bluuebunny/crossref_metadata_2025 huggingface dataset:
The Relationship of Dysbiosis of Duodenal Microbiome and Functional Dyspepsia
Authors: Kim Nayoung
Published: December 2024

Functional dyspepsia (FD) is a common gastrointestinal disorder characterized by chronic or recurrent epigastric pain or discomfort and postprandial fullness, without a definite organic cause. Despite the importance of FD in terms of decreased quality of life and recurrence, treatment modalities have been unsatisfactory, mainly because of their complex and heterogeneous nature. A link between microbiome dysbiosis and low-grade inflammation, along with mucosal barrier disruption of the duodenal mucosa, has been suggested and may be a potential target for FD treatment. This link supports the gut-brain (overactive visceral signaling and pain modulation) and the brain-gut (abnormal central processing) axes in FD. A definite increase in Streptococcus and a reduced abundance of Prevotella, Veillonella, and Actinomyces have also been observed. In addition, bacterial overgrowth is frequently observed in the small intestine, and rifaximin treatment improves the symptoms of FD, especially in women. This evidence highlights the importance of bacterial ecology in the development of FD symptoms. However, further research is necessary to prove the causal relationship between duodenal mucosal microbiota dysbiosis and FD.
Memoir of Seroepidemiological Study of Helicobacter pylori Infection in Asymptomatic People in South Korea Started in 1997
Authors: Kim Nayoung
Published: December 2024

To establish health policies for the prevention of Helicobacter pylori-related diseases, it is crucial to observe prevalence trends and identify risk factors for H. pylori infection. In 1997, the Korean H. pylori Study Group (currently the Korean College of Helicobacter and Upper Gastrointestinal Research) designed a nationwide multicenter study to assess H. pylori seroprevalence and identify risk factors in the asymptomatic Korean population. Sera were collected from 2687 females and 3049 males (mean age: 29.1 years; range: 1 month to 79 years) across Korea from March 1998 to October 1998. All asymptomatic participants completed an assessment questionnaire. An enzyme-linked immunosorbent assay (GENEDIA® H. pylori ELISA) was performed to detect immunoglobulin G antibodies to H. pylori. The seroprevalence rates were 17.2% in children (neonates to 15 years) and 66.9% in adults (16–79 years). A multivariate analysis indicated that variables such as sex, age, geographic area, crowding (number of persons per room) during childhood, economic status during childhood, and types of housing during childhood were significantly and independently associated with H. pylori seroprevalence in adults. For children, significant risk factors included age, geographic area, family income, maternal education, and drinking water sources. Socioeconomic conditions and close person-to-person contact during childhood were significant determinants of H. pylori infection in adults. Additionally, the source of drinking water emerged as a crucial risk factor for H. pylori infection in children, indicating fecal-oral transmission in Korea. This well-organized national study by the Korean H. pylori Study Group is an important milestone in the 30-year history of the Korean College of Helicobacter and Upper Gastrointestinal Research and should be remembered by the society’s members.
Gastrojejunocolic Fistula: A Late Complication After Gastrojejunostomy
Authors: Sin Seung Ho , Choi Hyun Ho
Published: December 2024

Gastrojejunocolic fistula, a rare but serious complication of gastrojejunostomy often results from inadequate resection or incomplete vagotomy during gastric surgery. The most common symptoms include feculent vomiting, chronic diarrhea, and weight loss, and surgical repair is the definitive treatment for this condition. A 51-year-old man presented to our hospital with upper abdominal pain and chronic diarrhea. He had a history of gastric surgery for gastric cancer, 20 years prior at another hospital. Upper endoscopy and abdominal computed tomography confirmed diagnosis of a gastrojejunocolic fistula. In this case report, we present the clinical features and diagnostic approaches for gastrojejunocolic fistulas.
Identidade, memória e colonialidade de gênero no conto “Tílburi de praça”, de Raul Pompéia
Authors: Willig Caroline Luiza , Schmidt Saraí Patrícia
Published: December 2024

Um clássico do modernismo brasileiro, “Tílburi de praça”, de Raul Pompéia, apresenta elementos que evidenciam a colonialidade de gênero que é estruturante na sociedade brasileira, no que tange à universalização da identidade de mulher aos moldes patriarcais, e também traços que permitem a desconstrução desta. A proposta deste escrito é elucidar a respeito das características que articulam o narrador-personagem aos eixos da identidade e da memória, a fim de observar como este constrói, a partir de sua cosmovisão, os demais personagens ao longo do conto. O aporte teórico-metodológico para a análise tem como base os escritos de Ricoeur (1994), Costa (1992), Maingueneau (2006; 2008), Reis (1995), Santos (2011), Lugones (2014) e Engels (1884).
Adoção e homoparentalidade no filme Patrik 1.5
Authors: Brandane Minari Amanda , Arantes de Oliveira-Cardoso Érika , Boffi Letícia Carolina , Dos Santos Manoel Antônio
Published: December 2024

Este artigo examina o processo de transição para a parentalidade adotiva em um casal homossexual masculino, por meio da análise de uma narrativa cinematográfica. Ao longo do filme Patrik 1.5, acompanhamos a história de uma adoção tardia e a formação do vínculo entre os pais e o filho adolescente. Alegrias e surpresas iniciais no cenário da adoção são abordadas, bem como seus desdobramentos na dinâmica conjugal do casal protagonista. Partindo da compreensão do filme como meio de reprodução de discursos que integram a vida social, analisamos cenas selecionadas à luz do arcabouço teórico da Psicanálise Vincular. Interpretamos as tramas envolvidas no processo de construção da vincularidade entre pais adotivos e filho, com foco nos processos vivenciados pelo casal na esfera conjugal, destacando os tensionamentos que levaram à ruptura momentânea. Com apoio do adolescente, o casal conseguiu reconfigurar o vínculo amoroso, ao mesmo tempo em que abriu espaço para acolher o novo membro familiar.
O corpo em evidência
Authors: Sousa Francisco das Chagas Alexandre Nunes de
Published: December 2024

Este artigo aborda como, a partir da década de 2000, Judith Butler realiza uma releitura criativa de conceitos de Hannah Arendt. Privilegiamos a apropriação feita da noção de “espaço de aparecimento” e suas implicações para as questões trans. Aqui, o espaço, mais do que uma geografia física, aparece com um entre-lugar [in-between] arendtiano que faz e se desfaz mediante o encontro dos corpos. Para dialogar com a questão do aparecimento e invisibilidade de pessoas trans no espaço público, utilizamos as reflexões de Viviane Namaste (2006); Susan Stryker e Stephen Whittle (2006); Viviane Vergueiro (2015).
Crime, Loucura e Castigo
Authors: Loureiro Martins Helena , Santana Leone de Souza Andrea
Published: December 2024

Entre o final do século XIX e começo do século XX, ganha destaque o debate internacional entre psiquiatria e criminologia acerca do lugar clínico dos(as) pacientes psiquiátricos(as) que cometem atos violentos de grande repercussão jurídica. Em relação às mulheres, atrelou-se a manifestação de violência a desequilíbrios de ordem hormonal. Em sentido diverso, este estudo objetivou discutir, à luz de seus precedentes sociológicos, o perfil das vítimas nos atos infracionais de mulheres recolhidas à custódia psiquiátrica. Para tanto, a pesquisa qualitativa recorreu ao estudo de caso da ala feminina do Hospital de Custódia e Tratamento Psiquiátrico da Bahia (HCTP-BA), em abordagem empírica com técnica de entrevistas semidiretas às pacientes e aos profissionais. Além disso, realizou-se uma revisão de literatura e normativa. Como resultado, identificou-se o perfil majoritário de companheiros e filhos(as) como vítimas dos atos infracionais cometidos por mulheres direcionadas ao HCTP. No contexto do cometimento dos atos no qual emergiu a crise psiquiátrica, sobressaltou a similitude de conflitos de gênero de ordem física, sexual e psicológica contra a mulher. Conclui-se que a categoria de vítimas se repete entre os casos em função de seu atrelamento à circunstância comum de violência no ambiente doméstico.
Transient receptor potential V4 channel stimulation induces reversible epithelial cell permeability in MDCK cell monolayers
Authors: Mukaiyama Minagi , Yamasaki Yohei , Usui Takeo , Nagumo Yoko
Published: June 2019

The transient receptor potential V4 channel (TRPV4) is responsive to a variety of physical and chemical stimuli, including a synthetic agonist GSK1016790A (GSK). Here, we show that TRPV4 is functionally expressed in, and that GSK induces the reversible opening of tight junctions (TJs) in epithelial Madin–Darby canine kidney II monolayers. Stimulation of TRPV4 by GSK induces an increase in fluorescein isothiocyanate‐conjugated dextran (4 kDa) permeability and a reduction in transepithelial resistance, and these responses are blocked by pretreatment with the specific TRPV4 antagonist. Small conductance, but not large conductance Ca2+‐activated K+ channels, TRPA1 channel, and cofilin activation are involved in TRPV4‐mediated reversible opening of TJs. These results suggest that a novel mechanism underlies TRPV4‐mediated regulation of the tightness of epithelial barriers.
The epitranscriptome in translation regulation: mRNA and tRNA modifications as the two sides of the same coin?
Authors: Ranjan Namit , Leidel Sebastian A.
Published: June 2019

Translation of mRNA is a highly regulated process that is tightly coordinated with cotranslational protein maturation. Recently, mRNA modifications and tRNA modifications – the so called epitranscriptome – have added a new layer of regulation that is still poorly understood. Both types of modifications can affect codon–anticodon interactions, thereby affecting mRNA translation and protein synthesis in similar ways. Here, we describe an updated view on how the different types of modifications can be mapped, how they affect translation, how they trigger phenotypes and discuss how the combined action of mRNA and tRNA modifications coordinate translation in health and disease.
Exploring site‐specific activation of bis‐N,N’‐dialkylaminophosphordiamidites and the synthesis of morpholinophosphoramidate oligonucleotides
Authors: Krishna Heera , Jastrzebska Katarzyna , Caruthers Marvin
Published: June 2019

Morpholinos are six‐membered rings that may provide higher conformational rigidity when incorporated into an oligonucleotide (ODN) backbone. Phosphorodiamidate morpholinos are chemically modified ODNs containing morpholinos in place of 2’‐deoxyribose moieties throughout their backbone and have garnered much interest in recent years due to their ability to function as highly effective steric blockers in exon skipping therapy. To further explore the biophysical and biological properties of ODNs derived from morpholino nucleosides, we have replaced the 2’‐deoxyribonucleotides of phosphodiester DNA with morpholinonucleotides to generate phosphoramidate ODNs. Here, we evaluate the mechanistic pathways observed during the solution‐phase synthesis of morpholinonucleoside phosphoramidites, solid‐phase synthesis of morpholinonucleotide phosphoramidates of mA, mG, mC and mT (prefix ‘m’ represents morpholino) and our first attempts directed at the solid‐phase synthesis of chimeric DNA‐phosphoramidate ODNs, as well as fully modified 22‐mer phosphoramidate ODNs.
Interpersonal prosodic correlation in frontotemporal dementia
Authors: Pressman Peter S. , Ross Elliott D. , Cohen Kevin B. , Chen Kuan‐Hua , Miller Bruce L. , Hunter Lawrence E. , Gorno‐Tempini Maria Luisa , Levenson Robert W.
Published: June 2019

Communication accommodation describes how individuals adjust their communicative style to that of their conversational partner. We predicted that interpersonal prosodic correlation related to pitch and timing would be decreased in behavioral variant frontotemporal dementia (bvFTD). We predicted that the interpersonal correlation in a timing measure and a pitch measure would be increased in right temporal FTD (rtFTD) due to sparing of the neural substrate for speech timing and pitch modulation but loss of social semantics. We found no significant effects in bvFTD, but conversations including rtFTD demonstrated higher interpersonal correlations in speech rate than healthy controls.
Many buprenorphine prescribers don't take Medicaid or uninsured patients
Authors: Knopf Alison
Published: June 2019

In a survey in which callers seeking buprenorphine treatment for opioid use disorder (OUD) posed as patients with either Medicaid or no insurance, researchers found that few were offered an appointment with the possibility of buprenorphine induction at the first visit. The calls were conducted in Massachusetts, Maryland, New Hampshire, West Virginia, Ohio and the District of Columbia, all of which have a high burden of OUD. The callers found that out of 546 clinicians on the buprenorphine prescriber database maintained by the Substance Abuse and Mental Health Services Administration (SAMHSA), new appointments were offered to 54% of Medicaid callers and 62% of uninsured (meaning cash‐paying) patients, but that only 27% of Medicaid and 41% of uninsured callers had a possibility of buprenorphine treatment, and not all would get it right away. In fact, the median wait time for the first appointment was six days.
A Polarization Insensitive Wide‐Band Perfect Absorber
Authors: Durmaz Habibe , Cetin Arif E. , Li Yuyu , Paiella Roberto
Published: June 2019

In this article, a wide‐band and polarization‐insensitive perfect absorber composed of 4 sandwiched layers of dielectric and metal disks is introduced. Compared to classical perfect absorbers, the system supports near‐unity absorption within a wider spectral window through multiple perfect absorption mechanisms that exist due to a constituting inter‐metal disk, functioning either as a dipolar antenna or a conducting ground for different perfect absorption mechanisms. Circular shape of the antenna makes the working mechanism of the system polarization insensitive. The working principle of the system is investigated through near‐ and far‐field calculations by finite difference time domain (FDTD) simulations. A fine‐tuning mechanism of the wide‐range perfect absorption window is introduced through geometrical device parameters. The multilayer perfect absorber system is fabricated through a high‐quality fabrication method based on electron beam lithography, lift‐off method, and multi‐step deposition of metal and dielectric layers. The spectral behavior of the perfect absorber system is finally experimentally investigated through Fourier transform infrared (FTIR) spectroscopy.
Progress in the Design of Cooperative Heterogeneous Catalytic Materials for C–C Bond Formation
Authors: Khoury Christine , Gadipelly Chandrakanth , Pappuru Sreenath , Shpasser Dina , Gazit Oz M.
Published: June 2019

The application of cooperative heterogeneous catalysts for the promotion of C–C bond formation is of great potential for making such chemical processes more sustainable. In the design of such materials, the main challenges are to form specific catalytic sites and to control the cooperative interactions. Because of the high complexity inherent to cooperative active site interactions, much of the research is focused on so called “enzyme inspired‐materials.” The current Progress Report identifies three material subgroups that are characterized by a rigid‐ordered backbone (layered material), a flexible backbone (polymer based), or a constrained‐flexible‐ordered backbone (metal organic frameworks). In each of these material types, examples that illustrate how key structural and chemical characteristics functions are associated with the efficient promotion of the cooperative mechanism are highlighted. The limitations and strengths of each of the systems are considered with the aim of providing an outlook with regard to the minimum requirements needed to construct an efficient cooperative catalytic material. Given the current accumulated common knowledge in this area, it is suggested that getting inspiration from the synthetic existing systems is perhaps more beneficial than from enzymes.
Dynamic Photomask‐Assisted Direct Ink Writing Multimaterial for Multilevel Triboelectric Nanogenerator
Authors: Chen Kaijuan , Zhang Lei , Kuang Xiao , Li Vincent , Lei Ming , Kang Guozheng , Wang Zhong Lin , Qi Hang Jerry
Published: June 2019

Triboelectric nanogenerator (TENG) devices are extensively studied as a mechanical energy harvester and self‐powered sensor for wearable electronics and physiological monitoring. However, the conventional TENG fabrication involving assembling steps and using the single property of matrix material suffers from simple devices shape and a single level of mechanical response for sensing and energy harvesting. Here, the printed multimaterial matrix for multilevel mechanical‐responsive TENG with on‐demand reconfiguration of shape is reported. A multimaterial 3D printing approach by using dynamic photomask‐assisted direct ink writing printing together with a two‐stage curing hybrid ink is first developed. Multimaterial structures with location‐specific properties, such as tensile modulus, failure stress, and glass transition temperature for controlled deformation, crack propagation path, and sequential shape memory, are directly printed. The printed multimaterial structure with sequential deformation behavior is used to fabricate a multilevel‐TENG (mTENG) device for multiple level mechanical energy harvesters and sensors. It is demonstrated that the mTENG can be embedded in shoe insoles to achieve both comfortable wearing and motion state monitoring. This work provides a new approach to combine multimaterial 3D printing with TENG devices for functional wearable electronics as energy harvester and sensors.
Kinetic Stabilization of the Sol–Gel State in Perovskites Enables Facile Processing of High‐Efficiency Solar Cells
Authors: Wang Kai , Tang Ming‐Chun , Dang Hoang X. , Munir Rahim , Barrit Dounya , De Bastiani Michele , Aydin Erkan , Smilgies Detlef‐M. , De Wolf Stefaan , Amassian Aram
Published: June 2019

Perovskite solar cells increasingly feature mixed‐halide mixed‐cation compounds (FA1−x−yMAxCsyPbI3−zBrz) as photovoltaic absorbers, as they enable easier processing and improved stability. Here, the underlying reasons for ease of processing are revealed. It is found that halide and cation engineering leads to a systematic widening of the anti‐solvent processing window for the fabrication of high‐quality films and efficient solar cells. This window widens from seconds, in the case of single cation/halide systems (e.g., MAPbI3, FAPbI3, and FAPbBr3), to several minutes for mixed systems. In situ X‐ray diffraction studies reveal that the processing window is closely related to the crystallization of the disordered sol–gel and to the number of crystalline byproducts; the processing window therefore depends directly on the precise cation/halide composition. Moreover, anti‐solvent dripping is shown to promote the desired perovskite phase with careful formulation. The processing window of perovskite solar cells, as defined by the latest time the anti‐solvent drip yields efficient solar cells, broadened with the increasing complexity of cation/halide content. This behavior is ascribed to kinetic stabilization of sol–gel state through cation/halide engineering. This provides guidelines for designing new formulations, aimed at formation of the perovskite phase, ultimately resulting in high‐efficiency perovskite solar cells produced with ease and with high reproducibility.
Ferroelectric Extended Nanofluidic Channels for Room‐Temperature Microfuel Cells
Authors: Pihosh Yuriy , Kazoe Yutaka , Mawatari Kazuma , Seo Hangyeol , Tabata Osamu , Tsuchiya Toshiyuki , Kitamura Kenji , Tosa Masahiro , Turkevych Ivan , Kitamori Takehiko
Published: June 2019

Integration of fuel cells into microfluidic devices requires development of innovative proton conductors. Conventional Nafion membranes are incompatible with planar‐type microfluidic devices and require a high operation temperature of over 100 °C to achieve rapid proton transfer. In contrast, glass nanochannels (NCs) work as proton conductors even at room temperature and can be seamlessly integrated into microfluidic devices, which in turn makes microfuel cells (µFCs) attractive for a wide range of practical applications, such as power sources for ultrasmall autonomous electronics and chemo‐ or biosensors. However, the conductivity of NCs is limited by their small cross‐sectional area. It is revealed that spontaneous polarization of lithium niobite (LiNbO3) used as the NC material enhances a surface charge of a SiO2 layer formed on LiNbO3 and induces a fast proton transfer in water in the NCs. It is demonstrated that a µFC containing the LiNbO3 NCs demonstrates a proton diffusion coefficient that is 1.8 times higher than that of a reference device with bare glass NCs. In addition, such a µFC achieves a remarkable power output of up to ≈54 mW cm−2 at room temperature, which is 1.4 times higher than that of the similar device with bare glass NCs.
The Relationship between Local Identification, Urban Disorder Sensitivity, and Prejudice Toward Immigrants: The Role of Autochthony
Authors: Gattino Silvia , Tartaglia Stefano , Rollero Chiara , De Piccoli Norma
Published: June 2019

Highlights

Local identification is related to both autochthony and sensitivity to urban disorder.

Local identification is directly and indirectly associated with ethnic prejudice.

Autochthony is a powerful ideology that can trigger exclusionary responses.
Stable Cross‐Conjugated Tetrathiophene Diradical
Authors: Zhang Cheng , Medina Rivero Samara , Liu Wuyue , Casanova David , Zhu Xiaozhang , Casado Juan
Published: June 2019

A tetracyano quinoidal tetrathiophene, having a central bi(thieno[3,4‐c]pyrrole‐4,6‐dione) acceptor, has been studied. The recovered aromaticity of the thiophenes produces a diradical species with cross‐conjugation between the inter‐dicyano and inter‐dione acceptor paths. A diradical character of y0=0.61 and a singlet–triplet gap of −2.76 kcal mol−1 were determined. Competition between the two cross‐conjugated paths enhances the disjointed character of the SOMOs and results in the confinement of the diradical to the molecular center, enabling a thermodynamic diradical stabilization featuring a half‐life of 262 hours. Cross‐conjugation effects have been also addressed in the anionic species (up to a radical trianion).
Tunable Surface Area, Porosity, and Function in Conjugated Microporous Polymers
Authors: Chen Jie , Yan Wei , Townsend Esther J. , Feng Jiangtao , Pan Long , Del Angel Hernandez Veronica , Faul Charl F. J.
Published: June 2019

Simple inorganic salts are used to tune N‐containing conjugated microporous polymers (CMPs) synthesized by Buchwald–Hartwig (BH) cross‐coupling reactions. Poly(triphenylamine), PTPA, initially shows a broad distribution of micropores, mesopores, and macropores. However, the addition of inorganic salts affects all porous network properties significantly: the pore size distribution is narrowed to the microporous range only, mimicking COFs and MOFs; the BET surface area is radically improved from 58 m2 g−1 to 1152 m2 g−1; and variations of the anion and cation sizes are used to fine‐tune the surface area of PTPA, with the surface area showing a gradual decrease with an increase in the ionic radius of salts. The effect of the salt on the physical properties of the polymer is attributed to adjusting and optimizing the Hansen solubility parameters (HSPs) of solvents for the growing polymer, and named the Beijing–Xi'an Jiaotong (BXJ) method.
Oxidative Amide Coupling from Functionally Diverse Alcohols and Amines Using Aerobic Copper/Nitroxyl Catalysis
Authors: Piszel Paige E. , Vasilopoulos Aristidis , Stahl Shannon S.
Published: June 2019

The aerobic Cu/ABNO catalyzed oxidative coupling of alcohols and amines is highlighted in the synthesis of amide bonds in diverse drug‐like molecules (ABNO=9‐azabicyclo[3.3.1]nonane N‐oxyl). The robust method leverages the privileged reactivity of alcohols bearing electronegative hetero‐ atoms (O, F, N, Cl) in the β‐position. The reaction tolerates over 20 unique functional groups and is demonstrated on a 15 mmol scale under air. Steric constraints of the catalyst allow for chemoselective amidation of primary amines in the presence of secondary amines. All catalyst components are commercially available, and the reaction proceeds under mild conditions with retention of stereocenters in both reaction partners, while producing only water as a by‐product.
Inhibition of Pathogen Adhesion by Bacterial Outer Membrane‐Coated Nanoparticles
Authors: Zhang Yue , Chen Yijie , Lo Christopher , Zhuang Jia , Angsantikul Pavimol , Zhang Qiangzhe , Wei Xiaoli , Zhou Zhidong , Obonyo Marygorret , Fang Ronnie H. , Gao Weiwei , Zhang Liangfang
Published: June 2019

Anti‐adhesion therapies interfere with the bacterial adhesion to the host and thus avoid direct disruption of bacterial cycles for killing, which may alleviate resistance development. Herein, an anti‐adhesion nanomedicine platform is made by wrapping synthetic polymeric cores with bacterial outer membranes. The resulting bacterium‐mimicking nanoparticles (denoted “OM‐NPs”) compete with source bacteria for binding to the host. The “top‐down” fabrication of OM‐NPs avoids the identification of the adhesins and bypasses the design of agonists targeting these adhesins. In this study, OM‐NPs are made with the membrane of Helicobacter pylori and shown to bind with gastric epithelial cells (AGS cells). Treatment of AGS cells with OM‐NPs reduces H. pylori adhesion and such anti‐adhesion efficacy is dependent on OM‐NP concentration and its dosing sequence.
Structural Engineering of Luminogens with High Emission Efficiency Both in Solution and in the Solid State
Authors: Wu Hongwei , Chen Zhao , Chi Weijie , Bindra Anivind Kaur , Gu Long , Qian Cheng , Wu Bing , Yue Bingbing , Liu Guofeng , Yang Guangbao , Zhu Liangliang , Zhao Yanli
Published: June 2019

Developing molecules with high emission efficiency both in solution and the solid state is still a great challenge, since most organic luminogens are either aggregation‐caused quenching or aggregation‐induced emission molecules. This dilemma was overcome by integrating planar and distorted structures with long alkyl side chains to achieve DAπAD type emitters. A linear diphenyl–diacetylene core and the charge transfer effect ensure considerable planarity of these molecules in the excited state, allowing strong emission in dilute solution (quantum yield up to 98.2 %). On the other hand, intermolecular interactions of two distorted cyanostilbene units restrict molecular vibration and rotation, and long alkyl chains reduce the quenching effect of the π–π stacking to the excimer, eventually leading to strong emission in the solid state (quantum yield up to 60.7 %).
Diagonally Related s‐ and p‐Block Metals Join Forces: Synthesis and Characterization of Complexes with Covalent Beryllium–Aluminum Bonds
Authors: Paparo Albert , Smith Cory D. , Jones Cameron
Published: June 2019

Additions of beryllium–halide bonds in the simple beryllium dihalide adducts, [BeX2(tmeda)] (X=Br or I, tmeda=N,N,N′,N′‐tetramethylethylenediamine), across the metal center of a neutral aluminum(I) heterocycle, [:Al(DipNacnac)] (DipNacnac=[(DipNCMe)2CH]−, Dip=2,6‐diisopropylphenyl), have yielded the first examples of compounds with beryllium–aluminum bonds, [(DipNacnac)(X)Al‐Be(X)(tmeda)]. For sake of comparison, isostructural Mg–Al and Zn–Al analogues of these complexes, viz. [(DipNacnac)(X)Al‐M(X)(tmeda)] (M=Mg or Zn, X=I or Br) have been prepared and structurally characterized. DFT calculations reveal all compounds to have high s‐character metal–metal bonds, the polarity of which is consistent with the electronegativities of the metals involved. Preliminary reactivity studies of [(DipNacnac)(Br)Al‐Be(Br)(tmeda)] are reported.
σ‐Noninnocence: Masked Phenyl‐Cation Transfer at Formal NiIV
Authors: Steen Jelte S. , Knizia Gerald , Klein Johannes E. M. N.
Published: June 2019

Reductive elimination is an elementary organometallic reaction step involving a formal oxidation state change of −2 at a transition‐metal center. For a series of formal high‐valent NiIV complexes, aryl–CF3 bond‐forming reductive elimination was reported to occur readily (Bour et al. J. Am. Chem. Soc. 2015, 137, 8034–8037). We report a computational analysis of this reaction and find that, unexpectedly, the formal NiIV centers are better described as approaching a +II oxidation state, originating from highly covalent metal–ligand bonds, a phenomenon attributable to σ‐noninnocence. A direct consequence is that the elimination of aryl–CF3 products occurs in an essentially redox‐neutral fashion, as opposed to a reductive elimination. This is supported by an electron flow analysis which shows that an anionic CF3 group is transferred to an electrophilic aryl group. The uncovered role of σ‐noninnocence in metal–ligand bonding, and of an essentially redox‐neutral elimination as an elementary organometallic reaction step, may constitute concepts of broad relevance to organometallic chemistry.
Influencing Epigenetic Information with a Hydrolytically Stable Carbocyclic 5‐Aza‐2′‐deoxycytidine
Authors: Wildenhof Thomas M. , Schiffers Sarah , Traube Franziska R. , Mayer Peter , Carell Thomas
Published: June 2019

5‐Aza‐2′‐deoxycytidine (AzadC) is an antimetabolite in clinical use, which reduces the level of the epigenetic modification 5‐methyl‐2′‐deoxycytidine (mdC). AzadC is incorporated into the genome of proliferating cells, where it inhibits DNA methyltransferases (DNMTs), leading to a reduction of mdC. The loss of mdC, which is a transcriptional silencer in the promoter region found upstream of genes, leads to the reactivation of the corresponding gene, including tumor‐suppressor genes, which elicits a beneficial effect. The problem associated with AzadC is that the compound is hydrolytically unstable. It decomposes during treatment to a variety of poorly characterized hydrolysis products. After its incorporation into the genome, this hydrolytic instability generates abasic sites. It is consequently difficult to dissect whether the activity of the compound is caused by DNMT inhibition or more generally by DNA lesion formation. We now discovered that a disarmed version of AzadC, in which the ribose oxygen was replaced by a CH2 group, is surprisingly stable under a variety of pH values while keeping activity against the DNMTs.
Guanitrypmycin Biosynthetic Pathways Imply Cytochrome P450 Mediated Regio‐ and Stereospecific Guaninyl‐Transfer Reactions
Authors: Liu Jing , Xie Xiulan , Li Shu‐Ming
Published: June 2019

Mining microbial genomes including those of Streptomyces reveals the presence of a large number of biosynthetic gene clusters. Unraveling this genetic potential has proved to be a useful approach for novel compound discovery. Here, we report the heterologous expression of two similar P450‐associated cyclodipeptide synthase‐containing gene clusters in Streptomyces coelicolor and identification of eight rare and novel natural products, the C3‐guaninyl indole alkaloids guanitrypmycins. Expression of different gene combinations proved that the cyclodipeptide synthases assemble cyclo‐l‐Trp‐l‐Phe and cyclo‐l‐Trp‐l‐Tyr, which are consecutively and regiospecifically modified by cyclodipeptide oxidases, cytochrome P450 enzymes, and N‐methyltransferases. In vivo and in vitro results proved that the P450 enzymes function as key biocatalysts and catalyze the regio‐ and stereospecific 3α‐guaninylation at the indole ring of the tryptophanyl moiety. Isotope‐exchange experiments provided evidence for the non‐enzymatic epimerization of the biosynthetic pathway products via keto–enol tautomerism. This post‐pathway modification during cultivation further increases the structural diversity of guanitrypmycins.
Natural polyelectrolyte complex‐based pH‐dependent delivery carriers using alginate and chitosan
Authors: Park Jun Woo , Park Kyu Ha , Seo Sungbaek
Published: June 2019

The pH‐dependent complexation behaviors of natural and counterionic polyelectrolyte complexes (PECs) without crosslinkers have been rarely studied. In this work, alginate (0.5–2.5 wt %) and chitosan (0.5–2 wt %) were combined to formulate turbid gel‐like assemblies. The PEC was consisted of ~100‐μm‐sized porous structure observed by scanning electron microscope images and electrostatic interactions inside the complex were newly formed characterized by Fourier transform infrared spectra. Based on visual monitoring and ultraviolet–visible absorption measurement, the complex maintained the gel‐like structure under acidic, while the complex was more dissolved under becoming basic. As a demonstration of potential pH‐dependent delivery, distinct release profiles of the complexes encapsulating rhodamine 6G (R6G) or doxorubicin, were observed when they were immersed in acidic, neutral, and basic medium. Within 2 h, 7.4, 35.4, and 73.7% of R6G were released under acidic, neutral, and basic condition, respectively, with reasons of degree of protonation or deprotonation of each natural polyelectrolyte at certain pH. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 48143.
Techniques for enhancing the tolerance of industrial microbes to abiotic stresses: A review
Authors: Lv Ziyao , Zhou Jie , Zhang Yue , Zhou Xinhai , Xu Ning , Xin Fengxue , Ma Jiangfeng , Jiang Min , Dong Weiliang
Published: June 2019

The diversity of stress responses and survival strategies evolved by microorganism enables them to survive and reproduce in a multitude of harsh environments, whereas the discovery of the underlying resistance genes or mechanisms laid the foundation for the directional enhancement of microbial tolerance to abiotic stresses encountered in industrial applications. Many biological techniques have been developed for improving the stress resistance of industrial microorganisms, which greatly benefited the bacteria on which industrial production is based. This review introduces the main techniques for enhancing the resistance of microorganisms to abiotic stresses, including evolutionary engineering, metabolic engineering, and process engineering, developed in recent years. In addition, we also discuss problems that are still present in this area and offer directions for future research.
Understanding Challenges of Cathode Materials for Sodium‐Ion Batteries using Synchrotron‐Based X‐Ray Absorption Spectroscopy
Authors: Chen Mingzhe , Chou Shu‐Lei , Dou Shi‐Xue
Published: June 2019

An in‐depth understanding of the electrochemical behavior of cathode materials in a complex chemical environment is critical for the development of state‐of‐the‐art sodium‐ion batteries. Advanced synchrotron‐based characterization is a powerful tool for collecting valuable information on complicated reaction mechanisms. X‐ray absorption spectroscopy can be used to precisely monitor the valence state and corresponding changes during cycling of various elements. Information on the local structure, such as coordination number and bond information can also be extracted from the fitting data in Fourier transform extended X‐ray absorption fine structure. In this review, we summarize findings on state‐of‐the‐art cathode materials using ex‐situ/in‐situ X‐ray absorption spectroscopy to probe fundamental discoveries on sodium‐ion battery systems and what important and valuable results have been obtained. Further possible improvements and practical operating advice are also discussed in detail.
Rosmarinic acid improved antioxidant properties and healthspan via the IIS and MAPK pathways in Caenorhabditis elegans
Authors: Lin Chunxiu , Xiao Jie , Xi Yun , Zhang Xiaoying , Zhong Qiqi , Zheng Huijuan , Cao Yong , Chen Yunjiao
Published: June 2019

Rosmarinic acid (RA) has a wide range of biological effects, including the antioxidation and antiaging. However, the detailed mechanisms remain unclear but highly attractive. Herein, RA promoted lifespan and motoricity in a dose‐dependent manner, and reduced fat store without threatening fertility in Caenorhabditis elegans. In term of antioxidant efficacy, catalase activity, glutathione peroxidas activity, reduced glutathione content, and reduced glutathione/oxidized glutathione ratio were enhanced. And malondialdehyde content was diminished significantly. Moreover, RA increased survival under acute oxidative and thermal stress, and suppressed intestinal lipofuscin accumulation. So the improvement of lifespan mediated by RA could be related with its strong antioxidant properties. Furthermore, RA was absorbed by worms. Further research in pursuit of the mechanism showed that longevity induced by RA was involved with the genes sod‐3, sod‐5, ctl‐1, daf‐16, ins‐18, skn‐1, and sek‐1, but was independent of subcellular localization of DAF‐16. These findings indicated that RA had a potential for promoting healthy lifespan.
RuO2‐coated MoS2 Nanosheets as Cathode Catalysts for High Efficiency LiO2 Batteries
Authors: Jeong Yo Sub , Jang Yu Jin , Park So‐Jung , Lee Yun Jung
Published: June 2019

Despite their potential for high capacity, lithium oxygen (Li–O2) batteries still suffer from the low round‐trip energy efficiency and limited cycle life, mainly due to the slow decomposition of discharge products. Therefore, developing efficient catalysts is a key issue for the practical application of Li‐O2 batteries. Ruthenium oxide (RuO2) is one of the most efficient catalysts developed thus far for lithium‐air batteries. However, the high price and limited availability of Ru prohibits its large‐scale use in practical device fabrications. Recently, molybdenum disulfide (MoS2) has been actively investigated in various catalytic systems, taking advantage of its two‐dimensional (2D) structure and catalytic activities. However, the low electrical conductivity of MoS2 limits the realization of fully operative MoS2‐based catalysts on its own. In this report, RuO2‐coated MoS2 nanosheets (RuO2/MoS2) are prepared and implemented as cathode catalysts for Li–O2 batteries. In this hybrid structure, RuO2 and MoS2 complement each other; the poor electrical conductivity of MoS2 is overcome by the nearly conformal coating of conducting RuO2, while 2D MoS2 nanosheets act as excellent supports for RuO2 catalysts and also contribute to the overall catalytic activities. These combined features result in excellent cathode performance, including improved efficiency and cycling lifetimes, with significantly reduced amounts of precious RuO2.
Optimization of integrated chromatography sequences for purification of biopharmaceuticals
Authors: Löfgren Anton , Yamanee‐Nolin Mikael , Tallvod Simon , Fons Joaquín G. , Andersson Niklas , Nilsson Bernt
Published: June 2019

With continued development of integrated and continuous downstream purification processes, tuning and optimization become increasingly complicated with additional parameters and codependent variables over the sequence. This article offers a novel perspective of nonlinear optimization of integrated sequences with regard to individual column sizes, flow rates, and scheduling. The problem setup itself is a versatile tool to be used in downstream design which is demonstrated in two case studies: a four‐column integrated sequence and a continuously loaded twin‐capture setup with five columns.
TRAIL‐Inspired Multivalent Dextran Conjugates Efficiently Induce Apoptosis upon DR5 Receptor Clustering
Authors: Schneider Hendrik , Yanakieva Desislava , Macarrón Arturo , Deweid Lukas , Becker Bastian , Englert Simon , Avrutina Olga , Kolmar Harald
Published: June 2019

Triggering apoptosis of tumor cells has been in focus of cancer‐inspired research since decades. As clustering of death receptor 5 (DR5), which is overexpressed on various cancer cells, leads to formation of the death‐inducing signaling cascade (DISC), DR5 has recently become a promising target for tumor treatment. Herein, we demonstrate that covalent multimerization of a death receptor targeting peptide (DR5TP) on a dextran scaffold generates potent apoptosis‐inducing conjugates (EC50=2–20 nm). A higher conformational flexibility compared to reported DR5TP multimerization approaches, introduced by the polysaccharide framework compensates the reported need for the defined ligand orientation that was considered as essential prerequisite for effective receptor clustering and apoptosis induction. Enzyme‐catalyzed ligation of a hydrophilic dextran conjugate bearing multiple DR5‐targeting sites to a human fragment crystallizable (Fc) receptor did not affect the potency (EC50=2–7 nm), providing an option for improved in vivo half‐life and prospective conjugation to an antibody of interest in view of bispecific tumor targeting.
Vicinal Diol‐Tethered Nucleobases as Targets for DNA Redox Labeling with Osmate Complexes
Authors: Havranová‐Vidláková Pavlína , Krömer Matouš , Sýkorová Veronika , Trefulka Mojmír , Fojta Miroslav , Havran Luděk , Hocek Michal
Published: June 2019

Six‐valent osmium (osmate) complexes with nitrogenous ligands have previously been used for the modification and redox labeling of biomolecules involving vicinal diol moieties (typically, saccharides or RNA). In this work, aliphatic (3,4‐dihydroxybutyl and 3,4‐dihydroxybut‐1‐ynyl) or cyclic (6‐oxo‐6‐(cis‐3,4‐dihydroxypyrrolidin‐1‐yl)hex‐2‐yn‐1‐yl, PDI) vicinal diols are attached to nucleobases to functionalize DNA for subsequent redox labeling with osmium(VI) complexes. The diol‐linked 2′‐deoxyribonucleoside triphosphates were used for the polymerase synthesis of diol‐linked DNA, which, upon treatment with K2OsO3 and bidentate nitrogen ligands, gave the desired Os‐labeled DNA, which were characterized by means of the gel‐shift assay and ESI‐MS. Through ex situ square‐wave voltammetry at a basal plane pyrolytic graphite electrode, the efficiency of modification/labeling of individual diols was evaluated. The results show that the cyclic cis‐diol (PDI) was a better target for osmylation than that of the flexible aliphatic ones (alkyl‐ or alkynyl‐linked). The osmate adduct‐specific voltammetric signal obtained for OsVI‐treated DNA decorated with PDI showed good proportionality to the number of PDI per DNA molecule. The OsVI reagents (unlike OsO4) do not attack nucleobases; thus offering specificity of modification on the introduced glycol targets.
Isolated pediatric transolecranon fracture‐dislocation of the elbow managed nonoperatively: A case report and review of literature
Authors: Arain Abdul Rehman , Haddad Stefanos , Anderson Matthew , Murtaza Hamza , Rosenbaum Andrew
Published: June 2019

We report on the sixth case of an isolated pediatric transolecranon fracture‐dislocation, and the first case utilizing nonoperative management in a cast following closed reduction resulting in an excellent outcome. Our case provides support for nonoperative management of these rare injuries, especially when surgery is not practical or desirable.
Aggregation Efficiency of Amorphous Silica Nanoparticles
Authors: Bałdyga Jerzy , Tyl Grzegorz , Bouaifi Mounir
Published: June 2019

Despite many attempts to understand the mechanisms of silica aggregation, there still is a gap to fill in the area of mathematical description of the process. Here, the problem of developing aggregation kernels of silica nanoparticles is addressed. A concept of efficiency of silica aggregation is based on the time scale analysis, which includes such phenomena as surface reactions bonding the particles and the particle Brownian and convective motions. This allows explaining the existence of the metastable region for pH values close to the isoelectric point and the fact that silica aggregates usually consist of primary particles very similar in size. It also helps to interpret the gelation process by considering aggregation and chemical bonding of fractal agglomerates.
Gelatin‐Based Capsules through Interfacial Polymerization: Batch and Continuous Flow Synthesis
Authors: Bacher Lisa , Maskos Michael , Musyanovych Anna
Published: June 2019

Cross‐linked gelatin capsules were prepared through interfacial polymerization in the inverse miniemulsion, using toluene diisocyanate (TDI) as a cross‐linker. Synthesis was performed in a batch process and in a continuous flow using a static micromixer. The obtained capsules were in the size range between 0.5 and 2 µm. The influence of TDI amount, pH of gelatin solution, and flow rates on the properties of capsules was studied by dynamic light scattering, transmission electron microscopy, and Fourier transform infrared spectroscopy. The thermoresponsive release of the hydrophilic dye sulforhodamine 101 was investigated by fluorescent spectroscopy. Furthermore, gelatin capsules loaded with magnetite nanoparticles were synthesized in a continuous way, showing the potential to produce capsules for drug release triggered by magnetic hyperthermia in large quantities.
Titanium(IV) Cations with Trigonal Monopyramidal Geometry: Unusual Lewis Acids Supported by a Triaryl Triamidoamine Ligand
Authors: Ghana Priyabrata , van Krüchten Franziska D. , Spaniol Thomas P. , Okuda Jun
Published: June 2019

Protonolysis of the titanium alkyl complex [Ti(CH2SiMe3)(Xy‐N3N)] (Xy‐N3N=[{(3,5‐Me2C6H3)NCH2CH2}3N]3−) supported by a triamidoamine ligand, with [NEt3H][B(3,5‐Cl2C6H3)4] or [PhNMe2H][B(C6F5)4] afforded the cations [Ti(Xy‐N3N)][A] (A−=[B(3,5‐Cl2C6H3)4]− (1[B(ArCl)4]; B(ArCl)4=tetrakis(3,5‐dichlorophenyl)borate); A−=[B(C6F5)4]− (1[B(ArF)4]; B(ArF)4=tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate). These Lewis acidic cations were reacted with coordinating solvents to afford the cations [Ti(L)(Xy‐N3N)][B(C6F5)4] (2‐L; L=Et2O, pyridine and THF). XRD analysis revealed a trigonal monopyramidal (TMP) geometry for the tetracoordinate cations in 1[B(ArX)4] and trigonal bipyramidal (TBP) geometry for the pentacoordinate cations in 2‐L. Variable‐temperature NMR spectroscopy showed a dynamic equilibrium for 2‐Et2O in solution, involving the dissociation of Et2O. Coordination to the titanium(IV) center activated the THF molecule, which, in the presence of NEt3, underwent ring‐opening to give the titanium alkoxide [Ti(O(CH2)4NEt3)(Xy‐N3N)][B(3,5‐Cl2C6H3)4] (3). Hydride abstraction from Cβ,eq of the triamidoamine ligand arm in [Ti(CH2SiMe3)(Xy‐N3N)] or [Ti(NMe2)(Xy‐N3N)] with [Ph3C][B(3,5‐Cl2C6H3)4] led to the diamidoamine–imine complex [Ti(R){(Xy‐N=CHCH2)(Xy‐NCH2CH2)2N}][B(3,5‐Cl2C6H3)4] (R=CH2SiMe3 (4 a); R=NMe2 (4 b)). Hydride addition to 4 b with [Li(THF)][HBPh3] gave [Ti(NMe2)(Xy‐N3N)], whereas KH deprotonated further to give [Ti(NMe2){(Xy‐NCH=CH)(Xy‐NCH2CH2)2N}] (5). XRD on single crystals of 3 and 4 b confirmed the proposed structures.