characteristics of the as formed SEIs. Electrochemical tests are conducted on full lithium‐ion cells using state‐of‐the‐art graphite and LiFePO4 electrodes. The time‐saving dual‐current protocol results in excellent cycling performance, and in a LiF‐rich SEI. Interestingly, the use of moderately high temperature (40 °C) does not strongly affect the SEI composition as evidenced by XPS analysis. On the other hand, the formation rate determines the degree of graphite surface amorphization, visualized by HRTEM.
Retracted: 14‐3‐3ζ promotes gliomas cells invasion by regulating Snail through the PI3K/AKT signaling
Authors: Li Junjun , Xu Hao , Wang Qiangping , Wang Sihua , Xiong Nanxiang
Published: January 2019

14‐3‐3ζ has been reported to function as critical regulators of diverse cellular responses. However, the role of 14‐3‐3ζ in gliomas progression remains largely unknown. The expression level of 14‐3‐3ζ and Snail was detected by Western blot analysis and quantitative polymerase chain reaction in different grades of human gliomas. The effect of 14‐3‐3ζ on gliomas progression was measured using cell migration and invasion assay, the colony formation experiment, and CCK‐8 assay. The effect of 14‐3‐3ζ on PI3K/AKT/Snail signaling protein expression levels was tested by Western blotting. Firstly, 14‐3‐3ζ was often up‐regulated in high‐grade gliomas relative to low‐grade gliomas, and this overexpression was significantly related to tumor size, Karnofsky Performance Scale score and weaker disease‐free survival. Secondly, the overexpression of 14‐3‐3ζ promoted gliomas cells proliferation, migration, and invasion. Conversely, the knockdown of 14‐3‐3ζ suppressed gliomas cells proliferation, migration, and invasion. Furthermore, subsequent mechanistic studies showed that 14‐3‐3ζ could activate PI3K/AKT/Snail signaling pathway to facilitate gliomas cells proliferation, migration, and invasion. This study shows that the overexpression of 14‐3‐3ζ can promote remarkably gliomas cells proliferation, migration, and invasion by regulating the Snail protein expression through activating PI3K/AKT signaling, and it may serve as a potential prognostic marker and therapeutic target for gliomas.
Synthesis and Biological Activity of New 4‐tert‐Butylcyclohexanone Derivatives
Authors: Kozioł Agata , Jasnowski Mateusz , Grela Ewa , Szczepanik Maryla , Gabryś Beata , Dancewicz Katarzyna , Lochyński Stanisław
Published: January 2019

In the synthesis performed in this study, derivatives of 4‐tert‐butylcyclohexanone 1 were obtained using typical reactions of organic synthesis. The bioactivity of the selected compounds was evaluated. 1‐(Bromomethyl)‐8‐tert‐butyl‐2‐oxaspiro[4.5]decan‐3‐one (5) was characterized by attractant properties against larvae and a weak feeding deterrent activity against adults of Alphitobius diaperinus Panzer. This bromolactone was a moderate antifeedant towards Myzus persicae Sulzer. In addition, ethyl (4‐tert‐butylcyclohexylidene)acetate (2) and bromolactone 5 displayed antibacterial activity. The strongest bacteriostatic effect was observed against Gram‐positive strains: Bacillus subtilis and Staphylococcus aureus. The bromolactone 5 also limited the growth of Escherichia coli strain.
Light‐Wavelength‐Based Quantitative Control of Dihydrofolate Reductase Activity by Using a Photochromic Isostere of an Inhibitor
Authors: Mashita Takato , Kowada Toshiyuki , Takahashi Hiroto , Matsui Toshitaka , Mizukami Shin
Published: January 2019

Photopharmacology has attracted research attention as a new tool for achieving optical control of biomolecules, following the methods of caged compounds and optogenetics. We have developed an efficient photopharmacological inhibitor—azoMTX—for Escherichia coli dihydrofolate reductase (eDHFR) by replacing some atoms of the original ligand, methotrexate, to achieve photoisomerization properties. This fine molecular design enabled quick structural conversion between the active “bent” Z isomer of azoMTX and the inactive “extended” E isomer, and this property afforded quantitative control over the enzyme activity, depending on the wavelength of irradiating light applied. Real‐time photoreversible control over enzyme activity was also achieved.
Use of prasugrel and clinical outcomes in African‐American patients treated with percutaneous coronary intervention for acute coronary syndromes
Authors: Faggioni Michela , Baber Usman , Chandrasekhar Jaya , Sartori Samantha , Weintraub William , Rao Sunil V. , Vogel Birgit , Claessen Bimmer , Kini Annapoorna , Effron Mark , Ge Zhen , Keller Stuart , Strauss Craig , Snyder Clayton , Toma Catalin , Weiss Sandra , Aquino Melissa , Baker Brian , Defranco Anthony , Bansilal Sameer , Muhlestein Brent , Kapadia Samir , Pocock Stuart , Poddar Kanhaiya L. , Henry Timothy D. , Mehran Roxana
Published: January 2019

Objective

To investigate the use of prasugrel after percutaneous coronary intervention (PCI) in African American (AA) patients presenting with acute coronary syndrome (ACS).

Background

AA patients are at higher risk for adverse cardiovascular outcomes after PCI and may derive greater benefit from the use of potent antiplatelet therapy.

Methods

Using the multicenter PROMETHEUS observational registry of ACS patients treated with PCI, we grouped patients by self‐reported AA or other races. Clinical outcomes at 90‐day and 1‐year included non‐fatal myocardial infarction (MI), major adverse cardiac events (composite of death, MI, stroke, or unplanned revascularization) and major bleeding.

Results

The study population included 2,125 (11%) AA and 17,707 (89%) non‐AA patients. AA patients were younger, more often female (46% vs. 30%) with a higher prevalence of diabetes mellitus, chronic kidney disease, and prior coronary intervention than non‐AA patients. Although AA patients more often presented with troponin (+) ACS, prasugrel use was much less common in AA vs. non‐AA (11.9% vs. 21.4%, respectively, P = 0.001). In addition, the use of prasugrel increased with the severity of presentation in non‐AA but not in AA patients. Multivariable logistic regression showed AA race was an independent predictor of reduced use of prasugrel (0.42 [0.37–0.49], P < 0.0001). AA race was independently associated with a significantly higher risk of MI at 90‐days and 1 year after PCI.

Conclusions

Despite higher risk clinical presentation and worse 1‐year ischemic outcomes, AA race was an independent predictor of lower prasugrel prescription in a contemporary population of ACS patients undergoing PCI.
Urothelial neoplasm in a 19‐year‐old male patient with urine discoloration, negative lab, and imaging workup: Should we investigate the findings or the symptom?
Authors: Symeonidis Evangelos N. , Symeonidis Asterios , Gkekas Chrysovalantis , Georgiadis Christos , Malioris Apostolos , Papathanasiou Michail
Published: January 2019

Key Clinical Message

With few cases of PUNLMPs in young adults being reported in the literature, we hope to raise clinical awareness of prompt and effective diagnosis, while maintaining a high index of suspicion among health professionals. Even in the absence of red blood cells in the urine and subsequent negative imaging workup, clinicians should not delay performance of diagnostic cystoscopy.
Beyond Cars: Fischer‐Tropsch Synthesis for Non‐Automotive Applications
Authors: Sun Jian , Yang Guohui , Peng Xiaobo , Kang Jincan , Wu Jinhu , Liu Guangbo , Tsubaki Noritatsu
Published: January 2019

As a century‐old classical reaction, Fischer‐Tropsch (F‐T) synthesis is undergoing new developments especially in its applications of producing jet fuel, olefins, aromatics and oxygenated chemicals, which are completely different from the conventional F‐T product, gasoline, diesel and wax. Producing above new products is not obeying famous ASF distribution law, requiring revolutionary design of new F‐T catalysts and reaction pathways. A mass of new research directions on F‐T synthesis for these liquid fuels and high‐value chemicals are successfully proposed. This review spotlights recent new advances based on F‐T synthesis for non‐automotive applications, and discusses its new possible directions in future.
Protonation and Anion Binding Properties of Aromatic Bis‐Urea Derivatives—Comprehending the Proton Transfer
Authors: Barišić Dajana , Cindro Nikola , Kulcsár Marina Juribašić , Tireli Martina , Užarević Krunoslav , Bregović Nikola , Tomišić Vladislav
Published: January 2019

A series of aromatic bis‐urea derivatives was prepared and their proton dissociation, as well as anion binding properties in DMSO were investigated. To this end, UV/Vis and 1H NMR spectroscopies and computational methods were employed. The synthesized molecules differed in the relative position of the urea moieties (ortho‐ and meta‐derivatives) and in the functional groups (−H, −CH3, −OCH3, −NO2) in the para‐position of the pendant phenyl groups. Remarkably high acidities of the compounds (logK1H≈14), were ascribed primarily to the stabilizing effect of the aromatic subunits. Quantum chemical calculations corroborated the conclusions drawn from experimental data and provided information from the structural point of view. Knowledge regarding protonation properties proved to be essential for reliable quantitative determination of anion binding affinities. Studied receptors were selective for acetate and dihydrogen phosphate among several anions. Formation of their complexes of 1:1 and 1:2 (ligand/anion) stoichiometries was quantitatively characterized. Proton transfer was taken into account in the course of data analysis, which was especially important in the case of AcO−. ortho‐Receptors were proven to be more efficient acetate binders, achieving coordination with all four NH groups. The meta‐analogues preferred dihydrogen phosphate, which acted as both hydrogen bond donor and acceptor. Cooperative binding was detected in the case of 1:2 H2PO4− complexes, which was assigned to formation of interanionic hydrogen bonds.
Understanding the Reactivity and Selectivity of Fluxional Chiral DMAP‐Catalyzed Kinetic Resolutions of Axially Chiral Biaryls
Authors: Maji Rajat , Ugale Heena , Wheeler Steven E.
Published: January 2019

Fluxional chiral DMAP‐catalyzed kinetic resolutions of axially chiral biaryls were examined using density functional theory. Computational analyses lead to a revised understanding of this reaction in which the interplay of numerous non‐covalent interactions control the conformation and flexibility of the active catalyst, the preferred mechanism, and the stereoselectivity. Notably, while the DMAP catalyst itself is confirmed to be highly fluxional, electrostatically driven π⋅⋅⋅π+ interactions render the active, acylated form of the catalyst highly rigid, explaining its pronounced stereoselectivity.
Pyrrhotite depression studies with DETA and SMBS on a Ni‐Cu sulphide ore
Authors: Multani Ravinder S. , Waters Kristian E.
Published: January 2019

Pyrrhotite (Po) is a common gangue mineral in Ni‐Cu sulphide ores (pentlandite {Pn}‐chalcopyrite {Cp}) and can be difficult to reject under certain circumstances. This paper summarizes the results of a lab‐scale flotation study on a reactive ore with a high Po/Pn ratio (7.5), 42 % hexagonal Po content (of total Po), and 85.9 % Ni deportment in Pn (remainder Ni largely reporting to Po), making Po rejection challenging and Ni recovery/grade targets difficult to obtain. The main objective was to assess whether the ore could be processed “as received” to achieve high Pn recovery (>85 %) while ensuring low Po recovery (<20 %), which will typically yield acceptable final concentrate grades after cleaning stages. Baseline testing showed Po depression was difficult by conventional means and required depressants. The test work was centered around the use of DETA (diethylenetriamine) for its proven effectiveness for Po depression (used with sodium metabisulphite (SMBS)). Several strategies were tested: DETA alone; DETA/SMBS; sulphuric acid/DETA/SMBS with/without aeration; and DETA/SMBS with concentrate regrind. The DETA was found to be effective as a Po depressant (both hexagonal and monoclinic Po) on this challenging ore. Overall, the DETA/SMBS with concentrate regrind exhibited the best results (∼11 % Po recovery at ∼85 % Pn recovery) and was found to be sufficient in achieving the outlined targets.