bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

Abstract5‐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

AbstractMining 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

ABSTRACTThe 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

AbstractThe 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

AbstractAn 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

AbstractRosmarinic 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.
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

AbstractWith 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

AbstractTriggering 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

AbstractSix‐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

AbstractWe 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

AbstractDespite 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

AbstractCross‐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

AbstractProtonolysis 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.
How Do Actinyls Interact with Hyperphosphorylated Yolk Protein Phosvitin?
Authors: Kumar Sumit , Creff Gaëlle , Hennig Christoph , Rossberg André , Steudtner Robin , Raff Johannes , Vidaud Claude , Oberhaensli François R. , Bottein Marie‐Yasmine Dechraoui , Den Auwer Christophe 
Published: June 2019

AbstractThe development of the nuclear industry has raised multiple questions about its impact on the biotope and humans. Proteins are key biomolecules in cell machinery and essential in deciphering toxicological processes. Phosvitin was chosen as a relevant model for phosphorylated proteins because of its important role as an iron, calcium, and magnesium storage protein in egg yolk. A multitechnique spectroscopic investigation was performed to reveal the coordination geometry of two oxocations of the actinide family (actinyl UVI, NpV) in speciation with phosvitin. IR spectroscopy revealed phosphoryl groups as the main functional groups interacting with UVI. This was confirmed through laser luminescence spectroscopy (U) and UV/Vis absorption spectroscopy (Np). For UVI, X‐ray absorption spectroscopy at the LIII edge revealed a small contribution of bidentate binding present, along with predominantly monodentate binding of phosphoryl groups; for NpV, uniquely bidentate binding was revealed. As a perspective to this work, X‐ray absorption spectroscopy speciation of UVI and NpV in the extracted yolk of living eggs of the dogfish Scyliorhinus canicula was determined; this corroborated the binding of phosphorous together with a reduction of the actinyl moiety. Such data are essential to pinpoint the mechanisms of heavy metals (actinyls) accumulation and toxicity in oviparous organisms, and therefore, contribute to a shift from descriptive approaches to predictive toxicology.
Intramolecular Catalyst Transfer on a Variety of Functional Groups between Benzene Rings in a Suzuki–Miyaura Coupling Reaction
Authors: Yokozawa Tsutomu , Harada Natsumi , Sugita Hajime , Ohta Yoshihiro 
Published: June 2019

AbstractSuzuki–Miyaura coupling reaction of BrC6H4‐X‐C6H4Br 1 (X=CH2, CO, N‐Bu, O, S, SO, and SO2) with arylboronic acid 2 was investigated in the presence of tBu3PPd precatalyst and CsF/[18]crown‐6 as a base to establish whether or not the Pd catalyst can undergo catalyst transfer on these functional groups. In the reaction of 1 (X=CH2, CO, N‐Bu, O, and SO2) with 2, aryl‐disubstituted product 3 (Ar‐C6H4‐X‐C6H4‐Ar) was exclusively obtained, indicating that the Pd catalyst undergoes catalyst transfer on these functional groups. On the other hand, the reaction of 1 e (X=S) and 1 f (X=SO) with 2 afforded only aryl‐monosubstituted product 4 (Ar‐C6H4‐X‐C6H4‐Br) and a mixture of 3 and 4, respectively, indicating that S and SO interfere with intramolecular catalyst transfer. Furthermore, we found that Suzuki–Miyaura polycondensation of 1 (X=CH2, CO, N‐Bu, O, and SO2) and phenylenediboronic acid 5 in the presence of tBu3PPd precatalyst afforded high‐molecular‐weight polymer even when excess 1 was used. The polymers obtained from 1 (X=CH2, N‐Bu, and O) and 5 turned out to be cyclic.
Photoluminescent Lanthanide(III) Single‐Molecule Magnets in Three‐Dimensional Polycyanidocuprate(I)‐Based Frameworks
Authors: Zakrzewski Jakub J. , Chorazy Szymon , Nakabayashi Koji , Ohkoshi Shin‐ichi , Sieklucka Barbara 
Published: June 2019

AbstractThree‐dimensional bimetallic cyanido‐bridged frameworks, [LnIII(2,2′‐bipyridine N,N′‐dioxide)2(H2O)][CuI2(CN)5]⋅5 H2O (Ln=Dy, 1; Yb, 2), are reported. They exhibit the effect of slow relaxation of magnetization, leading to a magnetic hysteresis loop, and sensitized visible‐to‐near‐infrared photoluminescence. Both physical properties are related to the eight‐coordinated lanthanide(III) complexes embedded in the unprecedented coordination skeleton composed of symmetry‐breaking polycyanidocuprate linkers. The three‐dimensional d–f cyanido‐bridged network was shown to serve as an efficient coordination scaffold to achieve emissive lanthanide single‐molecule magnets.
Back Cover: Lewis Acid‐Catalyzed Intramolecular [3 + 2] Cross‐Cycloaddition of Donor‐ Acceptor Epoxides with Alkenes for Construction of Oxa‐[n.2.1] Skeletons (Chin. J. Chem. 7/2019)
Authors: Chen Lu , Tian Jun , Zhan Yizhou , Ren Jun , Wang Zhong‐Wen 
Published: June 2019

The back cover picture shows the first LA‐catalyzed [3+2]IMCC of GDA‐epoxides with carbon‐carbon double bonds. This provides an efficient and general strategy for construction of bridged oxa‐[n.2.1] skeletons. A novel SN‐like mechanism through a carbon‐carbon bond cleavage of epoxide ring has been proposed. The colorful fireworks in the picture imply the generation of skeletal diversity from the epoxide‐diene, and express a dedication to the 100th Anniversary of Nankai University as well. More details are discussed in the article by Wang et al. on page 695–699.
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Development, implementation, and effects of a cancer center's exercise‐oncology program
Authors: Santa Mina Daniel , Au Darren , Auger Leslie E. , Alibhai Shabbir M. H. , Matthew Andrew G. , Sabiston Catherine M. , Oh Paul , Ritvo Paul G. , Chang Eugene B. , Jones Jennifer M. 
Published: June 2019

BackgroundNational and international bodies acknowledge the benefit of exercise for people with cancer, yet limited accessibility to related programing remains. Given their involvement in managing the disease, cancer centers can play a central role in delivering exercise‐oncology services. The authors developed and implemented a clinically integrated exercise‐oncology program at a major cancer center and evaluated its effectiveness and participant experience.MethodsA hospital‐based program with prescribed at‐home exercise was developed and accepted referrals over a 42‐month period (3.5 years). Implementation was conducted in 2 phases: a pilot phase for women with breast cancer and men with genitourinary cancer and a roll‐out phase for all patients with cancer. Enrolled patients were assessed and received an exercise prescription as well as a program manual, resistance bands, and a stability ball from a kinesiologist. Program participation and effectiveness were evaluated up to 48 weeks after the baseline assessment using intention‐to‐treat analyses. Participants in the roll‐out phase were asked to complete a program experience questionnaire at the completion of the 48‐week follow‐up.ResultsIn total, 112 participants enrolled in the pilot, and 150 enrolled in the roll‐out phase. Program attrition to 48 weeks was 48% and 65% in the pilot and roll‐out phases, respectively. In participants who consented to research evaluation of their performance, objective and patient‐reported measures of functional capacity improved significantly from baseline in both phases. Participants were highly satisfied with the program.ConclusionsDespite significant drop‐out to program endpoints, our cancer‐exercise program demonstrated clinically relevant improvement in functional outcomes and was highly appreciated by participants.